JP2021075680A - Aqueous resin dispersion for coating and aqueous coating composition - Google Patents

Abstract

To provide an aqueous resin dispersion for coating which is excellent in storage stability and exhibits excellent adhesion to a plurality of base materials (in particular, olefinic base material).SOLUTION: The aqueous resin dispersion for coating excluding an aqueous resin dispersion for inkjet ink contains water and a polyurethane resin (U). The polyurethane resin (U) is a polyurethane resin obtained by reacting an active hydrogen group-containing compound (W) and an isocyanate component (B). The active hydrogen group-containing compound (W) contains polymer polyol (A), and the polymer polyol (A) contains hydroxyl group-containing polyolefin (A1). A weight ratio [ethylene/α-olefin] of the ethylene that is a constituent monomer of the hydroxyl group-containing polyolefin (A1) to α-olefin (3 to 8 carbon atoms) is 5/95 to 65/35, and isotacticity of the α-olefin part of the hydroxyl group-containing polyolefin (A1) is 1-50%.SELECTED DRAWING: None

Description

The present invention relates to a water-based resin dispersion for paints and a water-based paint composition.

Aqueous polyurethane resins have conventionally been used in paints, adhesives, fiber processing agents, paper processing agents, inks and the like. There are a wide variety of coating base materials such as iron, wood, fibers, PET films, and olefin resin base materials. Recently, from the viewpoint of cost and reusability, the adoption of olefin resin base materials such as PP (polypropylene) is increasing. It's coming. In coating these substrates, different coating compositions are generally used in consideration of the characteristics of each substrate, softening temperature, etc., but from the viewpoint of shortening the coating process and matching hues, the coating compositions There is a request to standardize.

Further, since the olefin-based resin base material does not have a polar group in its molecule and is chemically inert, there is a problem that it is difficult to paint and adhere.
An aqueous polyurethane resin composition using a chlorinated polyol has been proposed in order to improve the adhesion to an olefin-based substrate (for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 06-172637

However, even with the technique of Patent Document 1, the storage stability is not sufficiently satisfactory, and improvement has been required. An object of the present invention is to provide an aqueous resin dispersion for paints which is excellent in storage stability and exhibits excellent adhesion to a plurality of substrates (particularly olefin-based substrates).

The present inventors have arrived at the present invention as a result of studies for achieving the above object.
That is, the present invention is an aqueous dispersion for coatings containing water and a polyurethane resin (U), wherein the polyurethane resin (U) contains an active hydrogen group-containing compound (W) and an isocyanate component (B). The active hydrogen group-containing compound (W) contains a high molecular weight polyol (A), the high molecular weight polyol (A) contains a hydroxyl group-containing polyolefin (A1), and the hydroxyl group-containing polyolefin is obtained. The weight ratio [ethylene / α-olefin] of ethylene, which is a constituent monomer of (A1), to α-olefin (3 to 8 carbon atoms) is 5/95 to 65/35, and the hydroxyl group-containing polyolefin (A1) The isotacticity of the α-olefin moiety of the above is 1 to 50%, and it is an aqueous resin dispersion for paints excluding the aqueous resin dispersion for inkjet ink.

The aqueous resin dispersion for paints of the present invention has the following effects.
(1) Excellent storage stability.
(2) The coating film has excellent substrate adhesion to a plurality of substrates (particularly olefin-based substrates).

<Polyurethane resin (U)>
The polyurethane resin (U) in the present invention is a polyurethane resin obtained by reacting the active hydrogen group-containing compound (W) with the isocyanate component (B). In addition, (U) may have a urea group, in which case (U) is a polyurethane urea resin.

The active hydrogen group-containing compound (W) contains a polymer polyol (A).

The polymer polyol (A) is a polyol containing a hydroxyl group-containing polyolefin (A1).

<Hydroxy group-containing polyolefin (A1)>
The hydroxyl group-containing polyolefin (A1) in the present invention is, for example, an acid-modified polyolefin (E) in which a polyolefin (A01) having a carbon-carbon double bond described later is modified with an unsaturated (poly) carboxylic acid (anhydrous) (E). It can be obtained by reacting X) with an amino alcohol (G), or by reacting an acid-modified polyolefin (X) with an alkylene oxide (hereinafter abbreviated as AO).

The polyolefin (A01) contains ethylene and an α-olefin (3 to 8 carbon atoms) as a constituent monomer.
The α-olefin (3 to 8 carbon atoms) is an α-olefin having 3 to 8 carbon atoms, and examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, and 1-hexene. , 1-octene.
Two or more types of α-olefins may be used in combination, but one type is preferable.
Among the above α-olefins, from the viewpoint of adhesion to a polyolefin-based substrate, a linear α-olefin (3 to 8 carbon atoms) is preferable, and a linear α-olefin (3 carbon atoms) is more preferable. ~ 6), and propylene is particularly preferable.

The weight ratio [ethylene / α-olefin] of ethylene, which is a constituent monomer of polyolefin (A01), to α-olefin (3 to 8 carbon atoms) is 5/95 to 65/35, preferably 10 /. It is 90 to 60/40, more preferably 15/85 to 40/60.
Since the weight ratio of ethylene of the polyolefin (A01) to the α-olefin having 3 to 8 carbon atoms is directly reflected in the weight ratio of ethylene of the hydroxyl group-containing polyolefin (A1) to the α-olefin having 3 to 8 carbon atoms, the weight ratio. When [ethylene / α-olefin] is less than 5/95, the storage stability is inferior, and when it exceeds 65/35, the substrate adhesion is inferior.
The weight ratio [ethylene / α-olefin] can be calculated by ^{, for example, 1 H-MNR.} The weight ratio of ethylene of polyolefin (A01) to α-olefin having 3 to 8 carbon atoms depends on the weight ratio of ethylene of high molecular weight polyolefin (A00) to α-olefin having 3 to 8 carbon atoms, which will be described later. Can be adjusted.

In the above (A01), other monomers may be used as constituent monomers in addition to ethylene and α-olefin (3 to 8 carbon atoms). In that case, based on the weight of all the monomers constituting (A01), the weight of the other monomers is preferably 10% by weight or less, more preferably 5% by weight or less, and particularly preferably 1% by weight or less. Is.
Examples of the other monomers include 2-butene, isobutene, α-olefins having 9 to 30 carbon atoms [sometimes abbreviated as C] (1-decene, 1-dodecene, etc.), and C4 to 30. Unsaturated monomers (eg, vinyl acetate) can be mentioned.

The number average molecular weight (Mn) of the polyolefin (A01) is preferably 800 to 5,800, more preferably 900 to 4,800, and particularly preferably 1,000, from the viewpoint of substrate adhesion and storage stability. ~ 3,800.

The measurement conditions for hydroxyl group-containing polyolefin (A1), polyolefin (A01), high molecular weight polyolefin (A00) and polyurethane resin Mn, and weight average molecular weight (Mw) described later by GPC (gel permeation chromatography) in the present invention are as follows. It is as follows.
Equipment: High temperature gel permeation chromatograph
["Alliance GPC V2000", manufactured by Waters Corp.]
Detector: Refractive index detector Solvent: Ortodichlorobenzene Reference substance: Polystyrene Sample concentration: 3 mg / ml
Column stationary phase: PLgel 10 μm, two MIXED-B in series
[Manufactured by Polymer Laboratories Co., Ltd.]
Column temperature: 135 ° C

The number of double bonds per 1000 carbon atoms of polyolefin (A01) [the number of carbon-carbon double bonds in the molecular terminal and / or molecular chain of (A01)] is the (poly) carboxylic acid (anhydrous anhydride) described later. ) From the viewpoint of reactivity with (E) and productivity, the number is preferably 1 to 30, more preferably 1.5 to 20, and particularly preferably 2 to 15.
Here, the number of double bonds ^{can be obtained from the spectrum of 1} H-NMR (nuclear magnetic resonance) spectroscopy of (A01). That is, the peak in the spectrum is assigned, and from the integrated value derived from the double bond and the integrated value derived from (A01) at 4.5 to 6 ppm of (A01), the number of double bonds of (A01) and (A01) The relative value of the number of carbon atoms of (A01) is obtained, and the number of double bonds in the molecular terminal and / or the molecular chain per 1,000 carbon atoms of (A01) is calculated. The number of double bonds in the examples described below was in accordance with the method.

The isotacticity of the α-olefin moiety of the polyolefin (A01) is preferably 1 to 50%, more preferably 5 to 45%, from the viewpoint of adhesion and storage stability.
The isotacticity of the α-olefin moiety of the polyolefin (A01) tends to be directly reflected in the isotacticity of the α-olefin moiety of the acid-modified polyolefin (X) and the hydroxyl-modified polyolefin (A1) described later. .. Further, since the isotacticity of the α-olefin portion of the polyolefin (A01) tends to reflect the isotacticity of the α-olefin portion of the polyolefin (A00) which will be described later, the polyolefin (A00) of the raw material to be used tends to be reflected. ) Can be adjusted.

The isotacticity can be calculated using, for example, ¹³ C-NMR (nuclear magnetic resonance spectroscopy). In general, side chain methyl groups are on both sides (triplet, triad), on both sides of the triplet (quintuplet, pentad), and on both sides of the quintuplet (seven-strand, heptad). It is known that peaks are observed at different chemical shifts under the influence of the configuration (meso or racemo) with the methyl group, and the evaluation of stereoregularity is generally performed for pentad. The isotacticity in is also able to be calculated based on the evaluation of the pentad.
That is, when the α-olefin is propylene, each peak (H) of the pentad and the isotactic in which the pentad is formed only by the mesostructure are obtained for the carbon peak derived from the side chain methyl group in the propylene obtained by ^{13 C-NMR.} Assuming that the peak (Ha) is derived from the methyl group in propylene, the isotacticity is calculated by the following formula.
Isotacticity (%) = [(Ha) / Σ (H)] x 100 (1)
However, in the equation, Ha is the peak height of the isotactic signal (pentad is formed only by the meso structure), and H is the peak height of each pentad.
The isotacticity of the α-olefin portions of (A01) and (X) can be measured in the same manner as described above.

The method for producing the polyolefin (A01) is, for example, a method of thermally reducing the high molecular weight (preferably Mn of 60,000 to 400,000, more preferably Mn of 80,000 to 250,000) polyolefin (A00). Can be mentioned.

The heat-decomposing method includes (1) a method of heat-decomposing the high-molecular-weight polyolefin (A00) in the absence of an organic peroxide at 300 to 450 ° C. for 0.5 to 10 hours, and (2) an organic method. A method of heat-decomposing in the presence of a peroxide [for example, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane] at 180 to 300 ° C. for 0.5 to 10 hours is included. ..
Of these, from the viewpoint of industrial viewpoints and modification characteristics, the method (1) is preferable because it is easy to obtain a method having a larger number of double bonds at the molecular terminal and / or the molecular chain.

As for the weight ratio [ethylene / α-olefin] of ethylene and α-olefin, which is the monomer constituting the above (A01), the weight ratio [ethylene / α-olefin] of the high molecular weight polyolefin (A00) is maintained as it is. Tends to be.
Further, the higher the heat decomposing temperature and the longer the heat decomposing time, the larger the number of double bonds per 1000 carbon atoms tends to be.
Further, the smaller the Mn of (A00), the higher the heat decomposing temperature, and the longer the heat decomposing time, the smaller the Mn of (A) tends to be.
Further, the larger the isotacticity of (A00) is, the larger the isotacticity of (A01) tends to be.

The unsaturated (poly) carboxylic acid (anhydride) (E) is a (poly) carboxylic acid having 3 to 30 carbon atoms having one polymerizable unsaturated group [hereinafter, may be abbreviated as C]. Anhydride) is included.
In the present invention, the unsaturated (poly) carboxylic acid (anhydrous) means an unsaturated monocarboxylic acid, an unsaturated polycarboxylic acid and / or an unsaturated polycarboxylic acid anhydride.

Among the (E), the unsaturated monocarboxylic acid includes an aliphatic monocarboxylic acid (C3 to 24, for example, acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, isocrotonic acid), and an alicyclic-containing monocarboxylic acid. Acids (C6-24, eg cyclohexenecarboxylic acids); unsaturated poly (2-3 or more) carboxylic acids (anhydrous) include unsaturated dicarboxylic acids (anhydrous) [aliphatic dicarboxylic acids (anhydrous) ( C4-24, such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and anhydrides thereof), alicyclic-containing dicarboxylic acid (anhydrous) (C8-24, eg cyclohexendicarboxylic acid, cyclohep Tendicarboxylic acid, bicycloheptenedicarboxylic acid, methyltetrahydrophthalic acid, and anhydrides thereof)] and the like can be mentioned. (E) may be used alone or in combination of two or more.
Of the above (E), unsaturated dicarboxylic acid anhydride is preferable, and maleic anhydride is more preferable, from the viewpoint of reactivity with polyolefin (A01), storage stability, and mechanical strength.

<Acid-modified polyolefin (X)>
The acid-modified polyolefin (X) in the present invention contains the polyolefin (A01) having a carbon-carbon double bond and an unsaturated (poly) carboxylic acid (anhydride) (E) as constituent units. Preferably, the polyolefin (A01) and an unsaturated (poly) carboxylic acid (anhydride) (E) are reacted in the absence or presence of a radical initiator.

The weight ratio of (A01) to (E) [(A01) / (E)] is preferably 80/20 to 99.5 / 0.5 from the viewpoint of the balance between substrate adhesion and storage stability. More preferably, the reaction is carried out at 90/10 to 99/1.

The acid-modified polyolefin (X) is preferably an organic solvent suitable for the polyolefin (A01) and the unsaturated (poly) carboxylic acid (anhydrous) (E) in the presence of the radical initiator (F). [C3-18, for example hydrocarbons (hexane, heptan, octane, dodecane, benzene, toluene, xylene, etc.), halogenated hydrocarbons (di, tri-, and tetrachloroethane, dichlorobutane, etc.), ketones (acetone, methylethylketone, etc.) , Di-t-butyl ketone, etc.), ether (ethyl-n-propyl ether, di-n-butyl ether, di-t-butyl ether, dioxane, etc.)] and react to produce.
Examples of the radical initiator (F) include known initiators (azobisisobutyronitrile and the like) and peroxide initiators (dicumyl peroxide and the like).
Of the above (F), the peroxide initiator is preferable.

The reaction temperature is preferably 100 to 270 ° C., more preferably 120 to 250 ° C., and particularly preferably 130 to 240 ° C. from the viewpoint of reactivity and productivity of (A01) and (E).

The acid value of the acid-modified polyolefin (X) is preferably 1 to 130 mgKOH / g, more preferably 3 to 75 mgKOH / g, and particularly preferably 5 to 50 mgKOH / g from the viewpoint of substrate adhesion. The acid value here is a value measured by the following procedures (i) to (iii) according to JIS K0070: 1992.
(I) Dissolve 1 g of (X) in 100 g of xylene whose temperature has been adjusted to 100 ° C.
(Ii) Titrate with 0.1 mol / L potassium hydroxide ethanol solution [trade name "0.1 mol / L ethanolic potassium hydroxide solution", manufactured by Wako Pure Chemical Industries, Ltd.] using phenolphthalein as an indicator at the same temperature. I do.
(Iii) The acid value (unit: mgKOH / g) is calculated by converting the amount of potassium hydroxide required for titration into mg.
In the above measurement, one acid anhydride group is equivalent to one carboxyl group.
Further, the acid value can be appropriately adjusted by the number of double bonds possessed by (A01), the weight of (A01), the type of (E), and the weight of (E).

The Mn of the acid-modified polyolefin (X) is preferably 900 to 5,900, more preferably 900 to 5,000, and particularly preferably 900 to 4,000, from the viewpoint of solvent solubility and substrate adhesion. is there.

The isotacticity of the α-olefin moiety of the acid-modified polyolefin (X) is preferably 1 to 50%, more preferably 5 to 45%, and particularly preferably 10 to 40, from the viewpoint of solvent solubility and substrate adhesion. %.

Examples of the hydroxyl group-modified polyolefin (A1) in the present invention include a reaction product of an acid-modified polyolefin (X) and an amino alcohol (G), a reaction product of an acid-modified polyolefin (X) and AO, and the like.

Amino alcohol (G) includes linear alkanolamines having 2 to 12 carbon atoms, cycloalkanolamines and alkylalkanolamines (for example, 2-aminoethanol, 3-aminopropanol, 1-amino-2-propanol, 2-amino). -2-Methyl-1-propanol, 4-aminobutanol, 5-aminopentanol, 6-aminohexanol, diethanolamine, di-n- or isopropanolamine, 3-aminomethyl-3,5,5-trimethylcyclohexanol, Methylethanolamine and ethylethanolamine) and the like, and 2-aminoethanol is preferable from the viewpoint of substrate adhesion.

As AO, AO having 2 to 12 carbon atoms (ethylene oxide, 1,2- or 1,3-propylene oxide, 1,2-, 2,3- or 1,3-butylene oxide, tetrahydrofuran, 3-methyl) Tetrahydrofuran, styrene oxide, α-olefin oxide, etc.) and the like are mentioned, and from the viewpoint of substrate adhesion, those having 2 to 4 carbon atoms are preferable, and ethylene oxide and propylene oxide are more preferable. One type of AO may be used alone or two or more types may be used in combination.
The number of moles of AO added is preferably 1 to 10 mol or more, more preferably 1 to 5 mol, and particularly preferably 1 mol, per 1 carboxy group of (X) from the viewpoint of substrate adhesion.

Modification of (X) with aminoalcohol (G) is performed by a known method, for example, in excess (for example, 1.1 to 2 times mol or more) with respect to the carboxyl group (carbonyl group in the case of anhydride) of (X). ) Is added and reacted, and then the unreacted aminoalcohol is removed by a method such as a distillation method. The reaction can be carried out in the presence or absence of an organic solvent. The reaction temperature is preferably 100 to 220 ° C., more preferably 120 to 200 ° C. from the viewpoint of reaction rate and reaction stability.
The modification of (X) by AO is carried out by a known method. For example, the reaction temperature when ring-opening addition polymerization of AO is preferably 40 to 200 ° C., more preferably 70 to 160 ° C. from the viewpoint of reaction rate and reaction stability. The reaction pressure is preferably −0.1 to 0.5 MPa. The reaction is carried out in the presence of a catalyst, if necessary.

The weight ratio [ethylene / α-olefin] of ethylene, which is a constituent monomer of the hydroxyl group-modified polyolefin (A1), to α-olefin (3 to 8 carbon atoms) is 5/95 to 65/35, preferably 5/95 to 65/35. It is 10/90 to 60/40, more preferably 15/85 to 40/60.
When the weight ratio [ethylene / α-olefin] is less than 5/95, the storage stability is inferior, and when it exceeds 65/35, the substrate adhesion is inferior.
The weight ratio of ethylene, which is a constituent monomer of the hydroxyl group-modified polyolefin (A1), to α-olefin having 3 to 8 carbon atoms is appropriately determined by the ratio of ethylene to α-olefin having 3 to 8 carbon atoms used in (A00). , Adjustable.

The isotacticity of the α-olefin moiety of the hydroxyl group-containing polyolefin (A1) is 1 to 50%, preferably 5 to 45%. If the isotacticity of the α-olefin moiety of (A1) is less than 1%, the substrate adhesion is poor, and if it exceeds 50%, the solvent solubility is poor.
The isotacticity of the α-olefin portion of the hydroxyl group-containing polyolefin (A1) can be appropriately adjusted by the isotacticity of (A01).

The Mn of the hydroxyl group-containing polyolefin (A1) is preferably 500 or more, preferably 1,000 to 10,000, more preferably 1,100 to 7,500 from the viewpoint of substrate adhesion and storage stability. , Particularly preferably 1,400 to 5,500.
The Mn of (A1) can be appropriately adjusted by controlling the Mn of (A01), the type and amount of (E) used, and the reaction between (A01) and (E).

The hydroxyl value (mgKOH / g) of the hydroxyl group-containing polyolefin (A1) is preferably 12 to 120, more preferably 15 to 110, and particularly preferably 20 to 80, from the viewpoint of substrate adhesion.
The hydroxyl value of (A1) can be appropriately adjusted by the number of double bonds possessed by (A01), the amount of (A01) used, the type and amount of (E), and the type and amount of (G) or AO. is there.
The acid value (mgKOH / g) of (A1) is preferably 0 to 50, more preferably 0 to 30, from the viewpoint of water resistance of the film.
The hydroxyl value and acid value of (A1) are values measured in accordance with JIS K0070-1992.

In the present invention, the number of hydroxyl groups per molecule of the hydroxyl group-modified polyolefin (A1) is preferably 1.5 to 2.0, more preferably 1.6 to 2.0, from the viewpoint of substrate adhesion. is there. The number of hydroxyl groups per molecule of the hydroxyl group-modified polyolefin (A1) can be calculated by the following mathematical formula (1).
Number of hydroxyl groups per molecule = Mn _A1 x OHV / 56100 (1)
_{Mn A1} : Mn of (A1)
OHV: Hydroxyl value of (A1) (mgKOH / g)

When the polyurethane resin (U) uses a plurality of types of hydroxyl group-modified polyolefins (A1), the weight average value of the number of hydroxyl groups of all the hydroxyl group-modified polyolefins (A1) constituting the polyurethane resin (U) is the polyurethane resin (U). From the viewpoint of substrate adhesion of U), 1.5 to 2.0 pieces are preferable, and 1.6 to 2.0 pieces are more preferable.

As the polymer polyol (A) other than the hydroxyl group-containing polyolefin (A1), the condensed polyester polyol (A2), the polylactone polyol (A3), the polycarbonate polyol (A4), the polyether polyol (A5) and the polyacrylic polyol (A6) One or more of these can be used together. In (A), one type may be used alone or two or more types may be used in combination. The above (A2) to (A6) are also described as high molecular weight polyols (A2) to high molecular weight polyols (A6).
The Mn of the polymer polyol (A) other than the hydroxyl group-containing polyolefin (A1) is preferably 500 or more, more preferably 500 to 5000, and particularly preferably 1000 to 4000 from the viewpoint of substrate adhesion.

The condensed polyester polyol (A2) includes a diol having a Mn of less than 500 and a dicarboxylic acid other than terephthalic acid or an ester-forming derivative thereof [acid anhydride, lower (1 to 4 carbon atoms) alkyl ester, acid halide, etc.]. Examples thereof include those obtained by condensation of.

Examples of diols having a Mn of less than 500 include aliphatic dihydric alcohols having 2 to 8 carbon atoms [straight-chain diols (ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol). And 1,6-hexanediol, etc.) and diols with branched alkyl chains (1,2-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propane) Diol, 1,2-, 1,3- or 2,3-butanediol, etc.)]; Alicyclic group-containing dihydric alcohol with 6 to 10 carbon atoms [1,4-bis (hydroxymethyl) cyclohexane and 2, 2-Bis (4-hydroxycyclohexyl) propane, etc.]; Arocyclic-containing dihydric alcohol having 8 to 20 carbon atoms [m- or p-xylylene glycol, bis (hydroxyethyl) benzene, bis (hydroxyethoxy) benzene]; AO adducts of bisphenols (bisphenol A, bisphenol S, bisphenol F, etc.), AO adducts of dihydroxynaphthalene, bis (2-hydroxyethyl) terephthalate, etc.] and the like can be mentioned. As for the diol having Mn less than 500, one type may be used alone or two or more types may be used in combination.

Examples of the dicarboxylic acid or its ester-forming derivative include aliphatic dicarboxylic acids having 2 to 15 carbon atoms [oxalic acid, succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, maleic acid, fumaric acid, etc.] and carbon atoms. 8 to 12 aromatic dicarboxylic acids [terephthalic acid, phthalic acid, isophthalic acid, etc.] and their ester-forming derivatives [acid anhydride, lower alkyl ester (dimethyl ester, diethyl ester, etc.), acid halide (acid chloride, etc.) Etc.] etc. One type of dicarboxylic acid may be used alone, or two or more types may be used in combination.

Specific examples of the condensed polyester polyol (A2) include polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyhexamethylene isophthalate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, and polyethylene butylene adipate. Diol, polybutylene hexamethylene adipate diol, poly (polyoxytetramethylene) adipate diol, poly (3-methylpentylene adipate) diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azelate diol and polybutylene sebacate Examples include diols. (A2) may be used alone or in combination of two or more.

As the polylactone polyol (A3), a lactone monomer (γ-butyrolactone, γ-valerolactone, ε-caprolactone, a mixture of two or more thereof, etc.) was ring-opened and polymerized using the diol having a Mn of less than 500 as an initiator. Things etc. can be mentioned. Specific examples of the polylactone polyol (A3) include polybutyrolactone diol, polyvalerolactone diol, polycaprolactone diol and the like. (A3) may be used alone or in combination of two or more.

Examples of the polycarbonate polyol (A4) include the diol having a Mn of less than 500, a low molecular weight carbonate compound (for example, a dialkyl carbonate having 1 to 6 carbon atoms in an alkyl group, an alkylene carbonate having an alkylene group having 2 to 6 carbon atoms, and carbon. Examples thereof include a polycarbonate diol produced by condensing a diaryl carbonate having an aryl group of No. 6 to 9 while carrying out a dealcohol reaction. (A4) may be used alone or in combination of two or more.

Specific examples of the polycarbonate polyol (A4) include polyhexamethylene carbonate diol, polypentamethylene carbonate diol, polytetramethylene carbonate diol and poly (tetramethylene / hexamethylene) carbonate diol (for example, 1,4-butanediol and 1, A diol obtained by condensing 6-hexanediol with a dialkyl carbonate while dealcoholizing it) and the like.

Examples of the polyether polyol (A5) include the AO adduct having 2 to 12 carbon atoms to a diol having a Mn of less than 500, and even if one type of AO is used alone, two or more types are block copolymerized. Alternatively, random copolymerization may be performed.

Among the polyether polyols (A5), those having a branched alkyl chain are preferable from the viewpoint of resolubility, that is, those using a diol having a branched alkyl chain among diols having a Mn of less than 500 as a raw material, or AO. As the AO in the adduct, 1,2-propylene oxide, 1,2-, 2,3- or 1,3-butylene oxide, 3-methyl tetrahydrofuran and the like are used, and more preferably, it has a branched alkyl. Aliphatic polyether diols of dihydric alcohols, particularly preferred are polyoxypropylene glycols. (A5) may be used alone or in combination of two or more.

The poly (meth) acrylic polyol (A6) is not particularly limited, and examples thereof include homopolymers and copolymers of (meth) acrylic acid esters having a hydroxy group.
The poly (meth) acrylic polyol can also be obtained by copolymerizing a compound having a polymerizable unsaturated bond in addition to the (meth) acrylic acid ester having a hydroxy group.
In the present invention, "(meth) acrylic" means "methacrylic and / or acrylic".

The (meth) acrylic acid ester having a hydroxy group includes one having one (meth) acryloyl group, for example, one having a hydroxyalkyl group having 2 to 20 carbon atoms {for example, (meth) acrylic acid. -2-Hydroxyethyl, -2-hydroxypropyl (meth) acrylate, -2-hydroxybutyl (meth) acrylate, -3-hydroxypropyl (meth) acrylate, -4-hydroxybutyl (meth) acrylate, etc. Hydroxyalkyl (meth) acrylic acid ester}, trivalent alcohol (meth) acrylic acid monoesteride {for example, glycerin (meth) acrylic acid monoester, trimethylpropan (meth) acrylic acid monoester, etc.} And so on.

The compound having a polymerizable unsaturated bond includes a compound having one polymerizable unsaturated bond, for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, (. Meta) -n-butyl acrylate, isobutyl (meth) acrylate, -n-hexyl (meth) acrylate, lauryl (meth) acrylate, glycidyl (meth) acrylate, -2-ethylhexyl (meth) acrylate, etc. (Meta) acrylic acid alkyl ester having 4 to 50 carbon atoms; unsaturated carboxylic acid having 3 to 50 carbon atoms such as (meth) acrylic acid, maleic acid, and itaconic acid; (meth) acrylamide, N-methylol (meth) Unsaturated amides having 3 to 50 carbon atoms such as acrylamide and diacetone (meth) acrylamide; other polymerizable monomers such as styrene, vinyltoluene, vinyl acetate, acryliconitrile and dibutyl fumarate can be mentioned.

Examples of the polymerization method of the (meth) acrylic acid ester having a hydroxy group and the compound having a polymerizable unsaturated bond include emulsion polymerization, suspension polymerization, dispersion polymerization, and solution polymerization. The emulsion polymerization can also be carried out stepwise.

Specific examples of the commercially available polyacrylic polyol include "ARUFON UH-2000, UH-2041, UH-2190, UHE-2012" manufactured by Toagosei Co., Ltd. and "Actflow UT-1001" manufactured by Soken Chemical Co., Ltd. , UMM-1001 "and the like.

Among the poly (meth) acrylic polyols (A6), -n-butyl (meth) acrylic acid, (meth) acrylic acid, is preferably used as the compound having the polymerizable unsaturated bond from the viewpoint of compatibility with the hydroxyl group-containing polyolefin (A1). ) A polyacrylic polyol using at least one selected from the group consisting of isobutyl acrylate, -n-hexyl (meth) acrylate, lauryl (meth) acrylate and -2-ethylhexyl (meth) acrylate. It is preferably a polyacrylic diol using -n-butyl (meth) acrylate and / or -2-ethylhexyl (meth) acrylate. (A6) may be used alone or in combination of two or more.

Condensed polyester polyol (A2), polylactone polyol (A3), polycarbonate polyol (A4), polyether polyol (A5) and / or poly (meth) acrylic polyol (A6) are used in combination with the hydroxyl group-containing polyolefin (A1). In the case, the weight of the hydroxyl group-containing polyolefin (A1) and the weight of the condensed polyester polyol (A2), the polylactone polyol (A3), the polycarbonate polyol (A4), the polyether polyol (A5) and the poly (meth) acrylic polyol (A6). The ratio of the total weight is preferably 100: 0 to 30:70, and more preferably 100: 0 to 50:50 from the viewpoint of substrate adhesion.

The number average molecular weight (Mn) and weight average molecular weight (Mw) of the polymer polyol (A) other than the hydroxyl group-containing polyolefin (A1) in the present invention can be measured by gel permeation chromatography, for example, under the following conditions. it can.
Equipment: "Waters Alliance 2695" [manufactured by Waters]
Columns: "Guardcolum Super HL" (1), "TSKgel"
One each of SuperH2000, TSKgel SuperH3000, and TSKgel SuperH4000 (all manufactured by Tosoh Corporation) are connected. "
Sample solution: 0.25 wt% tetrahydrofuran solution Injection volume: 10 μl
Flow rate: 0.6 ml / min Measurement temperature: 40 ° C
Detector: Refractive index detector Reference substance: Standard polyethylene glycol

<Isocyanate component (B)>
The isocyanate component (B) in the present invention includes aromatic polyisocyanate (B1) and carbon having 2 to 3 or more isocyanate groups and having 6 to 20 carbon atoms (excluding carbon in the isocyanate group, the same applies hereinafter). Aliphatic polyisocyanate (B2) having number 2 to 18, alicyclic polyisocyanate (B3) having 4 to 15 carbon atoms, aromatic aliphatic polyisocyanate (B4) having 8 to 15 carbon atoms and (B1) to (B4). (B5) and the like. The isocyanate component (B) may be used alone or in combination of two or more.

As the aromatic polyisocyanate (B1) having 6 to 20 carbon atoms, 1,3- or 1,4-phenylenediocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), 4,4'-or 2,4'-Diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate, 4,4', 4 "-triphenylmethane triisocyanate, m- or p-isocyanatophenylsulfonyl isocyanate, crude MDI and the like. Be done.

Aliphatic polyisocyanates (B2) having 2 to 18 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate and 2-. Isocyanatoethyl-2,6-diisocyanatohexanoate and the like can be mentioned.

Examples of the alicyclic polyisocyanate (B3) having 4 to 15 carbon atoms include isophorone diisocyanate (IPDI), 4,4-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, and methylcyclohexylene diisocyanate (hydrogenated TDI). Examples thereof include bis (2-isosianatoethyl) -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornan diisocyanate.

Examples of the aromatic aliphatic polyisocyanate (B4) having 8 to 15 carbon atoms include m- or p-xylene diisocyanate (XDI) and α, α, α', α'-tetramethylxylene diisocyanate (TMXDI). Be done.

The modified product (B5) of (B1) to (B4) has a urethane group, a carbodiimide group, an alohanate group, a urea group, a biuret group, a uretdione group, a uretoimine group, an isocyanurate group or an oxazolidone group (B1) to ( Examples thereof include modified products of B4).

Among the isocyanate components (B), the aliphatic polyisocyanate (B2) having 2 to 18 carbon atoms, the alicyclic polyisocyanate (B3) having 4 to 15 carbon atoms, and further, are preferable from the viewpoint of mechanical strength and weather resistance. (B3) is preferred, and IPDI and hydrogenated MDI are particularly preferred.

<Mn or chain extender (C) having a chemical formula of less than 500>
The polyurethane resin (U) may not only react the polymer polyol (A) with the isocyanate component (B), but may further react with the chain extender (C).
Examples of the chain extender (C) include a compound (c1) containing an ionic group and two active hydrogen atoms, a Mn or a polyhydric alcohol having a chemical formula of less than 500 (c2), and a polyalkylene polyamine (c3). Examples thereof include hydrazine or a derivative thereof (c4), an amino alcohol having 2 to 10 carbon atoms (c5), a polyepoxy compound having 2 to 30 carbon atoms (c6), water and the like.

The compound (c1) containing an ionic group and two active hydrogen atoms is also used to introduce an ionic group into the polyurethane resin (U).

As the chain extender (C), one of (c1) to (c6) may be used alone, or may be used in any combination.

<Compound (c1) containing an ionic polar group and two active hydrogen atoms>
The compound (c1) containing the ionic polar group and two active hydrogen atoms includes a compound (c11) containing an anionic group and an active hydrogen atom, and a cationic group and an active hydrogen atom. Compound (c12) can be mentioned. In (c1), one type may be used alone or two or more types may be used in combination.

The anionic group in (c11) means an acid group and a neutralized acid anion group. As (c11), for example, a compound containing a carboxyl group as an anionic group and having 2 to 10 carbon atoms [dialkylol alkanoic acid (for example, 2,2-dimethylol propionic acid, 2,2-dimethylol butanoic acid) , 2,2-Dimethylol heptanic acid and 2,2-dimethylol octanoic acid), tartrate and amino acids (eg glycine, alanine and valine)], containing a sulfonic acid group as an anionic group and having 2 to 2 carbon atoms. It contains 16 compounds [3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid, sulfoisophthalic acid di (ethylene glycol) ester, etc.], a sulfamic acid group as an anionic group, and has 2 to 10 carbon atoms. Compounds [N, N-bis (2-hydroxylethyl) sulfamic acid, etc.] and the like, and salts obtained by neutralizing these compounds with a neutralizing agent can be mentioned.

Examples of the neutralizing agent used for the salt of (c11) include ammonia, amine compounds having 1 to 20 carbon atoms, and alkali metal hydroxides (sodium hydroxide, potassium hydroxide, lithium hydroxide, etc.).
Examples of the amine compound having 1 to 20 carbon atoms include primary amines such as monomethylamine, monoethylamine, monobutylamine and monoethanolamine, and secondary amines such as dimethylamine, diethylamine, dibutylamine, diethanolamine and diisopropanolamine and methylpropanolamine. Examples thereof include amines and tertiary amines such as trimethylamine, triethylamine, dimethylethylamine, dimethylmonoethanolamine and triethanolamine.

As the neutralizing agent used for the salt of (c11), a compound having a high vapor pressure at 25 ° C. is preferable from the viewpoint of the drying property of the produced polyurethane resin aqueous dispersion and the water resistance of the obtained coating film. From this point of view, as the neutralizing agent used for the salt of (c11), ammonia, monomethylamine, monoethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine and dimethylethylamine are preferable.
Regarding the amount of the neutralizing agent added to the salt of (c11), the neutralization rate is 50 to 200% with respect to the amount of acidic groups of the polyurethane resin (U) from the viewpoint of water resistance and dispersion stability of the resin. Is preferable, and more preferably 60 to 150%.

Of (c11), 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid, and these, are preferable from the viewpoint of the resin physical properties of the obtained coating film and the dispersion stability of the polyurethane resin aqueous dispersion. Salts, more preferably neutralized salts of 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid with ammonia or an amine compound having 1 to 20 carbon atoms.

The cationic group in the compound (c12) containing a cationic group and an active hydrogen atom means a group in which a proton is added to a tertiary amino group, an unneutral tertiary amino group and a quaternary ammonium group.

Examples of (c12) include a compound having a tertiary amino group as a cationic group and a hydroxyl group as an active hydrogen atom, and a tertiary amino group-containing diol having 3 to 20 carbon atoms [N-alkyldialkanolamine (for example, N). -Methyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine and N-methyldipropanolamine) and N, N-dialkylmonoalkanolamines (eg, N, N-dimethylethanolamine), etc.] with neutralizers Examples include neutralized salts.

Examples of the neutralizing agent used in (c12) include monocarboxylic acids having 1 to 10 carbon atoms (formic acid, acetic acid, propanoic acid, etc.), carbonic acid, dimethyl carbonate, dimethyl sulfate, methyl chloride, benzyl chloride and the like. ..

The neutralizing agent used in (c11) and (c12) is added at any time before the urethanization reaction, during the urethanization reaction, after the urethanization reaction, before the water dispersion step, during the water dispersion step, or after the water dispersion. However, from the viewpoint of the stability of the urethane resin and the stability of the aqueous dispersion, it is preferable to add the urethane resin before the water dispersion step or during the water dispersion step. Further, the neutralizing agent volatilized at the time of solvent removal may be added after the solvent is removed, and the neutralizing agent type to be added can be freely selected from the above.

<Mn or polyhydric alcohol with a chemical formula less than 500 (c2)>
Examples of the Mn or polyhydric alcohol (c2) having a chemical formula amount of less than 500 include divalent alcohols having 2 to 20 carbon atoms [aliphatic diols (ethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, 1,6-Hexanediol, neopentyl glycol, 1,2- or 1,10-decanediol and 1,2- or 1,12-dodecanediol, etc.), alicyclic diols (1,2-, 1,3) -Or 1,4-cyclohexanediol and cyclohexanedimethanol, etc.), aromatic aliphatic diols {1-phenylethane-1,2-diol, 1,4-bis (hydroxyethyl) benzene, etc.}, ether group-containing diols {3 -Butoxy-1,2-propanediol, 3- (2-ethylhexoxy) -1,2-propanediol, 3-phenoxy-1,2-propanediol and 3- (p-tert-butylphenoxy) -1,2 -Propanediol, etc.} and halogen group-containing diols (3-chloro-1,2-propanediol, etc.), etc.], trivalent alcohols having 3 to 20 carbon atoms [aliphatic triol (glycerin, trimethylolpropane, etc.), etc.] and 4-8 valent alcohols with 5 to 20 carbon atoms [aliphatic polyols (pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, etc.) and sugars (sucrose, glucose, mannose, fructose, methylglucoside and derivatives thereof) )] And so on.

<Polyalkylene polyamine (c3)>
Examples of the polyalkylene polyamine (c3) include an aliphatic polyamine having 2 to 20 carbon atoms (ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc.) and an alicyclic having 6 to 20 carbon atoms. Formula polyamines (diaminocyclohexane, dicyclohexylmethanediamine, isophoronediamine, etc.), aromatic polyamines with 2 to 20 carbon atoms (phenylenediamine, triethyleneamine, diphenylmethanediamine, etc.), heterocyclic polyamines with 2 to 20 carbon atoms (piperazine and N-aminoethylpiperazin, etc.) and the like.

<Hydrazine or its derivative (c4)>
Examples of the hydrazine or a derivative thereof (c4) include hydrazine (hydrazine, monoalkyl hydrazine, etc.), dihydrazine (succinic acid dihydrazide, adipic acid dihydrazide, etc.) and the like.

<Amino alcohol (c5) with 2 to 10 carbon atoms>
Examples of the amino alcohol (c5) having 2 to 10 carbon atoms include ethanolamine, diethanolamine, 2-amino-2-methylpropanol, triethanolamine and the like.

<Polyepoxy compound (c6) having 2 to 30 carbon atoms>
Examples of the polyepoxy compound (c6) having 2 to 30 carbon atoms include AO having 2 to 4 carbon atoms, glycidol, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and p-tert-butyl phenyl glycidyl ether. Examples thereof include 1,2-epoxydecane, 1,2-epoxydodecane, cyclohexene oxide, styrene oxide, epichlorohydrin, 1,6-hexanediol diglycidyl ether and trimethylolpropane polyglycidyl ether.

The polyepoxide compound (c6) having 2 to 30 carbon atoms is used as a chain extender when the compound (c1) containing an ionic polar group and two active hydrogen atoms has a carboxyl group, and is used as an epoxy group. Reacts with the carboxyl group, so that the extension reaction proceeds.

Among the chain extenders (C), a compound (c1) containing an ionic group and two active hydrogen atoms, a polyhydric alcohol (c2), and a polyalkylene polyamine (c3) are preferable from the viewpoint of substrate adhesion. , Amino alcohol (c5), water, more preferably a compound (c1) containing an ionic group and two active hydrogen atoms, a dihydric alcohol, a trivalent alcohol, an aliphatic polyamine, an alicyclic polyamine, Amino alcohol (c5) and water.

Regarding the amount of (c1) used, the content of the ionic polar group in (U) is preferably 0.5 to 5.0% by weight, more preferably 0.5 to 0.5% by weight, based on the weight of (U). Adjust to 4.8% by weight, particularly preferably 0.5 to 4.5% by weight.
The content of the ionic polar group in the present invention means the weight% of the unneutralized cationic group or the anionic group, and does not include the weight of the counterion. For example, the content of the ionic polar group in (c11) is, in the case of the triethylamine salt of 2,2-dimethylolpropionic acid, the weight% of the carboxy group (-COOH), 3- (2,3-dihydroxypropoxy). ) -1- for triethylamine salt of sulfonic acid means the weight percent of the sulfo group _(-SO 3 H). Further, the content of the ionic polar group in (c12) means the weight% of only the nitrogen atom in the tertiary amino group.

If necessary, a reaction terminator can be used for the polyurethane resin (U) in the present invention. Reaction terminators include monoalcohols with 1 to 8 carbon atoms (methanol, ethanol, isopropanol, cellosolve, carbitol, etc.) and monoamines with 1 to 10 carbon atoms (monomethylamine, monoethylamine, monobutylamine, dibutylamine and monooctyl). Mono- or dialkylamines such as amines; mono- or dialkanolamines such as monoethanolamine, diethanolamine and diisopropanolamine) can be mentioned. The reaction terminator may be used alone or in combination of two or more.

The polyurethane resin (U) in the present invention may contain additives such as antioxidants, colorants, weather stabilizers, plasticizers and mold release agents, if necessary. The amount of these additives used is preferably as small as possible, preferably 10% by weight or less, based on the weight of (U), from the viewpoint of substrate adhesion, within the range in which the effects of the additives can be exhibited. It is preferably 3% by weight or less, and particularly preferably 1% by weight or less.

The urethane group content in the polyurethane resin (U) in the present invention is preferably 0.5 to 3.0 mmol / g, more preferably 0.7 to 2.5 mmol / g, from the viewpoint of substrate adhesion of the obtained coating film. , Particularly preferably 0.9 to 2.0 mmol / g.

Polyurethane by appropriately adjusting the polymer polyol (A) containing the hydroxyl group-containing polyolefin (A1) and the above-mentioned (A2) to (A6) to be used if necessary, the isocyanate component (B), and if necessary, the chain extender (C). The urethane group content of the resin (U) can be in a desired range.
The urethane group content is calculated from the N atom content quantified by a nitrogen analyzer, ^{the ratio of urethane groups to urea groups quantified by 1} H-NMR, and the alohanate group and burette group contents.

The urea group content in the polyurethane resin (U) is preferably 1.5 mmol / g or less, more preferably 1.2 mmol / g or less, based on the weight of (U), from the viewpoint of substrate adhesion. It is particularly preferably 1.0 mmol / g or less, and most preferably 0.8 mmol / g or less.

In order to make the urea group content in the polyurethane resin (U) within a desired range, the amino group content, the water content and the isocyanate group content in the raw material of (U) may be appropriately adjusted.
The urea group content is calculated from the N atom content quantified by a nitrogen analyzer, ^{the ratio of urethane groups to urea groups quantified by 1} H-NMR, and the alohanate group and burette group contents.

<Aqueous resin dispersion for paint (Q)>
The aqueous resin dispersion (Q) for paint of the present invention contains water and the polyurethane resin (U). Further, it may contain at least one resin selected from the group consisting of urethane resin, acrylic resin and polyester resin other than the polyurethane resin (U).

The urethane resin other than the urethane resin (U) may be an aqueous resin dispersion containing a urethane resin other than the urethane resin (U), and the aqueous resin dispersion is generally used for coating applications. You can use things. Commercially available products include, for example, Hydran series manufactured by DIC Co., Ltd., Takelac W series manufactured by Mitsui Chemicals Co., Ltd., Orestar UD series, DAOTAN series manufactured by Ornex Japan, and Ucoat series manufactured by Sanyo Kasei Kogyo Co., Ltd. , Permarin series, Superflex series manufactured by Daiichi Kogyo Co., Ltd., NeoRez series manufactured by Kusumoto Kasei Co., Ltd., Adeka Bontiter HUX series manufactured by ADEKA Corporation, and Evafanol manufactured by Nichika Kagaku Co., Ltd. Examples include the series and the neo-sticker series.

The acrylic resin may be an aqueous resin dispersion containing the acrylic resin, and the aqueous resin dispersion includes (meth) acrylic acid, (meth) acrylic acid ester, and, if necessary, a vinyl monomer. Acrylic resin emulsion obtained by copolymerizing the above, which is generally used for paints, can be used.

Examples of commercially available acrylic resin emulsions include Almatex E series manufactured by Mitsui Chemicals, Inc., SETAQUA series manufactured by Ornex Japan, AQUAPOL series, UCECRYL series, VIACRYL VSC series, and acrylic emulsion manufactured by Etec Co., Ltd. (AE872D). , AE986B, AE610H, AE981A, AE982, AE337, AE373D, etc.), Pegar series manufactured by High Pressure Gas Industry Co., Ltd., Acrylic series manufactured by Nippon Shokubai Co., Ltd., Boncoat series manufactured by DIC Co., Ltd., etc. Can be mentioned.

The polyester resin may be an aqueous resin dispersion containing the polyester resin, and as the aqueous resin dispersion, those generally used for paints can be used. Commercially available products include RESYDROLL series manufactured by Ornex Japan, Byronal series manufactured by Toyobo Co., Ltd., Aronmelt series manufactured by Toagosei Co., Ltd., Pluscoat series manufactured by Toagosei Co., Ltd., and DIC Corporation. ), Sepol John ES manufactured by Sumitomo Seika Chemical Co., Ltd., and the like.

The aqueous resin dispersion for paint (Q) can be produced, for example, by the following method.

(1) A solution of a polyurethane prepolymer (P) having an isocyanate group at the terminal containing a polymer polyol (A) containing a hydroxyl group-containing polyolefin (A1) and an isocyanate component (B) as constituent monomers (for example, described later). Make a solvent solution).
Next, water, if necessary, a solvent, a chain extender (C), and a neutralizing agent are added to emulsify the phase inversion, and if necessary, the solvent is distilled off to obtain an aqueous resin dispersion (Q) for paint. ..
(2) A solution of a polyurethane prepolymer (P) having an isocyanate group at the terminal containing a polymer polyol (A) containing a hydroxyl group-containing polyolefin (A1) and an isocyanate component (B) as constituent monomers (for example, described later). Organic solvent solution) is prepared.
Next, a mixture of water, if necessary, a solvent, a neutralizing agent, and a chain extender (C) is charged and dispersed by a known disperser, and if necessary, the solvent is distilled off to disperse an aqueous resin for paint. Get the body (Q).

(3) A solution of a polyurethane prepolymer (P) having an isocyanate group at the terminal containing a polymer polyol (A) containing a hydroxyl group-containing polyolefin (A1) and an isocyanate component (B) as constituent monomers (for example, described later). Make a solvent solution).
Next, the mixture containing the solution (P) and water is dispersed by a known disperser, a neutralizing agent and a reaction terminator are added if necessary, and a solvent is distilled off if necessary. , Obtain an aqueous resin dispersion (Q) for paint.
(4) A solvent solution of a polyurethane resin (U) containing a polymer polyol (A) containing a hydroxyl group-containing polyolefin (A1) and an isocyanate component (B) as constituent monomers is prepared.
Next, water is added and dispersed by, for example, a disperser, and if necessary, the solvent is distilled off to obtain an aqueous resin dispersion for paint (Q).

Further, in the step of obtaining the aqueous resin dispersion for paints, in addition to the polyurethane prepolymer (P), the solvent, the neutralizing agent, the chain extender (C), water, and the reaction terminator, if necessary, a known anionic surfactant is used. Activators, cationic surfactants, amphoteric surfactants and nonionic surfactants may be used.

Examples of the solvent include a ketone solvent (for example, acetone and methyl ethyl ketone), an ester solvent [for example, ethyl acetate and dibasic acid ester (DBE)], an ether solvent (for example, tetrahydrofuran), and an amide solvent (for example, N, N-dimethyl). Examples include organic solvents such as formamide and N-methylpyrrolidone), alcohol solvents (eg isopropyl alcohol) and aromatic hydrocarbon solvents (eg toluene).
Further, the above solvent may be contained in (Q).

The solid content concentration (content of components other than volatile components) of the aqueous resin dispersion for paint (Q) is preferably 20 to 65% by weight, more preferably 25 to 25% by weight, from the viewpoint of ease of handling of the dispersion. It is 55% by weight. Approximately 1 g of the aqueous resin dispersion for solids concentration paint is thinly spread on a Petri dish, weighed precisely, and then heated at 130 ° C. for 45 minutes using a circulating constant temperature dryer, and then weighed and weighed before heating. It can be obtained by calculating the ratio (percentage) of the residual weight after heating to the weight of.

The viscosity of the aqueous resin dispersion for paint (Q) at 25 ° C. is preferably 10 to 100,000 mPa · s, more preferably 10 to 5,000 mPa · s, from the viewpoint of handleability. The viscosity can be measured at a constant temperature of 25 ° C. using a BL type viscometer.

The pH of the aqueous resin dispersion (Q) for coating materials is preferably 2 to 12, more preferably 4 to 10 from the viewpoint of compounding stability. The pH can be measured at 25 ° C. with a pH Meter M-12 [manufactured by HORIBA, Ltd.].

The volume average particle diameter (Dv) of the particles (U) in the aqueous resin dispersion for paint (Q) of the present invention is preferably 0.01 to 1 μm, more preferably 0.02 to 0.02, from the viewpoint of dispersion stability. It is 0.7 μm, particularly preferably 0.03 to 0.4 μm. When (Dv) is 0.01 μm or more, the viscosity is appropriate and the handleability is good, and when it is 1 μm or less, the dispersion stability is good.

The volume average particle size (Dv) can be controlled by the amount of ionic polar groups in (U), the type of disperser used in the dispersion step, and operating conditions.

Further, the water-based coating composition of the present invention is a water-based coating composition containing the aqueous resin dispersion for coating materials. The water-based coating composition may contain one or two cross-linking agents, catalysts, pigments, pigment dispersants, viscosity modifiers, defoamers, leveling agents, preservatives, deterioration inhibitors, stabilizers, antifreeze agents, etc., if necessary. Can contain more than a seed.
The water-based coating composition of the present invention is particularly suitable as a water-based coating composition for building material coating or building coating and a water-based coating composition for automobiles.
The coating film is obtained, for example, by applying it to a base material (plastic film or the like) and heating and / or curing it if necessary.

As the cross-linking agent, specifically, at least one cross-linking agent selected from the group consisting of melamine resin, blocked isocyanate and epoxy compound can be used.
The amount of the cross-linking agent added is preferably 30% by weight or less, more preferably 0.1 to 20% by weight, based on the solid content weight of the aqueous resin dispersion for paint, from the viewpoint of substrate followability and substrate adhesion. Is.

As the melamine resin, those generally used as a cross-linking agent can be used. For example, an alkyl etherified melamine resin alkyl etherified with a monohydric alcohol such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol is preferable. Examples of the alkyl etherified melamine resin include the Uban series manufactured by Mitsui Chemicals, Inc. (Uban 120, 20HS, 2021, 2028, 228, 28-60, 22R, etc.) and the Cymel series manufactured by Ornex Japan (22R, etc.). Cymel 202, 232, 235, 250, 254, 285, 303, 325, 327, 328, 350, 370, 114, 1156, 1158, etc.).

The blocked isocyanate is not particularly limited as long as it has two or more blocked isocyanate groups in the molecule, and for example, the polyisocyanate compound exemplified as the isocyanate component (B) is known as a blocking agent [phenols, secondary. Or tertiary alcohols, oximes, aliphatic or aromatic secondary amines, phthalic acid imides, lactams, active methylene compounds (malonic acid dialkyl esters, etc.), pyrazole compounds (pyrazole and 3,5). -Dimethylpyrazole, etc.) and acidic sodium sulfite, etc.] and the like are blocked.

Commercially available blocked isocyanates include the Duranate series (Duranate 17B-60P, TPA-B80E, MF-B60B, MF-K60B, SBB-70P, SBN-70D, SBF-70E, E402-B80B) manufactured by Asahi Kasei Corporation. And WM44-L70G etc.) and the like.

The epoxy compound is not particularly limited as long as it is a compound having two or more epoxy groups in the molecule, for example, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol polyglycidyl. Examples thereof include ether, hydrogenated bisphenol A diglycidyl ether, trimethylpropan polyglycidyl ether, pentaerythritol polyglycidyl ether and polypropylene glycol diglycidyl ether.

As the pigment, various pigments such as a coloring pigment, an extender pigment, and a bright pigment can be used. Examples of the coloring pigments include inorganic pigments (yellow lead, iron oxide, yellow iron oxide, carbon black, titanium dioxide, etc.) and organic pigments (azochelate pigments, insoluble azo pigments, condensed azo pigments, phthalocyanine pigments, etc.). Indigo pigments, perinone pigments, perylene pigments, dioxane pigments, quinacridone pigments, isoindolinone pigments, metal complex pigments, etc.) can be mentioned. Examples of the extender pigment include calcium carbonate, precipitated barium sulfate, barite, talc, clay and the like. Examples of the bright pigment include aluminum flake pigment, alumina flake pigment, mica pigment, silica flake pigment, glass flake pigment and the like. These pigments may be used alone or in combination of two or more.

Examples of the pigment dispersant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants and other emulsion dispersants. The pigment dispersant may be used alone or in combination of two or more.

Examples of the nonionic surfactant include an AO-added nonionic surfactant and a polyhydric alcohol-based nonionic surfactant. Examples of the AO addition type include EO additions of aliphatic alcohols having 10 to 20 carbon atoms, EO additions of phenols, EO additions of nonylphenols, EO additions of alkylamines having 8 to 22 carbon atoms, and EO additions of polypropylene glycol. Examples of the polyhydric alcohol type include fatty acid (8 to 24 carbon atoms) esters of polyhydric (3 to 8 or more) alcohols (2 to 30 carbon atoms) (for example, glycerin monostearate and glycerin). Monooleate, sorbitan monolaurate, sorbitan monooleate, etc.) and alkyl (4 to 24 carbon atoms) poly (polymerization degree 1 to 10) glycoside and the like can be mentioned.

Examples of the anionic surfactant include ether carboxylic acid having a hydrocarbon group having 8 to 24 carbon atoms or a salt thereof [sodium lauryl ether acetate and (poly) oxyethylene (additional molars 1 to 100) sodium lauryl ether acetate and the like. ]; Sulfate or ether sulfate having a hydrocarbon group having 8 to 24 carbon atoms and salts thereof [sodium lauryl sulfate, (poly) oxyethylene (additional moles 1 to 100) sodium lauryl sulfate, (poly) oxyethylene (Additional moles 1 to 100) Sodium lauryl sulfate triethanolamine and (poly) oxyethylene (Additional moles 1 to 100) Palm oil fatty acid monoethanolamide sodium sulfate, etc.]; Acid salt [sodium dodecyl benzene sulfonate, etc.]; sulfosuccinate having one or two hydrocarbon groups having 8 to 24 carbon atoms; phosphate ester or ether phosphate ester having hydrocarbon groups having 8 to 24 carbon atoms And their salts [sodium lauryl phosphate and (poly) oxyethylene (additional moles 1 to 100) sodium lauryl ether phosphate, etc.]; fatty acid salts having a hydrocarbon group having 8 to 24 carbon atoms [sodium lauryl and laurin] Acid triethanolamine, etc.]; And acylated amino acid salts having a hydrocarbon group having 8 to 24 carbon atoms [coconut oil fatty acid methyl taurine sodium, palm oil fatty acid sarcosin sodium, coconut oil fatty acid sarcosin triethanolamine, N-palm oil fatty acid Acyl-L-glutamate triethanolamine, N-palm oil fatty acid acyl-L-sodium glutamate, sodium lauroylmethyl-β-alanine, etc.] can be mentioned.

Examples of the cationic surfactant include quaternary ammonium salt type [stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, distearyldimethylammonium chloride, lanolin fatty acid ethyl sulfate aminopropylethyldimethylammonium, etc.] and amine salt type [stearic acid. Diethylaminoethylamide lactate, dilaurylamine hydrochloride, oleylamine lactate, etc.].

Examples of amphoteric tenside agents include betaine-type amphoteric tenside agents [coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryl. Hydroxysulfobetaine and lauroylamide ethyl hydroxyethylcarboxymethylbetaine hydroxypropyl phosphate, etc.] and amino acid amphoteric tenside [β-laurylaminopropionate, etc.] can be mentioned.

Other emulsifying dispersants include, for example, polyvinyl alcohol, starch and derivatives thereof, cellulose derivatives such as carboxymethyl cellulose, methyl cellulose and hydroxyethyl cellulose, carboxyl group-containing (co) polymers such as sodium polyacrylate, and US Pat. No. 5,906,704. Examples thereof include an emulsion dispersant having a urethane group or an ester group described in the book [for example, a polycaprolactone polyol and a polyether diol linked with a polyisocyanate].

Examples of the leveling agent include an acrylic leveling agent, a vinyl leveling agent, a silicone leveling agent, a fluorine leveling agent, and the like.

Viscosity modifiers include thickeners such as inorganic viscosity regulators (sodium silicate, bentonite, etc.), cellulosic viscosity regulators (methyl cellulose with Mn of 20,000 or more, carboxymethyl cellulose, hydroxymethyl cellulose, etc.), proteins. Viscosity adjusters (casein, casein soda, ammonium casein, etc.), acrylics (sodium polyacrylate with Mn of 20,000 or more, ammonium polyacrylate, etc.) and vinyl viscosity adjusters (Mn of 20,000 or more) (Polyvinyl alcohol, etc.) can be mentioned.
Examples of the defoaming agent include long-chain alcohols (octyl alcohol and the like), sorbitan derivatives (sorbitan monooleate and the like), silicone oils (polymethylsiloxane and polyether-modified silicones and the like) and the like.

Examples of the preservative include an organic nitrogen-sulfur compound-based preservative and an organic sulfur halide-based preservative.
Examples of the deterioration inhibitor and stabilizer (ultraviolet absorber, antioxidant, etc.) include hindered phenol-based, hindered amine-based, hydrazine-based, phosphorus-based, benzophenone-based or benzotriazole-based deterioration inhibitor and stabilizer. ..
Examples of the antifreeze agent include ethylene glycol and propylene glycol.
The contents of the viscosity regulator, antifoaming agent, preservative, deterioration inhibitor, stabilizer and antifreeze agent are added from the viewpoint of substrate adhesion based on the weight of each of the above compositions in the intended use. The amount is preferably as small as possible within the range in which the effect of the agent can be exhibited, and is preferably 5% by weight or less, more preferably 3% by weight or less, respectively.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto.

<Manufacturing example 1>
Polyolefin (A001) containing 91% by weight of propylene and 9% by weight of ethylene as constituent monomers in a reaction vessel [Mn: 113,000, isotacticity: 50%, trade name "Vistamaxx3980", manufactured by Exxonmobil] 1000 parts by weight was charged, heated and melted with a mantle heater while aerating nitrogen into the liquid phase, and heat-reduced at 370 ° C. for 85 minutes while stirring to obtain polyolefin (A01-1).
In the reaction vessel, 100 parts by weight of the obtained polyolefin (A01-1) and 6.5 parts by weight of maleic anhydride (E-1) (described in parts by weight after deducting the distillate described later) are described. (Same as above) is charged, and after nitrogen substitution, the temperature is raised to 180 ° C. under nitrogen aeration to uniformly dissolve the radical initiator [Dikumil peroxide, trade name "Parkmill D", manufactured by Nichiyu Co., Ltd.]. A solution prepared by dissolving 0.5 part by weight of (F-1) in 5 parts by weight of xylene was added dropwise over 5 minutes, and then stirring was continued for 1 hour under reflux of xylene. Then, unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa) to obtain an acid-modified polyolefin (X-1).
Next, in the reaction vessel, 100 parts by weight of (X-1) and 6.4 parts by weight of 2-aminoethanol (G-1) (described in parts by weight after deducting the distillate to be described later are described. Also in the following production examples. The same applies.) Was charged, and the mixture was reacted at 180 ° C. for 1 hour in a nitrogen gas atmosphere.
Then, unreacted 2-aminoethanol was distilled off under a reduced pressure of 180 ° C. and 2.7 kPa to obtain a hydroxyl group-containing polyolefin (A1-1).
The hydroxyl value of (A1-1) was 29, the acid value was 0.2, Mn was 3,500, and the isotacticity was 43%. The number of double bonds per 1,000 carbons of the polyolefin (A01-1) used for the modification was 7.5.

<Manufacturing example 2>
Polyolefin (A001) containing 91% by weight of propylene and 9% by weight of ethylene as constituent monomers in a reaction vessel [Mn: 113,000, isotacticity: 50%, trade name "Vistamaxx3980", manufactured by Exxonmobil] 1000 parts by weight was charged, heated and melted with a mantle heater while aerating nitrogen into the liquid phase, and heat-reduced at 380 ° C. for 65 minutes while stirring to obtain a polyolefin (A01-2).
In a reaction vessel, 100 parts by weight of the obtained polyolefin (A01-2) and 8 parts by weight of maleic anhydride (E-1) were charged, and after nitrogen substitution, the temperature was raised to 180 ° C. under nitrogen aeration to uniformly dissolve. The mixture was allowed to stir for 1 hour. Then, unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa) to obtain an acid-modified polyolefin (X-2).
Next, 100 parts by weight of (X-2) and 6.4 parts by weight of 2-aminoethanol (G-1) were charged in the reaction vessel, and the mixture was reacted at 180 ° C. for 1 hour in a nitrogen gas atmosphere.
Then, unreacted 2-aminoethanol was distilled off under a reduced pressure of 180 ° C. and 2.7 kPa to obtain a hydroxyl group-containing polyolefin (A1-2).
The hydroxyl value of (A1-2) was 29, the acid value was 0.1, Mn was 3,300, and the isotacticity was 43%. The number of double bonds per 1,000 carbons of the polyolefin (A01-2) used for the modification was 8.8.

<Manufacturing example 3>
Polyolefin (A00-2) containing 85% by weight of propylene and 15% by weight of ethylene as constituent monomers in a reaction vessel [Mn: 76,000, isotacticity: 20%, trade name "Vistamaxx6202", manufactured by Exxonmobil] 1000 parts by weight was charged, heated and melted with a mantle heater while aerating nitrogen into the liquid phase, and heat-reduced at 400 ° C. for 50 minutes while stirring to obtain a polyolefin (A01-3).
In a reaction vessel, 100 parts by weight of the obtained polyolefin (A01-3) and 11 parts by weight of maleic anhydride (E-1) were charged, and after nitrogen substitution, the temperature was raised to 180 ° C. under nitrogen aeration to uniformly dissolve the mixture. After 5 minutes, a solution prepared by dissolving 3 parts by weight of a radical initiator [Dikumil peroxide, trade name "Parkmill D", manufactured by Nichiyu Co., Ltd.] (F-1) in 10 parts by weight of xylene was added dropwise. , Stirring was continued for 1 hour under reflux with xylene. Then, unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa) to obtain an acid-modified polyolefin (X-3).
Next, 100 parts by weight of (X-3) and 10 parts by weight of 2-aminoethanol (G-1) were charged in a reaction vessel, and the mixture was reacted at 180 ° C. for 1 hour in a nitrogen gas atmosphere.
Then, unreacted 2-aminoethanol was distilled off under a reduced pressure of 180 ° C. and 2.7 kPa to obtain a hydroxyl group-containing polyolefin (A1-3).
The hydroxyl value of (A1-3) was 46, the acid value was 0.1, Mn was 2,300, and the isotacticity was 18%. The number of double bonds per 1,000 carbons of the polyolefin (A01-3) used for the modification was 9.5.

<Manufacturing example 4>
Polyolefin (A00-2) containing 85% by weight of propylene and 15% by weight of ethylene as constituent monomers in a reaction vessel [Mn: 76,000, isotacticity: 20%, trade name "Vistamaxx6202", manufactured by Exxonmobil] 1000 parts by weight was charged, heated and melted with a mantle heater while aerating nitrogen through the liquid phase, and heat-reduced at 400 ° C. for 100 minutes with stirring to obtain a polyolefin (A01-4).
In a reaction vessel, 100 parts by weight of the obtained polyolefin (A01-4) and 23.5 parts by weight of maleic anhydride (E-1) were charged, and after nitrogen substitution, the temperature was raised to 180 ° C. under nitrogen aeration to make it uniform. A solution prepared by dissolving 3 parts by weight of a radical initiator [Dicmil peroxide, trade name "Parkmill D", manufactured by Nichiyu Co., Ltd.] (F-1) in 10 parts by weight of xylene was added dropwise in 5 minutes. After that, stirring was continued for 1 hour under reflux of xylene. Then, unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa) to obtain an acid-modified polyolefin (X-4).
Next, 100 parts by weight of (X-4) and 27 parts by weight of 2-aminoethanol (G-1) were charged in a reaction vessel, and the mixture was reacted at 180 ° C. for 1 hour in a nitrogen gas atmosphere.
Then, unreacted 2-aminoethanol was distilled off under a reduced pressure of 180 ° C. and 2.7 kPa to obtain a hydroxyl group-containing polyolefin (A1-4).
The hydroxyl value of (A1-4) was 108, the acid value was 0.2, Mn was 1,050, and the isotacticity was 17%. The number of double bonds per 1,000 carbons of the polyolefin (A01-4) used for the modification was 22.4.

<Manufacturing example 5>
Polyolefin (A00-3) [Mn: 200,000, isotacticity: 33%, trade name "Toughmer S4030", Mitsui Chemicals, Inc. containing 73% by weight of propylene and 27% by weight of ethylene as constituent monomers in the reaction vessel. Manufactured] 1000 parts by weight was charged, heated and melted with a mantle heater while aerating nitrogen into the liquid phase, and heat-reduced at 380 ° C. for 80 minutes while stirring to obtain polyolefin (A01-5). It was.
In a reaction vessel, 100 parts by weight of the obtained polyolefin (A01-5) and 4.5 parts by weight of maleic anhydride (E-1) were charged, and after nitrogen substitution, the temperature was raised to 180 ° C. under nitrogen aeration to make it uniform. A solution prepared by dissolving 0.5 parts by weight of a radical initiator [Dicmil peroxide, trade name "Parkmill D", manufactured by Nichiyu Co., Ltd.] (F-1) in 5 parts by weight of xylene was dissolved in 5 parts by weight of xylene for 5 minutes. After dropping in, stirring was continued for 1 hour under reflux with xylene. Then, unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa) to obtain an acid-modified polyolefin (X-5).
Next, 100 parts by weight of (X-5) and 4.6 parts by weight of 2-aminoethanol (G-1) were charged in a reaction vessel, and the mixture was reacted at 180 ° C. for 1 hour in a nitrogen gas atmosphere.
Then, unreacted 2-aminoethanol was distilled off under a reduced pressure of 180 ° C. and 2.7 kPa to obtain a hydroxyl group-containing polyolefin (A1-5).
The hydroxyl value of (A1-5) was 21, the acid value was 0.2, Mn was 4,500, and the isotacticity was 31%. The number of double bonds per 1,000 carbons of the polyolefin (A01-5) used for the modification was 5.4.

<Comparative manufacturing example 1>
In a reaction vessel, a polyolefin (ratio A001) containing 98% by weight of propylene and 2% by weight of ethylene as constituent monomers [Mn: 100,000, isotacticity: 90%, trade name "Sun Aroma PZA20A", Sun Aroma ( Made by Co., Ltd.] 1000 parts by weight was charged, heated and melted with a mantle heater while aerating nitrogen into the liquid phase, and heat-decomposed at 400 ° C. for 1200 minutes with stirring to obtain polyolefin (ratio A01-1). ) Was obtained.
In a reaction vessel, 100 parts by weight of the obtained polyolefin (ratio A01-1) and 28 parts by weight of maleic anhydride (E-1) were charged, and after nitrogen substitution, the temperature was heated to 180 ° C. under nitrogen aeration to make it uniform. A solution prepared by dissolving 3 parts by weight of the radical initiator [Dicmil peroxide, trade name "Parkmill D", manufactured by Nichiyu Co., Ltd.] (F-1) in 10 parts by weight of xylene was added dropwise over 5 minutes. After that, stirring was continued for 1 hour under reflux with xylene. Then, unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa) to obtain an acid-modified polyolefin (ratio X-1).
Next, 100 parts by weight (ratio X-1) and 22 parts by weight of 2-aminoethanol (G-1) were charged in the reaction vessel, and the reaction was carried out at 180 ° C. for 1 hour in a nitrogen gas atmosphere.
Then, unreacted 2-aminoethanol was distilled off under a reduced pressure of 180 ° C. and 2.7 kPa to obtain a hydroxyl group-containing polyolefin (ratio A1-1).
The hydroxyl value of (ratio A1-1) was 122, the acid value was 0.2, Mn was 940, and the isotacticity was 84%. The number of double bonds per 1,000 carbons of the polyolefin (ratio A01-1) used for the modification was 22.5.

<Comparative manufacturing example 2>
Polyolefin (ratio A00-2) [Mn: 40,000, isoactivity: 3%, trade name "Toughmer P0280", Mitsui Chemicals, which contains 27% by weight of propylene and 73% by weight of ethylene as constituent monomers in the reaction vessel. Manufactured by Co., Ltd.] 1000 parts by weight was charged, heated and melted with a mantle heater while aerating nitrogen into the liquid phase, and heat-decomposed at 385 ° C. for 210 minutes with stirring to obtain polyolefin (ratio A01-). 2) was obtained.
In a reaction vessel, 100 parts by weight of the obtained polyolefin (ratio A01-2) and 9 parts by weight of maleic anhydride (E-1) were charged, and after nitrogen substitution, the temperature was heated to 180 ° C. under nitrogen aeration to make it uniform. A solution prepared by dissolving 0.5 parts by weight of the radical initiator [Dicmil peroxide, trade name "Parkmill D", manufactured by Nichiyu Co., Ltd.] (F-1) in 5 parts by weight of xylene was dissolved in 5 minutes. After the dropping, stirring was continued for 1 hour under reflux with xylene. Then, unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa) to obtain an acid-modified polyolefin (ratio X-2).
Next, 100 parts by weight (ratio X-2) and 10 parts by weight of 2-aminoethanol (G-1) were charged in the reaction vessel, and the mixture was reacted at 180 ° C. for 1 hour in a nitrogen gas atmosphere.
Then, unreacted 2-aminoethanol was distilled off under a reduced pressure of 180 ° C. and 2.7 kPa to obtain a hydroxyl group-containing polyolefin (ratio A1-2).
The hydroxyl value of (ratio A1-2) was 35, the acid value was 0.1, Mn was 3,000, and the isotacticity was 1%. The number of double bonds per 1,000 carbons of the polyolefin (ratio A01-2) used for the modification was 10.5.

<Example 1>
(Manufacturing of urethane prepolymer)
A simple pressurizing reaction device equipped with a stirrer and a heating device contains 179.26 parts by weight of hydroxyl group-containing polyolefin (A1-1), 92.19 parts by weight of high molecular weight polyol (A2-1), and an isocyanate component (B-1). 82.65 parts by weight of [IPDI, isophorone diisocyanate], 4.18 parts by weight of [1,4-butanediol] as chain extender (C), 17.03 parts by weight of [2,2-dimethylolpropionic acid]. , 124.69 parts by weight of an organic solvent [THF, tetrahydrofuran] was charged, and the mixture was stirred at 85 ° C. for 10 hours to carry out a urethanization reaction to produce a THF solution (P-1) of urethane prepolymer.
(Manufacturing of water-based resin dispersion for paint)
A simple pressurizing reaction device equipped with a stirrer and a heating reaction device was charged with 500 parts by weight of the obtained THF solution (P-1) of the urethane prepolymer, and while stirring at 50 ° C., THF 359.28 parts by weight and triethylamine (medium). After adding 12.81 parts by weight of Japanese agent) and homogenizing at 60 rpm for 30 minutes, keeping the temperature at 50 ° C., stirring at 500 rpm, and gradually adding 676.04 parts by weight of ion-exchanged water to emulsify. , Chain extender (C-3) [5 wt% diethylenetriamine aqueous solution] 86.82 parts by weight was added, THF was distilled off under reduced pressure at 65 ° C. for 12 hours, and an aqueous resin dispersion for coating (Q-1) was added. ) Was obtained.

<Examples 2 to 25, Comparative Examples 1 to 3>
Aqueous resin dispersions for paints (Q-2) to (Q-25), (Ratio Q) of each example in the same manner as in Example 1 except that the raw materials shown in Tables 1 to 4 were used as raw materials. -1) to (ratio Q-3) were obtained.
The obtained aqueous resin dispersions for paints (Q-1) to (Q-25) and (ratio Q-1) to (ratio Q-3) of each example were evaluated by the procedure described later. The results are shown in Tables 1 to 4.

The volume average particle size (Dv) was measured using a laser diffraction type particle size distribution measuring device "LA-750" [manufactured by HORIBA, Ltd.].

The raw materials used in the examples and comparative examples in Tables 1 to 4 are as follows. The amount of each raw material is a part by weight of high molecular weight polyol (A2-1):
-Kuraray Polyol P-2010: Poly (3-methyl-1,5-pentanediol, adipic acid polycondensate) with Mn = 2,000, manufactured by Kuraray Co., Ltd.]
Polymer polyol (A2-2):
-Kuraray Polyol P-2011: Mn = 2,000 poly (3-methyl-1,5-pentanediol, adipic acid, terephthalic acid polycondensate), manufactured by Kuraray Co., Ltd.]
High molecular weight polyol (A2-3):
-Kuraray Polyol P-2012: Poly with Mn = 2,000 (3-methyl-1,5-pentanediol, adipic acid, isophthalic acid polycondensate), manufactured by Kuraray Co., Ltd.]
Polymer polyol (A2-4):
-Kuraray Polyol P-2020: Poly (3-methyl-1,5-pentanediol, terephthalic acid polycondensate) with Mn = 2,000, manufactured by Kuraray Co., Ltd.]
Polymer polyol (A4-1):
Ethanacole UH-200: Polyhexamethylene carbonate diol with Mn = 2,000 [manufactured by Ube Industries, Ltd.]
Polymer polyol (A5-1):
-PTMG2000: Poly (oxytetramethylene) glycol with Mn = 2,000 [manufactured by Mitsubishi Chemical Corporation]
High molecular weight polyol (A5-2):
-PTMG3000: Poly (oxytetramethylene) glycol with Mn = 3,000 [manufactured by Mitsubishi Chemical Corporation]
Polymer polyol (A6-1):
-Actflow UT-1001: Mn = 2000 polyacrylic diol [manufactured by Soken Chemical Co., Ltd.]
High molecular weight polyol (A6-2):
-ARUFON UH-2032: Polyacrylic diol with Mn = 2000 [manufactured by Toagosei Co., Ltd.]
-Neostan U-600: Bismuth Tris (2-ethylhexanoate) [manufactured by Nitto Kasei Co., Ltd.]
Emalmin 50: Ethylene oxide (EO) adduct of higher alcohol [manufactured by Sanyo Chemical Industries, Ltd.]

<Evaluation method for room temperature dry water-based paint composition>
1. 1. Preparation of water-based paint composition for weather resistance evaluation (water-based paint composition for building material painting or building painting) In a polyethylene container, 20 parts by weight of ion-exchanged water, 66 parts by weight of titanium oxide, and "Orotan 731" as a dispersant. 6 parts by weight of aqueous solution (manufactured by Dow Chemical Co., Ltd.) adjusted to a solid content concentration of 10% by weight, 0.2 parts by weight of "SN Deformer 777" (manufactured by Sannopco Co., Ltd.) as a defoaming agent, ethylene as a wetting agent 2 parts by weight of glycol and 500 parts by weight of zirconia beads were added, and the mixture was kneaded with a paint conditioner [manufactured by Red Devil] for 1 hour. The obtained dispersion was filtered through a wire mesh having a mesh size of 75 μm to remove zirconia beads, and a pigment dispersion was obtained.

55.6 parts by weight of the aqueous resin dispersion for paint, which was previously adjusted to a solid content concentration of 24% by weight with ion-exchanged water in a glass container, acrylic emulsion "AE986B" (manufactured by E-Tech Co., Ltd., solid content 35% by weight) ) 38.2 parts by weight, 25.6 parts by weight of the pigment dispersion liquid, and 2.2 parts by weight of an aqueous solution prepared by adjusting "Natrosol 250MR" (manufactured by Ashland Specialty Chemicals) as a thickener in advance to a solid content concentration of 4% by weight. , 1.1 parts by weight of an aqueous solution prepared by adjusting "Adecanol UH-420" [manufactured by ADEKA Co., Ltd.] as a thickener in advance to a solid content concentration of 10% by weight, and texanol (2,2,4) as a film-forming aid. Add 0.9 parts by weight of −trimethyl-1,3-pentanediol 2-methylpropanoart) and knead with a kneader (“Awatori Kentarou AR-550L-3” manufactured by Shinky Co., Ltd.) for 3 minutes. Obtained an aqueous coating composition.

2. Evaluation method of weather resistance A water-based paint composition for weather resistance test was applied onto a glass plate (length 10 cm x width 10 cm x thickness 0.5 cm) using a bar coater so that the film thickness after drying was 80 μm. .. This was dried in a constant temperature and humidity chamber at 25 ° C. and 50% RH for 24 hours to obtain a sample for evaluation.

Weather resistance test of the obtained evaluation sample using a weather resistance tester [“SUV-W151” manufactured by Iwasaki Electric Co., Ltd.] [Test conditions: Irradiation intensity 75 mW / cm ^{2 under the conditions of “73 ° C × 50% RH”} After irradiation for 3.8 hours, under the condition of 38 ° C. × 95% RH, “no irradiation for 1.0 hour” is set as one cycle, and 10 cycles are repeated. ] Was performed, the glossiness before and after the test was measured, and the glossiness retention rate was calculated from the following formula. The glossiness was measured using a gloss meter [VG-1D manufactured by Nippon Denshoku Kogyo Co., Ltd.] under the conditions of incident angle / reflection angle = 60 ° / 60 °. The retention rate of glossiness was evaluated according to the following criteria.
Gloss retention rate (%) = Gloss after irradiation / Gloss before irradiation x 100
⊚: Gloss retention rate is 70% or more 〇: 50% or more and less than 70% Δ: 30% or more and less than 50% ×: less than 30%

<Evaluation method for adhesion to polypropylene>
A commercially available polypropylene test piece is coated with the above-mentioned water-based coating composition for weather resistance test with a bar coater so as to have a film thickness of 20 μm, and dried in a constant temperature and humidity chamber at 25 ° C. and 50% RH for 24 hours. To obtain a test piece on which a coating film was formed. Six orthogonal cuts were made in each of the vertical and horizontal directions at 1 mm intervals on the coating film surface, and then a peeling test was performed with cellophane tape (registered trademark) to check the number of 1 mm square coating films remaining. Adhesion was evaluated according to the following criteria.
⊚: Residual number 24 or more ○: Residual number 20 or more and less than 24 Δ: Residual number 15 or more and less than 20 ×: Residual number less than 15

<Evaluation method for adhesion to steel sheet>
The surface of a commercially available cold-rolled steel sheet test piece is polished with water-resistant abrasive paper, degreased with toluene, and then coated with a bar coater so that the film thickness is 20 μm. , 25 ° C., 50% RH, and a constant temperature and humidity chamber for 24 hours to obtain a test piece on which a coating film was formed. Six orthogonal cuts were made in each of the vertical and horizontal directions at 1 mm intervals on the coating film surface, and then a peeling test was performed with cellophane tape (registered trademark) to check the number of 1 mm square coating films remaining. Adhesion was evaluated according to the following criteria.
⊚: Residual number 24 or more ○: Residual number 20 or more and less than 24 Δ: Residual number 15 or more and less than 20 ×: Residual number less than 15

<Evaluation method of baking type water-based paint composition>
1. 1. Preparation of water-based paint composition for adhesion evaluation (water-based paint composition for automobiles) 70 parts by weight of rutile-type titanium dioxide, 10 parts by weight of "Disperbyk190" (manufactured by Big Chemie Japan), carbon black [Orion Engineered Carbons Co., Ltd. )] 0.5 parts by weight and 34.3 parts by weight of ion-exchanged water were premixed and then dispersed with a paint shaker for 30 minutes to obtain a pigment-dispersed paste. 116.7 parts by weight of the aqueous resin dispersion for paints, which was previously adjusted to a solid content concentration of 24% by weight with ion-exchanged water, 84 parts by weight of "Byronal MD1480" (manufactured by Toyo Boseki Co., Ltd.), and " 23.3 parts by weight of "Simel 327" (manufactured by Ornex Japan Co., Ltd.) is added and mixed uniformly, and then N, N-dimethyl-2-aminoethanol is added to adjust the pH of the paint to 8.0 to 9.0. To obtain a water-based coating composition for adhesion evaluation.

<Evaluation method for adhesion to electrodeposition plate>
The above-mentioned water-based coating composition for adhesion evaluation is coated on a commercially available cationic electrodeposition coating test piece with a bar coater so that the film thickness is 20 μm, preheated at 80 ° C. for 5 minutes, and then 30 at 120 ° C. Heat curing was carried out for 1 minute to obtain a test piece on which a coating film was formed. Six orthogonal cuts were made in each of the vertical and horizontal directions at 1 mm intervals on the coating film surface, and then a peeling test was performed with cellophane tape (registered trademark) to check the number of 1 mm square coating films remaining. Adhesion was evaluated according to the following criteria.
⊚: Residual number 24 or more ○: Residual number 20 or more and less than 24 Δ: Residual number 15 or more and less than 20 ×: Residual number less than 15

<Evaluation method for adhesion to polypropylene>
A commercially available polypropylene test piece is coated with the above-mentioned water-based coating composition for adhesion evaluation with a bar coater so that the film thickness is 20 μm, preheated at 80 ° C. for 5 minutes, and then at 120 ° C. for 30 minutes. Heat curing was performed to obtain a test piece on which a coating film was formed. Six orthogonal cuts were made in each of the vertical and horizontal directions at 1 mm intervals on the coating film surface, and then a peeling test was performed with cellophane tape (registered trademark) to check the number of 1 mm square coating films remaining. Adhesion was evaluated according to the following criteria.
⊚: Residual number 24 or more ○: Residual number 20 or more and less than 24 Δ: Residual number 15 or more and less than 20 ×: Residual number less than 15

<Evaluation method of storage stability>
The viscosity of the above-mentioned water-based coating composition for evaluation of adhesion was measured (V1). After storing the composition at 40 ° C. for 10 days, the viscosity was measured (V2). The thickening rate was calculated by the following formula, and the storage stability was evaluated according to the following criteria.
Thickening rate (%) = (V2-V1) / V1 × 100
◯: -50% ≤ thickening rate ≤ + 50%
Δ: -100% ≤ thickening rate <-50% or + 50% <thickening rate ≤ + 100%
X: Viscosity rate <-100% or + 100% <Viscosity rate <Viscosity measurement conditions>
Measuring equipment: B-type viscometer Rotation speed: 60 rpm

From the results of Tables 3 to 4, the aqueous coating composition containing the aqueous resin dispersion for coating materials of the present invention has excellent adhesion to different types of substrates (particularly polypropylene substrates) and excellent storage stability. I understand. On the other hand, it can be seen that some of the comparative examples have poor adhesion to the polypropylene base material and are inferior in storage stability.

The aqueous resin dispersion of the present invention can be suitably used for aqueous coating compositions other than aqueous coating compositions for inkjet inks. Here, the inkjet ink is a method of ejecting ink as droplets from a nozzle having a diameter of several micrometers and applying the ink, and this application is excluded in the present invention.

Claims (6)

An aqueous dispersion for paints containing water and a polyurethane resin (U), wherein the polyurethane resin (U) reacts an active hydrogen group-containing compound (W) with an isocyanate component (B). A polyurethane resin, wherein the active hydrogen group-containing compound (W) contains a polymer polyol (A), the polymer polyol (A) contains a hydroxyl group-containing polyolefin (A1), and the constitution of the hydroxyl group-containing polyolefin (A1). The weight ratio [ethylene / α-olefin] of ethylene as a monomer to α-olefin (3 to 8 carbon atoms) is 5/95 to 65/35, and the α-olefin portion of the hydroxyl group-containing polyolefin (A1). Isotacticity of 1 to 50%, and is an aqueous resin dispersion for paints excluding the aqueous resin dispersion for inkjet ink. The aqueous resin dispersion for paints according to claim 1, wherein the hydroxyl value (mgKOH / g) of the hydroxyl group-containing polyolefin (A1) is 12 to 120. The aqueous resin dispersion for paint according to claim 1 or 2, further comprising at least one resin selected from the group consisting of a urethane resin other than the polyurethane resin (U), an acrylic resin, and a polyester resin. A water-based paint composition for inkjet ink, which comprises the water-based resin dispersion for paint according to any one of claims 1 to 3 and at least one cross-linking agent selected from the group consisting of a melamine resin, a blocked isocyanate and an epoxy compound. Water-based paint composition excluding. The water-based paint composition according to claim 4, which is a water-based paint composition for painting a building material or a building. The water-based coating composition according to claim 4, which is a water-based coating composition for automobiles.