KR20130099070A - Aqueous polyurethane resin dispersion, manufacturing method therefor, and use therefor - Google Patents

Abstract

An aqueous polyurethane resin dispersion having good storage stability and excellent adhesion to various plastics (ABS resin, acrylic resin, polycarbonate resin) of the coating film after active energy ray (for example, ultraviolet ray) curing, and coating film having high hardness It provides an aqueous polyurethane resin dispersion to provide. The present invention is an aqueous polyurethane resin dispersion obtained by dispersing at least a polyurethane resin (A) having a polymerizable unsaturated bond and a compound (B) having a polymerizable unsaturated bond in an aqueous medium, a poly having a polymerizable unsaturated bond. The urethane resin (A) can react with a polycarbonate diol (a) having an alicyclic structure in the main chain, an acidic group-containing polyol (b), a polyisocyanate (d), and at least one isocyanato group in one molecule The present invention relates to an aqueous polyurethane resin dispersion comprising a compound (e) having an existing group and at least one polymerizable unsaturated bond, a coating composition and a coating composition containing the same, and a method for producing the same.

Description

Aqueous polyurethane resin dispersion, its manufacturing method, and its use {AQUEOUS POLYURETHANE RESIN DISPERSION, MANUFACTURING METHOD THEREFOR, AND USE THEREFOR}

The present invention relates to an aqueous urethane resin dispersion curable by active energy ray irradiation including ultraviolet rays, a method for producing the same, and a use thereof.

Polycarbonate polyol is a useful compound which is a raw material of a polyurethane resin, and can be used to produce polyurethane resins used for rigid foams, flexible foams, paints, adhesives, synthetic leathers, ink binders, and the like by reaction with isocyanate compounds. Moreover, the coating film obtained by apply | coating the water-based polyurethane resin dispersion which used the polycarbonate polyol as a raw material is known to be excellent in light resistance, heat resistance, hydrolysis resistance, and oil resistance (refer patent document 1).

Especially, it is known that the coating film obtained by apply | coating the water-based urethane resin dispersion using an aliphatic polycarbonate polyol is used as an undercoat agent in the adhesiveness with respect to a base material, and blocking property improving (refer patent document 2). Moreover, in order to improve the hardness and durability of a coating film, the water-based polyurethane resin dispersion using the polycarbonate polyol which has alicyclic structure is also proposed (refer patent document 3, 4, and 5).

On the other hand, since a radically polymerizable compound is excellent in sclerosis | hardenability also by methods other than heating, it is generally recognized as having a characteristic from a viewpoint of productivity and energy saving. The active energy ray-curable resin composition which has a radically polymerizable compound is used as an active component, such as various coatings and adhesives, such as a metal paint, an overcoating agent for various plastic films, a woodworking paint, and a printing ink, in view of such a characteristic. For example, the energy-beam curable aqueous resin composition which disperse | distributed the (meth) acrylate type compound with respect to the aqueous polyurethane resin dispersion is proposed (refer patent document 6).

Moreover, the energy-beam curable aqueous resin composition formed by disperse | distributing a (meth) acrylated polyurethane and a (meth) acryl compound in an aqueous medium is also proposed (refer patent document 7).

Japanese Patent Laid-Open No. 10-120757 Japanese Patent Laid-Open No. 2005-281544 Japanese Patent Laid-Open No. 6-248046 WO2009 / 145242 publication WO2010 / 004951 publication Japanese Patent Publication No. 2008-248014 Japanese Patent Publication No. 2009-533504

However, in the aqueous polyurethane resin dispersion using a polycarbonate polyol as a raw material, when only the aliphatic polycarbonate polyol is used as the polycarbonate polyol, the adhesion and hardness of the coating film obtained by applying the aqueous polyurethane resin dispersion are, for example, There has been a problem that it is not sufficient in the field of coatings or coatings such as exterior panels of airplanes and automobiles, exterior walls and floors of houses. On the other hand, when a polycarbonate polyol having an alicyclic structure is used, there is a problem in that dispersibility in an aqueous medium is deteriorated, which causes problems in handling and stability of the aqueous polyurethane resin dispersion, and a satisfactory adhesiveness and hardness are obtained. It is not confirmed.

On the other hand, in the patent document 6 which was pointed out about the energy-beam hardening type water-based resin composition, the (meth) acrylate type compound is disperse | distributed to an aqueous polyurethane resin dispersion using surfactant, and surfactant remains in a coating film Thereby, there was a problem that the coating film performance was lowered. In this composition, when the amount of the surfactant is reduced or not used, a problem arises in that the storage stability is lowered.

In addition, in patent document 7, in the combination of the (meth) acrylic-polyurethane polyol and (meth) acryl compound specifically disclosed, the coating film obtained from an energy-beam curable aqueous resin composition is applied to various plastics (especially ABS resin, acrylic resin). There was a problem that the adhesiveness against the.

The present invention is an active energy ray (for example, ultraviolet ray) curable aqueous polyurethane resin dispersion, which has good dispersibility and storage stability in an aqueous medium, and a coating film after active energy ray (for example, ultraviolet ray) curing. It is an object of the present invention to obtain an aqueous polyurethane resin dispersion having excellent adhesion to various kinds of plastics (ABS resin, acrylic resin, polycarbonate resin, and the like). Moreover, this invention makes it a subject to obtain the aqueous polyurethane resin dispersion which the coating film after hardening an active energy ray (for example, ultraviolet-ray) has high hardness.

MEANS TO SOLVE THE PROBLEM As a result of performing various examination in order to overcome the problem of the said prior art, as an aqueous polyurethane resin dispersion which disperse | distributes the polyurethane resin which has a polymerizable unsaturated bond, and the compound which has a polymerizable unsaturated bond in an aqueous medium, It has been found that the problem can be solved by using a polycarbonate polyol having an alicyclic structure as a raw material of the polyurethane resin.

The present invention (1) is an aqueous polyurethane resin dispersion obtained by dispersing at least a polyurethane resin (A) having a polymerizable unsaturated bond and a compound (B) having a polymerizable unsaturated bond in an aqueous medium,

The polyurethane resin (A) which has a polymerizable unsaturated bond is one in at least one polycarbonate diol (a) which has an alicyclic structure in a principal chain, an acidic group containing polyol (b), polyisocyanate (d), and one molecule The polyurethane resin obtained by reacting the above-mentioned isocyanato group with the group which can react with the compound (e) which has 1 or more polymerizable unsaturated bonds is related to the aqueous polyurethane resin dispersion characterized by the above-mentioned.

This invention (2) relates to the aqueous polyurethane resin dispersion of this invention (1) in which the compound (B) which has a polymerizable unsaturated bond contains the compound which has at least 3 (meth) acryloyl group.

This invention (3) is to the aqueous polyurethane resin dispersion of this invention (1) or (2) in which the compound (B) which has a polymerizable unsaturated bond contains the compound which has at least 5 (meth) acryloyl group. It is about.

The present invention (4) is a group in which a compound capable of reacting with one or more isocyanato groups in one molecule and a compound (e) having one or more polymerizable unsaturated bonds can react with one isocyanato group The aqueous polyurethane resin dispersion in any one of this invention (1)-(3) containing the compound which has one or more (meth) acryloyl groups.

This invention (5) is a group which can react with the group which can react with 1 or more isocyanato groups in 1 molecule, and the compound (e) which has 1 or more polymerizable unsaturated bonds can react with one isocyanato group. The aqueous polyurethane resin dispersion in any one of this invention (1)-(4) containing the compound which has three or more (meth) acryloyl groups.

In the present invention (6), a compound (e) having a group capable of reacting with one or more isocyanato groups and one or more polymerizable unsaturated bonds in one molecule contains two hydroxyl groups and two (meth) acryloyl groups. The aqueous polyurethane resin dispersion in any one of this invention (1)-(5) containing the compound which has a.

In the present invention (7), a polyurethane resin having a polymerizable unsaturated bond includes a polycarbonate diol (a) having an alicyclic structure in its main chain, an acid group-containing polyol (b), a polyisocyanate (d), and one molecule Any of the present inventions (1) to (6) obtained by reacting a compound (e) having one or more polymerizable unsaturated bonds with a group capable of reacting with at least one isocyanato group and a chain extender (C) in the It relates to one aqueous polyurethane resin dispersion.

This invention (8) relates to the aqueous polyurethane resin dispersion of this invention (7) whose chain extender (C) is a primary polyamine compound.

The present invention (9) reacts at least one isocyanato group in at least one polycarbonate diol (a) having an alicyclic structure in the main chain, an acidic group-containing polyol (b), a polyisocyanate (d) and one molecule. Reacting a group with a compound (e) having at least one polymerizable unsaturated bond to obtain a polyurethane resin (A),

Regarding the method for producing the aqueous polyurethane resin dispersion according to any one of the present invention (1) to (6), which comprises dispersing a polyurethane resin (A) and a compound (B) having a polymerizable unsaturated bond in an aqueous medium. will be.

The present invention (10) is capable of reacting at least a polycarbonate polyol (a) having an alicyclic structure in the main chain, an acidic group-containing polyol (b), a polyisocyanate (d), and at least one isocyanato group. A step (α1) of reacting a group with a compound (e) having at least one polymerizable unsaturated bond to obtain a polyurethane prepolymer (A1),

Process (β) of neutralizing the acidic group of the polyurethane prepolymer (A1), and

Step (γ) of dispersing the compound (B) having a polyurethane prepolymer (A1) and a polymerizable unsaturated bond in an aqueous medium,

The present invention comprising the step (δ) of reacting a polyurethane prepolymer (A1) with a chain extender (C) having a reactivity with the isocyanato group of the polyurethane prepolymer (A1) to obtain an aqueous polyurethane resin ( It relates to a method for producing the aqueous polyurethane resin dispersion of 7) or (8).

This invention (11) relates to the water-based polyurethane resin dispersion in any one of this invention (1)-(8) which further contains a photoinitiator.

This invention (12) relates to the coating composition containing the aqueous polyurethane resin dispersion in any one of this invention (1)-(8) and (11).

This invention (13) relates to the coating composition containing the aqueous polyurethane resin dispersion in any one of this invention (1)-(8) and (11).

According to the present invention, it has good dispersibility and storage stability in an aqueous medium, and adhesiveness to various plastics (ABS resin, acrylic resin, polycarbonate resin, etc.) of the coating film after hardening active energy ray (for example, ultraviolet ray). Excellent aqueous polyurethane resin dispersions and methods for their preparation are provided. Moreover, according to this invention, the aqueous polyurethane resin dispersion which provides the coating film which has high hardness, and its manufacturing method are provided. The aqueous polyurethane resin dispersion of the present invention is a synthetic resin molded body such as outer boards such as aircraft and automobiles, interior materials of automobiles, mobile phone cases, home appliance cases, personal computer cases, decorative films, optical films, floorings such as floorings, and outer walls. It can be used as a raw material such as a paint (including a primer), an ink, an adhesive, a coating agent, a coating composition, and can be used for a wide range of applications.

The present invention is an aqueous polyurethane resin dispersion obtained by dispersing at least a polyurethane resin (A) having a polymerizable unsaturated bond and a compound (B) having a polymerizable unsaturated bond in an aqueous medium, and having a polymerizable unsaturated bond. The polyurethane resin (A) can react with at least one polycarbonate diol (a) having an alicyclic structure in the main chain, an acidic group-containing polyol (b), a polyisocyanate (d) and at least one isocyanato group. It is related with the aqueous polyurethane resin dispersion obtained by making compound (e) which has a group which exists and reacting with 1 or more polymerizable unsaturated bonds.

<Polyurethane resin (A) having a polymerizable unsaturated bond>

In the present invention, the polyurethane resin (A) having a polymerizable unsaturated bond includes at least a polycarbonate diol (a) having an alicyclic structure in the main chain, an acidic group-containing polyol (b), a polyisocyanate (d), It is obtained by making the compound (e) which has one or more polymerizable unsaturated bonds react with the group which can react with one or more isocyanato groups.

Ⅰ. Polycarbonate polyol having an alicyclic structure in the main chain (a)

Since the polycarbonate polyol used by this invention is excellent in the storage stability of an aqueous polyurethane resin dispersion, and the coating film excellent in adhesiveness is obtained, the polycarbonate polyol (a) (henceforth "polycarbonate polyol") which has an alicyclic structure in a principal chain (a) "may be referred to).

The polycarbonate polyol (a) is not particularly limited, and for example, a polycarbonate polyol obtained by reacting a polyol having an alicyclic structure in a main chain with a carbonate ester, or a polyol having an alicyclic structure in a main chain, reacts with another polyol and a carbonate ester The copolymerized polycarbonate polyol obtained etc. are mentioned. In the present specification, the alicyclic structure includes those having a hetero atom such as an oxygen atom or a nitrogen atom in the ring.

The preferable number average molecular weight of polycarbonate polyol (a) is 400-3000. If a number average molecular weight is this range, appropriate viscosity and favorable handleability will be obtained easily. Moreover, it is easy to ensure the performance as a soft segment, it is easy to suppress a generation | occurrence | production of a crack when a coating film is formed using the obtained water-based polyurethane resin dispersion, and sufficient reactivity with polyisocyanate (d) is urethane prepolymer. Can be efficiently produced. As for polycarbonate polyol (a), it is more preferable that number average molecular weights are 400-1500, and it is especially preferable that it is 500-1300.

In this invention, a number average molecular weight is taken as the number average molecular weight computed based on the hydroxyl value measured based on JISK1557. Specifically, the hydroxyl value is measured and calculated as (mg KOH / g) (56.1 x 1000 x singer) / hydroxyl value by the terminal group quantification method. In the above formula, the valence is the number of hydroxyl groups in one molecule, and when the polycarbonate polyol is a polycarbonate diol, the valence is two.

The polyol having an alicyclic structure in the main chain is not particularly limited, and for example, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclopentanediol, 1,4-cycloheptanediol, 2,5-bis (hydroxymethyl) -1,4-dioxane, 2,7-norbornanediol, tetrahydrofuran dimethanol, 1,4-bis (hydroxye Dicyclo etc. which have alicyclic structure in the principal chain, such as each structural isomer or mixture thereof, such as the tricyclodecane dimethanol represented by the oxy) cyclohexane, the tricyclo [5.2.1.0 ^2,6 ] decane dimethanol, dimer acid diol, etc. are mentioned. have. Especially, 1, 4- cyclohexane dimethanol is preferable from the availability.

When using another polyol together, the said other polyol is not specifically limited, For example, aliphatic polyol, aromatic polyol, polyester polyol, polyether polyol, etc. are mentioned.

The aliphatic polyol is not particularly limited, and examples thereof include aliphatic polyols having 2 to 12 carbon atoms. Specifically, 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol Linear aliphatic diols such as 1,9-nonanediol and the like; Branched aliphatic diols such as 2-methyl-1,3-propanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, and 2-methyl-1,9-nonanediol; And trifunctional or higher polyhydric alcohols such as 1,1,1-trimethylolpropane and pentaerythritol.

The aromatic polyol is not particularly limited, and for example, 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,2-benzenedimethanol, 4,4'-naphthalenedimethanol, 3,4'-naphthalene Dimethanol, and the like.

The polyester polyol is not particularly limited, and for example, dicarboxylic acid such as polyester polyol of hydroxycarboxylic acid and diol, such as polyester polyol of 6-hydroxycaproic acid and hexanediol, and polyester polyol of adipic acid and hexanediol The polyester polyol of an acid and a diol, etc. are mentioned.

The polyether polyol is not particularly limited, and examples thereof include polyethylene glycol (for example, diethylene glycol, triethylene glycol, tetraethylene glycol, etc.), polyalkylene glycols such as polypropylene glycol and polytetramethylene glycol, and the like. have.

The carbonate ester is not particularly limited, and examples thereof include aliphatic carbonate esters such as dimethyl carbonate and diethyl carbonate, aromatic carbonate esters such as diphenyl carbonate, and cyclic carbonate esters such as ethylene carbonate. In addition, phosgene etc. which can produce a polycarbonate polyol can also be used. Among them, aliphatic carbonates are preferred from the ease of producing polycarbonate polyols, and dimethyl carbonate is particularly preferred.

As a method for producing a polycarbonate polyol from a polyol and a carbonate ester, for example, an carbonate ester and an excessive mole number polyol relative to the number of moles of the carbonate ester are added in a reactor to a temperature of 160 to 200 ° C. and a pressure of 50 mmHg to 5 to 6 After making time react, the method of making it react at 200-220 degreeC for several hours at the pressure of several mmHg or less is mentioned again. In the said reaction, it is preferable to make it react, extracting the alcohol byproduced out of a system. At this time, when the carbonate ester comes out of the system by azeotroping with the by-produced alcohol, an excess amount of carbonate ester may be added. In the above reaction, a catalyst such as titanium tetrabutoxide may also be used.

It is preferable that the alicyclic structure content rate in a polycarbonate polyol (a) is 20 to 65 weight%. When alicyclic structure content rate is this range, the coating film excellent in hardness is easy to be obtained by presence of an alicyclic structure, and adhesiveness with respect to various plastics of a coating film is also enough. On the other hand, the content rate of alicyclic structure becomes large too much, the viscosity of the prepolymer at the time of manufacturing an aqueous polyurethane resin dispersion becomes high, it is easy to avoid the situation which becomes difficult to handle, and favorable storage stability can be obtained easily. As for alicyclic structure content rate, it is more preferable that it is 30 to 55 weight%.

Here, alicyclic structure content rate shall say the weight ratio of the alicyclic group which occupies for a polycarbonate polyol (a). For example, a cycloalkane residue such as a cyclohexane residue (part in the case of 1,4-hexanedimethanol excluding two hydrogen atoms from cyclohexane), and an unsaturated heterocyclic residue such as tetrahydrofuran residue (tetrahydrofuran In the case of dimethanol, the value computed based on tetrahydrofuran and the part except two hydrogen atoms) is mentioned.

In view of the dispersibility of the aqueous medium, the polycarbonate polyol (a) is preferably a copolymerized polycarbonate polyol using another polyol in combination. As other polyols, aliphatic polyols, aromatic polyols, polyester polyols, polyether polyols can be used, and the above specific examples apply. Especially, the combination of the polyol and aliphatic polyol which has alicyclic structure in a principal chain is preferable, and the copolymerization polycarbonate polyol obtained by using together 1, 4- cyclohexane dimethanol and 1, 6- hexanediol is especially preferable.

Polycarbonate polyol (a) may be used independently and may use multiple types together.

Ⅱ. Acid group-containing polyol (b)

The acidic group-containing polyol (b) used in the present invention is not particularly limited as long as it contains two or more hydroxyl groups and one or more acidic groups in one molecule. Examples of the acidic group include a carboxyl group, sulfonic acid group, phosphoric acid group, and phenolic hydroxyl group. It is preferable to contain the compound which has two hydroxyl groups and one carboxyl group in 1 molecule especially as acidic group containing polyol (b). An acidic group containing polyol (b) may be used independently and may use multiple types together.

Specific examples of the acidic group-containing polyol (b) include dialkanolalkanoic acids including dimethylolalkanoic acid such as 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid; N, N-bishydroxyethylglycine, N, N-bishydroxyethylalanine, 3,4-dihydroxybutanesulfonic acid, 3,6-dihydroxy-2-toluenesulfonic acid, acidic group-containing polyether polyol, Acidic group containing polyester polyol etc. are mentioned. Among them, from the standpoint of ease of availability, dialkanolalkanoic acid containing two alkanol groups is preferable, and alkanoic acid (dimethylolalkanoic acid) having 4 to 12 carbon atoms containing two methylol groups is more preferable, and dimethylol 2, 2- dimethylol propionic acid is especially preferable among alkanoic acid.

Ⅲ. Other polyols (c)

In addition to the polycarbonate polyol (a) and the acidic group-containing polyol (b), other polyols (c) (hereinafter sometimes referred to as "other polyols (c)") can be used. As another polyol (c), polymeric polyols, such as a polymer polyol, and a low molecular polyol are mentioned. Examples of the polymer polyols include those having a number average molecular weight of 400 to 6000. The polyol may be a diol or a trihydric or higher polyhydric alcohol. Other polyols may be used independently and may use multiple types together. The low molecular polyol is preferable at the point which the hardness of a coating film becomes high, and a low molecular diol is especially preferable.

Polymeric polymer polyols are not particularly limited, and polyester polyols, polyether polyols, acrylic polyols, polydiene polyols, and polycarbonate polyols having no alicyclic structure in the main chain can be preferably used.

The polyester polyol is not particularly limited, and for example, polyethylene adipate polyol, polybutylene adipate polyol, polyethylene butylene adipate polyol, polyhexamethylene isophthalate adipate polyol, polyethylene succinate polyol, polybutylene succinate Polyol, polyethylene sebacate polyol, polybutylene sebacate polyol, poly-ε-caprolactone polyol, poly (3-methyl-1,5-pentylene adipate) polyol, polycondensation of 1,6-hexanediol and dimer acid A compound etc. are mentioned.

The polyether polyol is not particularly limited, and examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide and propylene oxide, random copolymers of ethylene oxide and butylene oxide, block copolymers, and the like. Can be. Moreover, polyether polyester polyol etc. which have an ether bond and ester bond can also be used.

The polydiene polyol is not particularly limited, and examples thereof include a polydiene polyol including units derived from butadiene, isoprene, 1,3-pentadiene, chloroprene, cyclopentadiene and the like. Specific examples of the polydiene polyol include, for example, hydroxyl group terminal liquid polybutadiene ("Poly bd" manufactured by Idemitsukosan Co., Ltd.), difunctional hydroxyl group terminal liquid polybutadiene ("Crasol (KRASOL)" manufactured by Idemitsukosan Co., Ltd.), and hydroxyl group terminal liquid polypoly. Isoprene ("Poly ip" by Idemitsu Kosan Co., Ltd.), a hydroxyl group terminal liquid polyolefin ("Epol" by Idemitsu Kosan Co., Ltd.), etc. are mentioned.

The polyacrylic polyol is not particularly limited, and for example, acrylic acid esters having active hydrogens such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 2-hydroxybutyl acrylate, or monoesters of glycerin Or a single or mixture selected from the group of methacrylate monoester, acrylate monoester of trimethylolpropane or methacrylate monoester and methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate Acrylic acid ester, methacrylic acid-2-hydroxyethyl, methacrylic acid-2-hydroxypropyl, methacrylic acid-2-hydroxybutyl, methacrylic acid-3-hydroxypropyl, methacrylic acid-4 -Methacrylic acid ester which has active hydrogen, such as hydroxybutyl, or methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, methacrylic acid Acrylic acid, methacrylic acid, maleic acid, ita using a single or a mixture selected from the group of methacrylic acid esters, such as -n-butyl, isobutyl methacrylate, n-hexyl methacrylate, and lauryl methacrylate; Unsaturated amides such as unsaturated carboxylic acids such as choline, acrylamide, N-methylol acrylamide, diacetone acrylamide, and glycidyl methacrylate, styrene, vinyltoluene, vinyl acetate, acrylonitrile, dibutyl fumarate The polyacryl polyol obtained by superposing | polymerizing in presence or absence of single or mixture selected from the group of other polymerizable monomers, such as these, is mentioned. Examples of the polymerization method include emulsion polymerization, suspension polymerization, dispersion polymerization, solution polymerization, and the like. In emulsion polymerization, it can also superpose | polymerize in steps.

The polycarbonate polyol having no alicyclic structure in the main chain is not particularly limited, and examples thereof include aliphatic polycarbonate diols such as polytetramethylene carbonate diol, polypentamethylene carbonate diol, and polyhexamethylene carbonate diol; Aromatic polycarbonate diols such as poly 1,4-xylylene carbonate diol; Copolymerized polycarbonate diols which are reaction products of plural kinds of aliphatic diols and carbonate esters; Copolymerized polycarbonate diol, such as copolymerized polycarbonate diol which is a reaction product of aliphatic diol, aromatic diol, and carbonate ester, etc. can be used.

As copolymerized polycarbonate diol, for example, the reaction of copolymerized polycarbonate diol, 1,4-butanediol, 1,5-pentanediol, and carbonate ester, which is a reaction product of 1,3-propanediol, 1,4-butanediol, and carbonate ester Copolymerized polycarbonate diol, a product of 1,5-pentanediol, a reaction product of 1,6-hexanediol, and a carbonate ester. Copolymerized polycarbonate diol, a reaction product of 1,4-butanediol, 1,6-hexanediol, and a carbonate ester. The copolymerization polycarbonate diol which is a reaction product of phosphorus copolymerization polycarbonate diol, 1, 3- propanediol, 1, 6- hexanediol, and carbonate ester, etc. are mentioned.

The low molecular polyol is not particularly limited, and the number average molecular weight may be 60 or more and less than 400. For example, ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3- Propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octane Aliphatic diols having 2 to 9 carbon atoms such as diol, diethylene glycol, triethylene glycol and tetraethylene glycol; 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,4-bis (hydroxyethyl) cyclohexane, 2,7-norbornanediol, tetrahydro Diols having an alicyclic structure having 6 to 12 carbon atoms such as furan dimethanol and 2,5-bis (hydroxymethyl) -1,4-dioxane; And aromatic diols such as 1,4-benzenedimethanol, 1,3-benzenedimethanol, and 1,4-dihydroxybenzene. Moreover, low molecular weight polyhydric alcohol more than trifunctional, such as trimethylol propane, pentaerythritol, and sorbitol, can also be used as a low molecular weight polyol.

It is preferable that the ratio of the other polyol (c) with respect to a polycarbonate polyol (a) is 40 weight% or less. If it is this range, it will be easy to avoid that the adhesiveness of the coating film obtained falls or manufacture of an aqueous polyurethane resin dispersion becomes difficult. The ratio of the other polyol (c) is more preferably 20% by weight or less.

IV. Polyisocyanate (d)

The polyisocyanate (d) that can be used in the present invention is not particularly limited, and examples thereof include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.

Specifically as an aromatic polyisocyanate, 1, 3- phenylene diisocyanate, 1, 4- phenylene diisocyanate, 2, 4- tolylene diisocyanate (TDI), 2, 6- tolylene diisocyanate, 4, 4'- diphenylmethane Diisocyanate (MDI), 2,4-diphenylmethane diisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'- Dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4 ', 4 "-triphenylmethanetriisocyanate, m-isocyanatophenylsulfonyl isocyanate, p-iso Cyanatophenyl sulfonyl isocyanate etc. are mentioned.

Specifically as aliphatic polyisocyanate, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11- undecane triisocyanate, 2,2,4-trimethylhexamethylene Diisocyanate, lysine diisocyanate, 2,6-diisocyanate methylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6 -Diisocyanatohexanoate, etc. are mentioned.

Specifically as alicyclic polyisocyanate, isophorone diisocyanate (IPDI), 4,4'- dicyclohexyl methane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI) , Bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate, etc. are mentioned.

These polyisocyanates may be used independently and may use multiple types together.

Two isocyanate groups per molecule of the polyisocyanate are usually two, but the polyisocyanate having three or more isocyanato groups such as triphenylmethane triisocyanate within the range in which the polyurethane resin in the present invention does not gel. Can also be used.

Among polyisocyanates, 4,4'-diphenylene methane diisocyanate (MDI), isophorone diisocyanate (IPDI), and 4,4'- dicyclohexyl methane di from viewpoints of control of reactivity, high hardness, and strength provision. Isocyanates (hydrogenated MDI) are preferred.

Ⅴ. Compound (e) having a group capable of reacting with at least one isocyanato group in one molecule and at least one polymerizable unsaturated bond

Polymerization in the compound (e) (hereinafter sometimes referred to as "unsaturated compound (e)") having a group capable of reacting with at least one isocyanato group in one molecule and at least one polymerizable unsaturated bond. An unsaturated bond is a bond contained in the unsaturated group which can superpose | polymerize with the radical etc. which were generate | occur | produced, for example by a photoinitiator. As such an unsaturated group, a well-known thing may be sufficient and the group containing an ethylenically unsaturated bond is mentioned, A (meth) acryloyl group is preferable at the point which is easy to obtain, and the point of high reactivity. In this specification, a (meth) acryloyl group means an acryloyl group and / or a methacryloyl group, (meth) acrylate means an acrylate or / and methacrylate, and (meth) acrylic acid It means acrylic acid and / or methacrylic acid. The unsaturated compound (e) has one or more polymerizable unsaturated bonds in the molecule.

As a group which can react with the isocyanato group in an unsaturated compound (e), a hydroxyl group, an amino group, an isocyanato group, a thiol group, etc. are mentioned, for example. Especially, a hydroxyl group is preferable at the point of the ease of handling of an unsaturated compound (e). The unsaturated compound (e) has at least one group in the molecule capable of reacting with isocyanato groups.

As the unsaturated compound (e), a compound (e ') having at least one hydroxyl group and at least one polymerizable unsaturated bond is preferable in view of ease of handling. Examples of the unsaturated compound (e ') include an unsaturated compound (e'-1) having one hydroxyl group and one polymerizable unsaturated bond in one molecule, and an unsaturated compound having one hydroxyl group and two or more polymerizable unsaturated groups in one molecule. Compound (e'-2), an unsaturated compound having two or more hydroxyl groups and one polymerizable unsaturated group in one molecule (e'-3), an unsaturated compound having two or more hydroxyl groups and two or more polymerizable unsaturated groups in one molecule (e'-4) etc. are mentioned.

Examples of the unsaturated compound (e'-1) having one hydroxyl group and one polymerizable unsaturated bond in one molecule include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate etc. are mentioned.

Examples of the unsaturated compound (e'-2) having one hydroxyl group and two or more polymerizable unsaturated bonds in one molecule include glycerin di (meth) acrylate, diglycerol tri (meth) acrylate, and trimethylolpropanedi. (Meth) acrylic acid adduct of (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, sorbitol penta (meth) acrylate, glycidyl (meth) acrylate Etc. can be mentioned.

Examples of the unsaturated compound (e'-3) having two or more hydroxyl groups and one polymerizable unsaturated bond in one molecule include glycerin mono (meth) acrylate, diglycerin mono (meth) acrylate, and pentaerythritol mono. (Meth) acrylate, dipentaerythritol mono (meth) acrylate, sorbitol mono (meth) acrylate, etc. are mentioned.

As an unsaturated compound (e'-4) which has two or more hydroxyl groups and two or more polymerizable unsaturated bonds in 1 molecule, it is diglycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, di Pentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, sorbitol di (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (Meth) acrylate, reaction product of 2 molecule (meth) acrylic acid, and 1 molecule 1,6-hexanediol diglycidyl (for example, "DA-212" by Nagase Chemtech Co., Ltd.), 2 molecule epoxy ( Reaction product of meth) acrylic acid and one molecule of neopentyl glycol diglycidyl, reaction product of two molecules of (meth) acrylic acid and one molecule of bisphenol A diglycidyl (for example, DA-250 manufactured by Nagase Chemtech Co., Ltd.) ), Two-molecule (meth) arc Reaction product of diglycidyl product of an propylene oxide adduct of an acid and bisphenol A, reaction product of (meth) acrylic acid of 2 molecules and diglycidyl phthalate of 1 molecule (for example, "DA-721" by Nagase Chemtech Co., Ltd.) , Reaction product of two-molecule (meth) acrylic acid and one-molecular polyethyleneglycol diglycidyl (for example, "DM-811", "DM-832", "DM-851" by Nagase Chemtech Co., Ltd.), two molecules The reaction product of (meth) acrylic acid and polyol diglycidyl, such as the reaction product of (meth) acrylic acid and 1 molecule of polypropylene glycol diglycidyl, etc. are mentioned.

As an unsaturated compound (e), the compound which has an isocyanato group can also be used, for example, 2-isocyanatoethyl acrylate (Karenzu AO made by Showa Denko) as a (meth) acryl compound which has an isocyanato group. And 2-isocyanatoethyl methacrylate (Carenz MOI) and 1,1-bis (acryloyloxymethyl) ethyl isocyanate (Carenz BEI). N-isopropyl (meth) acrylamide etc. can also be used as an unsaturated compound (e).

Moreover, the commercially available unsaturated compound (e) including an unsaturated compound (e ') can also be used as it is. An unsaturated compound (e) may be used independently and may use multiple types together. For example, only 1 type of unsaturated compounds (e'-1)-(e'-4) may be used, and 2 or more types may be used together.

The amount of the unsaturated compound (e) added is 100% of the solid content of the aqueous polyurethane resin dispersion (including the compound (B) having a polymerizable unsaturated bond) in terms of the hardness of the coating film obtained and the adhesion between the coating film and the substrate. When it is weight part, Preferably it is 2-50 weight part, More preferably, it is 5-40 weight part. By making the addition amount of an unsaturated compound (e) into 2 weight part or more, it can suppress that the surface hardness of the coating film obtained falls. By making the addition amount of an unsaturated compound (e) into 50 weight part or less, it can suppress that the adhesiveness of the coating film obtained and a base material falls.

The unsaturated compound (e) is preferably a compound having one hydroxyl group in the unsaturated compound (e ') from the viewpoint of improving the storage stability of the polyurethane water dispersion, and specifically, one hydroxyl group and one polymerizable polymer in one molecule. It is preferable to include the unsaturated compound (e'-1) which has an unsaturated bond, and / or the unsaturated compound (e'-2) which has one hydroxyl group and 2 or more polymerizable unsaturated bonds in 1 molecule. Especially, since the hardness of the coating film obtained improves, it is more preferable to include the unsaturated compound (e'-2) which has one hydroxyl group and two or more polymerizable unsaturated groups in 1 molecule, and is unsaturated compound (e'-2) Among these, compounds having one hydroxyl group and three (meth) acryloyl groups in one molecule are more preferable.

The amount of the unsaturated compound (e'-1) and / or the unsaturated compound (e'-2) used is 100 parts by weight of the total amount of solids (including the compound (B) having a polymerizable unsaturated bond) in the aqueous polyurethane resin dispersion. In one case, it is preferably 2 to 50 parts by weight, more preferably 5 to 40 parts by weight.

The unsaturated compound (e) is preferably a compound having two or more hydroxyl groups among the unsaturated compounds (e ') in terms of the hardness of the coating film obtained, and specifically, two or more hydroxyl groups and one polymerizable unsaturated bond in one molecule. It is preferable to include unsaturated compound (e'-3) which has, and / or unsaturated compound (e'-4) which has 2 or more hydroxyl group and 2 or more polymerizable unsaturated bond in 1 molecule. Especially, it is more preferable to contain the unsaturated compound (e'-4) which has 2 or more hydroxyl groups and 2 or more polymerizable unsaturated groups in 1 molecule from the ease of acquisition, and 1 molecule among unsaturated compounds (e'-4) The compound which has two hydroxyl groups and two (meth) acryloyl groups in this is more preferable.

The amount of the unsaturated compound (e'-3) and / or the unsaturated compound (e'-4) used is 100 parts by weight of the total amount of solids (including the compound (B) having a polymerizable unsaturated bond) in the aqueous polyurethane resin dispersion. In one case, it is preferably 2 to 30 parts by weight, more preferably 5 to 20 parts by weight.

VI. Hydroxyl equivalent of the polyol-containing component

In this invention, it is preferable that the hydroxyl group equivalent number of a polyol containing component is 100-500. When the hydroxyl equivalent number is within this range, the production of an aqueous polyurethane resin dispersion is easy, and a coating film excellent in storage stability and hardness of a good aqueous polyurethane resin dispersion is easily obtained. From the viewpoint of the hardness of the coating film, it is preferably 120 to 300, more preferably 150 to 250. Wherein the polyol-containing component is in addition to the polycarbonate polyol (a), the acidic group-containing polyol (b), and any other polyol (c), wherein the unsaturated compound (e) is an unsaturated compound (e'-3) and / or In the case of (e'-4), these unsaturated compounds (e'-3) and / or (e'-4) are included.

The hydroxyl equivalent number can be calculated by the following formulas (1) and (2).

Hydroxyl equivalent number of each polyol = molecular weight of each polyol / number of hydroxyl groups of each polyol

... (One)

Hydroxyl equivalent number of the sum total of a polyol = M / total mol number of a polyol. (2)

In formula (2), M is [the number of hydroxyl groups equivalent of a polycarbonate polyol (a) x the number of moles of a polycarbonate polyol (a)] + [the number of hydroxyl groups equivalent of an acidic group containing polyol (b) x an acidic group containing polyol ( number of moles of b)] + [number of hydroxyl equivalents of other polyol (c) x number of moles of other polyol (c)] + [number of hydroxyl equivalents of (e'-3) x (e'-3)]] + [Number of hydroxyl equivalents of (e'-4) x number of moles of (e'-4)]].

VII. Polyurethane resin (A) or polyurethane prepolymer (A1)

The polyurethane resin (A) in this invention is a polyurethane obtained by making at least a polycarbonate polyol (a), an acidic group containing polyol (b), a polyisocyanate (d), and an unsaturated compound (e) react. Or a polycarbonate polyol (a), an acidic group-containing polyol (b), a polyisocyanate (d), and an unsaturated compound (e) to obtain a polyurethane prepolymer (A1), which is a chain extender. It is a polyurethane resin obtained by making it react with (C) further.

In the case of obtaining a polyurethane resin (A), all the hydroxyl groups of a polycarbonate polyol (a), an acidic group containing polyol (b), and other polyol (c) and unsaturated compound (e ') which exist in some cases are present. As for the ratio of the number-of-moles of the isocyanate group of polyisocyanate (d) with respect to the number-of-moles, 0.85-1.1 are preferable. When larger or smaller than this range, the molecular weight of a polyurethane resin (A) may become small and tack free property may be inferior. The ratio of the number of moles of isocyanate groups of the polyisocyanate (d) to the number of moles of all hydroxyl groups of the above components is preferably 0.90 to 1.05, particularly preferably 0.95 to 1.01.

The polyurethane resin (A) and the polyurethane prepolymer (A1) are polycarbonate polyols (a), acidic group-containing polyols (b), other polyols (c), polyisocyanates (d) and unsaturated compounds ( or a polycarbonate polyol (a), an acidic group-containing polyol (b), another polyol (c), a polyisocyanate (d), and an unsaturated compound (e). Polyurethane resin obtained by obtaining a polyurethane prepolymer (A1) and reacting this further with a chain extender (C) may be sufficient.

When the polyurethane prepolymer (A1) and the chain extender (C) are reacted to obtain a polyurethane resin, the reaction temperature of the polyurethane prepolymer (A1) and the chain extender (C) is, for example, 0 to 80. ° C, preferably 0 to 60 ° C.

In the case of obtaining a polyurethane prepolymer (A1), the whole of a polycarbonate polyol (a), an acidic group containing polyol (b), and the other polyol (c) and unsaturated compound (e ') which exist in some cases. The ratio of the number of moles of the isocyanate group of the polyisocyanate (d) to the number of moles of the hydroxyl group is preferably 1.01 to 2.5. If it is this range, the mole number of the hydroxyl group of the said hydroxyl-containing component will become large, and the polyurethane prepolymer (A1) which does not have an isocyanato group in a molecular terminal will increase, and the molecule | numerator which does not react with a chain extender (C) will be It becomes easy to avoid the problem that the intensity | strength of the coating film obtained by apply | coating an aqueous polyurethane resin dispersion increases, and the number of hydroxyl groups of the said hydroxyl-containing component is too small, and a large amount of unreacted polyisocyanate (d) exists in a reaction system. It is also easy to avoid the problem that unevenness occurs in a coating film obtained by reacting with a chain extender or by reacting with water to cause molecular elongation to apply an aqueous polyurethane resin dispersion. The ratio of the number of moles of isocyanate groups of the polyisocyanate (d) to the number of moles of all hydroxyl groups of the above components is preferably 1.2 to 2.2, particularly preferably 1.3 to 2.0.

In the case of obtaining a polyurethane resin (A) or a polyurethane prepolymer (A1), a polycarbonate polyol (a), an acidic group-containing polyol (b), optionally other polyols (c), and an unsaturated compound (e) Reaction of the component and polyisocyanate (d) containing () may make (a), (b), optionally (c), (e) react with (d) in random order, and It may also react with (d) by mixing. A catalyst can also be used when making the said component and polyisocyanate (d) react.

The catalyst is not particularly limited, and examples thereof include metals such as tin-based catalysts (trimethyltin laurate, dibutyltin dilaurate, etc.) and lead-based catalysts (such as lead octylate), salts of organic and inorganic acids, and organic metal derivatives, Amine catalysts (triethylamine, N-ethyl morpholine, triethylenediamine, etc.), a diazabicyclo undecene type catalyst, etc. are mentioned. Among them, dibutyltin dilaurate is preferable from the viewpoint of reactivity.

Although the reaction temperature at the time of making the said component and polyisocyanate (d) react is not specifically limited, 40-120 degreeC is preferable. If it is this range, melt | dissolution of a raw material is enough, the viscosity of the obtained polyurethane (A) or urethane prepolymer (A1) is suitable, it is easy to stir, and a polymerizable unsaturated bond in an unsaturated compound (e) raises a polymerization reaction and gelatinizes, And side problems of isocyanate groups in the polyisocyanate (d) are easily avoided. The reaction temperature is more preferably 60 to 100 ° C.

When reacting an unsaturated compound (e) and a polyisocyanate (d), in order to avoid unnecessary consumption of the polymerizable unsaturated bond in an unsaturated compound (e), it is preferable to carry out in presence of oxygen.

In the present invention, in the step of obtaining a polyurethane resin (A) or a polyurethane prepolymer (A1), a polymerization inhibitor is added to the reaction system in order to avoid unnecessary consumption of the polymerizable unsaturated bonds of the unsaturated compound (e). It may be.

Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, benzoquinone, 2-tert-butylhydroquinone, p-tert-butylcatechol, 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone, 2 Quinone polymerization inhibitors such as, 5-bis (1,1-dimethylbutyl) hydroquinone; 2,6-bis (1,1-dimethylethyl) -4-methylphenol, 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl-4,6 Alkylphenol polymerization inhibitors such as -dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, and 2,4,6-tri-tert-butylphenol; Aromatic amine polymerization inhibitors such as phenothiazine; Alkylated diphenylamine, N, N'-diphenyl-p-phenylenediamine, phenothiazine, 4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2 , 6,6-tetramethylpiperidine, 1,4-dihydroxy-2,2,6,6-tetramethylpiperidine, 1-hydroxy-4-benzoyloxy-2,2,6,6 Amine polymerization inhibitors such as -tetramethylpiperidine, di-p-fluorophenylamine, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO); 2,2-diphenylpicrylhydrazyl (DPPH), tri-p-nitrophenylmethyl, N- (3N-oxyanilino-1,3-dimethylbutylidene) -aniline oxide, benzyltrimethylammonium Quaternary ammonium chlorides such as chloride; Diethylhydroxylamine, cyclic amide, nitrile compound, substituted urea, benzothiazole, bis- (1,2,2,6,6-pentamethyl-4-piperidinyl) sepacate, lactic acid, oxalic acid, citric acid, Organic acids such as tartaric acid and benzoic acid; Organic phosphines, phosphites and the like. These may be used individually by 1 type and may use multiple types together. In particular, by using a quinone type polymerization inhibitor and an alkylphenol type polymerization inhibitor together, consumption by polymerization of a polymerizable unsaturated bond can be reduced more.

The addition amount of a polymerization inhibitor can be 0.001-1 weight part with respect to 100 weight part of polyurethane resins (A), Preferably it is 0.01-0.5 weight part.

The reaction of the polycarbonate polyol (a), the acidic group-containing polyol (b), optionally the other polyol (c), and the unsaturated compound (e) with the polyisocyanate (d) may be solvent-free or by adding an organic solvent. You can also do it. Examples of the organic solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dioxane, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, N-ethylpyrrolidone, and ethyl acetate. . Among them, acetone, methyl ethyl ketone and ethyl acetate are preferable because they can be removed by heating and decompression after dispersion and extension reaction of the polyurethane prepolymer with water. In addition, N-methylpyrrolidone and N-ethylpyrrolidone are preferable because they function as film forming aids when producing a coating film from the obtained aqueous polyurethane resin dispersion. The amount of the organic solvent added is preferably 0 to 2.0 times by weight based on the total amount of polycarbonate polyol (a), acidic group-containing polyol (b), optionally other polyol (c), and unsaturated compound (e). More preferably, it is 0.1-0.7 times. If it is this range, favorable dispersion can be obtained by making the viscosity at the time of obtaining a polyurethane prepolymer (A1) into an appropriate range. On the other hand, the time required for the removal of the organic solvent does not take too long, and the situation where the coating film physical properties are lowered can be easily avoided by remaining of the organic solvent in the coating film obtained by using the aqueous polyurethane resin dispersion.

In the present invention, the acid value of the polyurethane resin (A) or the polyurethane prepolymer (A1) is preferably 20 to 50 mgKOH / g. If it is this range, it will be easy to ensure the favorable dispersibility with respect to an aqueous medium, and the water resistance of a coating film. The acid value is more preferably 25 to 45 mgKOH / g, still more preferably 30 to 40 mgKOH / g.

Here, the acid value of the polyurethane resin (A) or the polyurethane prepolymer (A1) means a solvent and a polyurethane prepolymer (A1) used when producing the polyurethane resin (A) or the polyurethane prepolymer (A1). Average content of acid groups in so-called solids, excluding neutralizers for dispersion in an aqueous medium, polycarbonate polyols (a), acidic group-containing polyols (b), optionally other polyols (c), unsaturated compounds (e) and poly From the weight of an isocyanate (d) and the acidic group contained in an acidic group containing polyol (b), it can obtain | derive by following formula (3).

[Acid Value of Polyurethane Resin (A) or Polyurethane Prepolymer (A1)] = [Moles of Acidic Groups of Acidic Group-Containing Polyols (b)] × 56.11 / [Polycarbonate Polyols (a), Acidic Group-Containing Polyols (b) ), Optionally the weight of the sum of other polyols (c), unsaturated compounds (e) and polyisocyanates (d)]. (3)

When the polyurethane prepolymer (A1) is obtained and dispersed in an aqueous solvent and chain extended with a chain extender (C) to obtain the aqueous polyurethane resin dispersion of the present invention, the acid value is a polyurethane prepolymer. It is synonymous with the acid value of (A1).

When obtaining a polyurethane resin (A) or a polyurethane prepolymer (A1) WHEREIN: When the solid content (including the compound (B) which has a polymerizable unsaturated bond) of an aqueous polyurethane resin dispersion is 100 weight part. The polycarbonate polyol (a) is preferably 2 to 50 parts by weight, the acidic group-containing polyol (b) is preferably 2 to 15 parts by weight, and the other polyol (c) is preferably 0 to 30 parts by weight. The unsaturated compound (e) is preferably 5 to 50 parts by weight. When polycarbonate polyol (a) is the said range, the adhesiveness of the coating film obtained from an aqueous polyurethane resin dispersion is high, the dispersibility to the aqueous medium of a polyurethane resin (A) is favorable, and excellent film forming property is obtained easily. . The polycarbonate polyol (a) is more preferably 3 to 40 parts by weight, particularly preferably 5 to 30 parts by weight. If acidic group containing polyol (b) is the said range, the water resistance of the coating film obtained from an aqueous polyurethane resin dispersion will be favorable, and the dispersibility with respect to the aqueous medium of a polyurethane resin (A) will be favorable. The acidic group-containing polyol (b) is more preferably 3 to 10 parts by weight, particularly preferably 4 to 7 parts by weight. When an unsaturated compound (e) is the said range, the hardness and adhesiveness of the coating film obtained from an aqueous polyurethane resin dispersion are favorable, and the thing excellent also in the storage stability of an aqueous polyurethane resin dispersion is obtained. The unsaturated compound (e) is more preferably 10 to 40 parts by weight.

VIII. Chain Extender (C)

Polyurethane resin (A) which has a polymerizable unsaturated bond in this invention has little stickiness to the dry coating film before irradiation of an active energy ray (for example, ultraviolet-ray) by using a chain extender (C), and it is tack free It is preferable that it is manufactured using the chain extending agent (C) in order to become. As the chain extender (C), for example, ethylenediamine, 1,4-tetramethylenediamine, 2-methyl-1,5-pentanediamine, 1,4-butanediamine, 1,6-hexamethylenediamine, 1,4 -Hexamethylenediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, 1,3-bis (aminomethyl) cyclohexane, xylylenediamine, piperazine, 2,5-dimethylpiperazine, hydrazine Amine compounds such as adipoyldihydrazide, diethylenetriamine, triethylenetetramine, diol compounds such as ethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol, and poly ole glycol Alkylene glycols, water, etc. are mentioned, Especially, it is preferable that the chain extender (C) is an organic compound from the point of hardness of the coating film after hardening active energy ray (for example, ultraviolet-ray) of the coating film obtained, It is more preferable that it is a polyamine compound, Especially it is a primary polyamine compound Preferable. These may be used independently and may use multiple types together.

It is preferable that the addition amount of a chain extender (C) is below the equivalent of the isocyanato group used as the chain extension origin in a polyurethane prepolymer (A1), More preferably, it is 0.7-0.99 equivalent of an isocyanato group. If it is this range, the molecular weight of a chain-extended polyurethane resin (A) may be made into an appropriate range, and also the intensity | strength of the coating film obtained by apply | coating the aqueous polyurethane resin dispersion containing this can be made favorable. The chain extender (C) may be added after dispersion of the polyurethane prepolymer (A1) to water, or may be added during dispersion. Chain extension can also be performed with water. In this case, water as a dispersion medium also serves as a chain extender.

<Compound (B) having a polymerizable unsaturated bond)

The compound (B) having a polymerizable unsaturated bond in the present invention is preferably polymerized in the coexistence of an optical radical generator or in the coexistence of a thermal radical generator, but the compound that does not react with the isocyanato group at 25 ° C. It is preferable to use.

As a compound (B) which has a polymerizable unsaturated bond, the compound which has ethylenically unsaturated bonds, such as a vinyl group or an allyl group, is mentioned, The compound which has a (meth) acryloyl group is mentioned. The compound (B) having a polymerizable unsaturated bond may be a monofunctional compound having one group having a polymerizable unsaturated bond such as a (meth) acryloyl group, a polyfunctional compound having a plurality thereof, The compound which has a methacryloyl group, and the compound which has five or more (meth) acryloyl group can also be used preferably.

As a compound (B) which has a polymerizable unsaturated bond, a (meth) acrylate compound is preferable. As a (meth) acrylate compound, the (meth) acrylate compound of monomers, a polyurethane (meth) acrylate compound, a polyester (meth) acrylate type compound, a polyalkylene (meth) acrylate type compound, etc. are mentioned. Can be.

As a (meth) acrylate compound of monomers, it is mono (meth) acrylate, di (meth) acrylate, tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acryl. Mono (meth) acrylates and poly (meth) acrylates, such as a rate, can be used.

As said mono (meth) acrylate, 2-ethylhexyl (meth) acrylate, methyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth ) Acrylate, dicyclopentenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth ) Acrylates and the like.

As the di (meth) acrylate, for example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, Alkylene glycol di (meth) acrylates such as 1,6-hexanediol di (meth) acrylate, tricyclodecanedimethanoldi (meth) acrylate, and bisphenol A di (meth) acrylate; Polyether di (meth) acrylates such as polyethylene glycol di (meth) acrylate and polypropylene glycol di (meth) acrylate; Bisphenol A ethylene oxide modified di (meth) acrylate, bisphenol A propylene oxide modified di (meth) acrylate, neopentyl glycol ethylene oxide modified di (meth) acrylate, neopentyl glycol propylene oxide modified di (meth) Alkylene oxide modified di (meth) acrylates such as) acrylate; 1,6-hexanediol epoxydi (meth) acrylate, neopentyl glycol epoxydi (meth) acrylate, bisphenol A epoxydi (meth) acrylate, bisphenol A propylene oxide modified epoxydi (meth) acrylate, phthalic acid Epoxy di (meth) acrylates, such as an epoxy di (meth) acrylate, a polyethylene glycol epoxy (meth) acrylate, and a polypropylene glycol epoxy (meth) acrylate, etc. are mentioned.

As the tri (meth) acrylate, for example, trimethylolpropane triacrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, pentaerythritol tree ( Meth) acrylate, and the like.

As tetra (meth) acrylate, for example, dipentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, and ethylene oxide (4 mol) modified pentaerythritol tetra (meth) acrylate (di Alkylene oxide modified pentaerythritol tetra (meth) acrylates, such as Cell Cytec Co., Inc. and Ebecryl 40, Ditrimethylol propane tetraacrylate, etc. are mentioned.

As penta (meth) acrylate, dipentaerythritol penta (meth) acrylate etc. are mentioned, for example.

As hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate etc. are mentioned, for example.

Among the (meth) acrylate compounds of these monomers, in terms of hardness, di (meth) acrylate, tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate Poly (meth) acrylate is preferable. This is because having a plurality of (meth) acryloyl groups in the molecule makes it easier to form higher molecular weight than in the case of mono (meth) acrylates. Especially, in terms of hardness, tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate are preferable. More preferably, they are penta (meth) acrylate and hexa (meth) acrylate.

As (meth) acrylate of polymers, in addition to the (meth) acrylate which has a polyalkylene glycol structure, a polyurethane (meth) acrylate compound, polyester (meth) acrylate type compound, polyalkylene (meth) acrylate The compound etc. can be used, For example, the acryl-type polymer etc. which have a polymerizable unsaturated bond in a molecule | numerator can be used, For example, the polybutyl acrylate which has a polymerizable double bond in a molecule | numerator single terminal ("Acte" Flow BGV-100T ") and polybutyl acrylate (" Acflow "by Soken Chemical Co., Ltd.) which has a polymerizable double bond in a molecular sock end, etc. are mentioned.

As a compound (B) which has a polymerizable unsaturated bond, the compound containing vinyl groups and allyl groups other than (meth) acrylate compounds, such as acryloyl morpholine, styrene, and N-vinyl-2-pyrrolidone, can also be used.

As a compound (B) which has a polymerizable unsaturated bond, what is marketed can also be used as it is. The compound (B) which has a polymerizable unsaturated bond may be used independently, and may use multiple types together.

When the total amount of solids (including the compound (B) having a polymerizable unsaturated bond) of the aqueous polyurethane resin dispersion is 100 parts by weight, preferably 2 to 50 parts by weight, more preferably 5 to 40 parts by weight. to be.

The compound (B) having a polymerizable unsaturated bond is preferably 10 to 60 parts by weight when the total amount of solids (including the polyurethane resin (A)) of the aqueous polyurethane resin dispersion is 100 parts by weight. If it is this range, it will be easy to make the adhesiveness and hardness of the coating film obtained from an aqueous polyurethane resin dispersion favorable, and favorable storage stability with respect to an aqueous polyurethane resin dispersion can be obtained. The compound (B) having a polymerizable unsaturated bond is more preferably 20 to 50 parts by weight, particularly preferably 30 to 45 parts by weight.

<Aqueous Polyurethane Resin Dispersion>

Ⅹ. Aquatic medium

In the present invention, the polyurethane resin (A) is dispersed in an aqueous medium. As an aqueous medium, water, the mixed medium of water and a hydrophilic organic solvent, etc. are mentioned.

As water, a constant, ion-exchange water, distilled water, ultrapure water, etc. are mentioned, for example. Among them, ion-exchanged water is preferable in consideration of the availability of particles and the instability of particles due to the influence of salts.

As a hydrophilic organic solvent, Lower monohydric alcohols, such as methanol, ethanol, a propanol; Polyhydric alcohols such as ethylene glycol and glycerin; Aprotic hydrophilic organic solvents, such as N-methylmorpholine, dimethyl sulfoxide, dimethylformamide, and N-methylpyrrolidone, etc. are mentioned. As an amount of the hydrophilic organic solvent in an aqueous medium, 0-20 weight% is preferable.

XI. Process for producing an aqueous polyurethane resin dispersion

Next, the manufacturing method of an aqueous polyurethane resin dispersion is demonstrated.

The aqueous polyurethane resin of the present invention comprises at least one isocyanato group in at least one polycarbonate diol (a), an acidic group-containing polyol (b), a polyisocyanate (d) and one molecule having an alicyclic structure in a main chain thereof. Reacting with a group capable of reacting with a compound (e) having at least one polymerizable unsaturated bond to obtain a polyurethane resin (A), the polyurethane resin (A) and a compound (B) having a polymerizable unsaturated bond It is obtained by dispersing in a medium.

Moreover, the manufacturing method of the water-based polyurethane resin dispersion of this invention reacts with a polycarbonate polyol (a), an acidic group containing polyol (b), a polyisocyanate (d), and one or more isocyanato groups. (A1) of obtaining a polyurethane prepolymer (A1) by reacting a compound having a group capable of reacting with a compound (e) having at least one polymerizable unsaturated bond,

Process (β) of neutralizing the acidic group of the polyurethane prepolymer (A1), and

Step (γ) of dispersing the compound (B) having a polyurethane prepolymer (A1) and a polymerizable unsaturated bond in an aqueous medium,

The step (?) Of reacting the polyurethane prepolymer (A1) with the chain extender (C) having a reactivity with the isocyanato group of the polyurethane prepolymer (A1) to obtain an aqueous polyurethane resin can be included.

Further, polycarbonate polyol (a), acidic group-containing polyol (b), other polyols (c), polyisocyanates (d), and groups capable of reacting with at least one isocyanato group and at least one Step (α2) of reacting the compound (e) having a polymerizable unsaturated bond to obtain a polyurethane prepolymer (A1),

Process (β) of neutralizing the acidic group of the polyurethane prepolymer (A1), and

Step (γ) of dispersing the compound (B) having a polyurethane prepolymer (A1) and a polymerizable unsaturated bond in an aqueous medium,

The step (?) Of reacting the polyurethane prepolymer (A1) with the chain extender (C) having a reactivity with the isocyanato group of the polyurethane prepolymer (A1) to obtain an aqueous polyurethane resin can be included.

The steps (α1) and (α2) for obtaining the polyurethane prepolymer (A1) are preferably performed in the presence of oxygen in order to avoid unnecessary consumption of the polymerizable unsaturated bonds. Moreover, it is preferable to add a polymerization inhibitor into a reaction system as needed. Temperature of the process ((alpha) 1) and ((alpha) 2) which obtains a polyurethane prepolymer (A1) can be performed at 0-120 degreeC, in order to avoid unnecessary superposition | polymerization of a polymerizable unsaturated bond. It is preferable to carry out at 0-100 degreeC preferably.

As an acidic group neutralizer which can be used in the process ((beta)) which neutralizes the acidic group of a polyurethane prepolymer (A1), trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanol Organic amines such as amine, N-phenyldiethanolamine, dimethylethanolamine, diethylethanolamine, N-methylmorpholine and pyridine; Inorganic alkalis such as sodium hydroxide and potassium hydroxide, ammonia and the like. Especially, it is preferably organic amines, More preferably, it is tertiary amine, Most preferably, triethylamine. Here, the acidic group of a polyurethane prepolymer (A1) means a carboxylic acid group, a sulfonic acid group, etc.

The amount of the acidic group neutralizing agent to be used is preferably such that the molar number of the acidic group of the polyurethane prepolymer (A1) is 0.8 to 1.5. When it is this range, the dispersibility with respect to the water of a polyurethane prepolymer (A1) is enough, the storage stability of the obtained aqueous polyurethane resin dispersion does not fall, and the odor of an aqueous polyurethane resin dispersion becomes strong. It can also be easily avoided.

In the step (γ) of dispersing the compound (B) having a polyurethane prepolymer (A1) and a polymerizable unsaturated bond in an aqueous medium, the method can be used as long as it can disperse (A1) and (B) in the aqueous medium. And the operation procedure are not particularly limited. For example, a method of mixing (B) with (A1) and dispersing it in an aqueous medium, or a method of mixing (B) with (B) and dispersing it in an aqueous medium; Method of mixing and dispersing (B) after dispersing A1) in an aqueous medium, method of mixing and dispersing (A1) after dispersing (B) in an aqueous medium, or (A1) and (B) in an aqueous medium, respectively. The method of mixing after disperse | distributing in the inside, etc. are mentioned.

A well-known stirring apparatus, such as a homo mixer and a homogenizer, can be used for the said mixing, stirring, and dispersion | distribution. In addition, a hydrophilic organic solvent, water, or the like may be added to the polyurethane prepolymer (A1) or the compound (B) having a polymerizable unsaturated bond before mixing for the purpose of viscosity adjustment, workability improvement, and dispersibility improvement. .

In addition, the step (γ) of mixing the polyurethane prepolymer (A1) with the compound (B) having a polymerizable unsaturated bond is preferably performed in the presence of oxygen in order to avoid unnecessary consumption of the polymerizable unsaturated bond. Moreover, you may add a polymerization inhibitor as needed. The temperature at the time of mixing a polyurethane prepolymer (A1) and the compound (B) which has a polymerizable unsaturated bond can be performed at 0-100 degreeC, in order to avoid unnecessary consumption of a polymerizable unsaturated bond, and is 0-80 degreeC It is more preferable to carry out at, more preferably at 0 to 70 ° C, and particularly preferably at 50 to 70 ° C.

In the manufacturing method of this invention, the process ((beta)) which neutralizes the acidic group of a polyurethane prepolymer (A1), and the compound (B) which has a polyurethane prepolymer (A1) and a polymerizable unsaturated bond are disperse | distributed in an aqueous medium. The step (γ) may be performed either first or simultaneously. In this case, (A1), (B), an aqueous medium, and an acidic group neutralizing agent may be mixed at once, and an acidic group neutralizing agent may be previously mixed with an aqueous medium or (B), and these and (A1) may be mixed. .

Aqueous polyurethane is made by reacting a polyurethane prepolymer (A1) with a compound (B) having a polymerizable unsaturated bond in an aqueous medium and a polyurethane prepolymer (A1) with a chain extender (C). The step (δ) of obtaining the resin may be performed at the same time. In this case, (A1), (C), (B) and an aqueous medium may be mixed at once, (C) may be previously mixed with an aqueous medium, and these and (A1) or (B) may be mixed. .

Step (β) of neutralizing the acidic group of the polyurethane prepolymer (A1), step (γ) of dispersing the compound (B) having a polymerizable unsaturated bond with the polyurethane prepolymer (A1) in an aqueous medium, and a polyurethane The step (δ) of reacting the prepolymer (A) with the chain extender (C) to obtain an aqueous polyurethane resin may be performed simultaneously. In this case, (A1), (C) and (B), the acidic group neutralizing agent and the aqueous medium may be mixed at once, and (C) and the acidic group neutralizing agent are previously mixed with the aqueous medium or (B), You may mix (A1) and (B).

In step (δ) in which the polyurethane prepolymer (A1) and the chain extender (C) are reacted to obtain an aqueous polyurethane resin, the reaction may be performed slowly under cooling, and in some cases, heating conditions of 60 ° C. or lower. It can also be carried out by accelerating the reaction under the following conditions. The reaction time under cooling may be about 0.5 to 24 hours, and the reaction time under heating conditions of 60 ° C. or less may be about 0.1 to 6 hours.

When the total amount of solids (including the compound (B) having a polymerizable unsaturated bond) of the aqueous polyurethane resin dispersion is 100 parts by weight, the polyurethane resin (A) is preferably 5 to 60 parts by weight, more preferably Is 15 to 50 parts by weight, more preferably 25 to 40 parts by weight. It is preferable that the number average molecular weights of a polyurethane resin (A) are 1,000-1,000,000. From the standpoint of the tag-free property of the dry coating film before photocuring, More preferably, it is 10,000-1,000,000.

XII. Photopolymerization initiator

You may add a photoinitiator to the aqueous polyurethane resin dispersion of this invention. The photoinitiator is not particularly limited and known ones can be used. Specifically, a photo-initiation type or a hydrogen-releasing type photopolymerization initiator can be used, which is easily cleaved by irradiation with active energy rays (for example, ultraviolet rays) to generate two radicals. These can also be used together.

As such a photoinitiator, for example, acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, benzophenone, 2-chlorobenzophenone, p, p'-bisdiethylaminobenzophenone, Benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin n-butyl ether, benzoin dimethyl ketal, thioxanthone, p-isopropyl-α-hydroxyiso Butylphenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclocyclohexylphenyl ketone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1- On, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 2,2-dimethoxy-1,2-diphenyl Tannon etc. are mentioned. Especially, hydroxycyclohexyl phenyl ketone is preferable.

When adding a photoinitiator, it is preferable to add after a process (delta) which makes a polyurethane prepolymer (A1) and a chain extender (C) react, and obtains an aqueous polyurethane resin (A). As addition amount of a photoinitiator, 0.5-5 weight part is preferable with respect to the total solid (compound (B) which has a polymerizable unsaturated bond) of an aqueous polyurethane resin dispersion.

ⅩⅢ. additive

Moreover, additives, such as a thickener, a photosensitizer, a curing catalyst, an ultraviolet absorber, an optical stabilizer, an antifoamer, a plasticizer, a surface regulator, and a sedimentation inhibitor, can also be added to the aqueous polyurethane resin dispersion of this invention as needed. An additive may be used independently and may use multiple types together. It is preferable that the aqueous polyurethane resin dispersion of this invention does not contain a protective colloid, an emulsifier, and surfactant substantially from the hardness of the coating film obtained, and chemical-resistance point.

Coating Compositions and Coating Compositions

The present invention also relates to a coating composition and a coating composition containing the aqueous polyurethane resin dispersion.

In addition to the said aqueous polyurethane resin dispersion, other resin can also be added to the coating composition and coating composition of this invention. Other resins include polyester resins, acrylic resins, polyether resins, polycarbonate resins, polyurethane resins, epoxy resins, alkyd resins, polyolefin resins, and the like. These may be used independently and may use multiple types together.

It is preferable that other resin has one or more hydrophilic group. Examples of the hydrophilic group include hydroxyl group, carboxyl group, sulfonic acid group and polyethylene glycol group.

It is preferable that other resin is at least 1 sort (s) chosen from the group which consists of a polyester resin, an acrylic resin, and a polyolefin resin.

Polyester resin can be manufactured by esterification reaction or transesterification reaction of an acid component and an alcohol component normally. As an acid component, the compound normally used as an acid component at the time of manufacture of a polyester resin can be used. As the acid component, for example, an aliphatic polybasic acid, an alicyclic polybasic acid, an aromatic polybasic acid, or the like can be used.

As for the hydroxyl value of a polyester resin, about 10-300 mgKOH / g is preferable, About 50-250 mgKOH / g is more preferable, About 80-180 mgKOH / g is still more preferable. The acid value of the polyester resin is preferably about 1 to 200 mgKOH / g, more preferably about 15 to 100 mgKOH / g, still more preferably about 25 to 60 mgKOH / g.

500-500,000 are preferable, as for the weight average molecular weight of a polyester resin, 1,000-300,000 are more preferable, and 1,500-200,000 are more preferable.

As an acrylic resin, a hydroxyl group containing acrylic resin is preferable. The hydroxyl group-containing acrylic resin is a polymerizable unsaturated monomer copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer and the hydroxyl group-containing polymerizable unsaturated monomer, for example, a solution polymerization method in an organic solvent, an emulsion polymerization method in water, and the like. It can manufacture by copolymerizing by a method.

The hydroxyl group-containing polymerizable unsaturated monomer is a compound having one or more hydroxyl groups and one or more polymerizable unsaturated bonds in one molecule. For example, (2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. ( Monoesterified product of meth) acrylic acid and dihydric alcohol having 2 to 8 carbon atoms; Ε-caprolactone modified product of these monoesters; N-hydroxymethyl (meth) acrylamide; Allyl alcohol; (Meth) acrylate etc. which have a polyoxyethylene chain whose molecular terminal is a hydroxyl group are mentioned.

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

As for the hydroxyl value of a hydroxyl-containing acrylic resin, about 1-200 mgKOH / g is preferable from a viewpoint of storage stability of an aqueous polyurethane resin dispersion, the water resistance of the coating film obtained, etc., about 2-100 mgKOH / g is more preferable, 3 About 60 mgKOH / g is more preferable.

When the hydroxyl group-containing acrylic resin has acidic groups such as carboxyl groups, the acid value of the hydroxyl group-containing acrylic resin is preferably about 1 to 200 mgKOH / g, more preferably about 2 to 150 mgKOH / g, from the viewpoint of the water resistance of the coating film to be obtained, About 5-100 mgKOH / g is more preferable.

1,000-200,000 are preferable, as for the weight average molecular weight of a hydroxyl-containing acrylic resin, 2,000-100,000 are more preferable, More preferably, it exists in the range of 3,000-50,000.

As a polyether resin, the polymer or copolymer which has an ether bond is mentioned, For example, Aromatic poly, such as polyoxyethylene type polyether, polyoxypropylene type polyether, polyoxybutylene type polyether, bisphenol A, or bisphenol F, etc. And polyethers derived from hydroxy compounds.

As a polycarbonate resin, the polymer manufactured from the bisphenol compound is mentioned, For example, bisphenol A polycarbonate etc. are mentioned.

As a polyurethane resin, resin which has a urethane bond obtained by reaction of various polyol components, such as an acryl, polyester, polyether, polycarbonate, and polyisocyanate is mentioned.

As an epoxy resin, resin etc. which are obtained by reaction of a bisphenol compound and epichlorohydrin are mentioned. As bisphenol, bisphenol A and bisphenol F are mentioned, for example.

Alkyd resins include alkyds obtained by further reacting polybasic acids, such as phthalic acid, terephthalic acid, succinic acid, and polyhydric alcohols with denaturants such as fats and oils and fatty acids (soybean oil, linseed oil, palm oil, stearic acid, etc.), and natural resins (such as rosin and pumpkin). Resin can be mentioned.

As polyolefin resin, the polyolefin resin obtained by superposing | polymerizing or copolymerizing an olefinic monomer suitably with another monomer according to a conventional polymerization method is obtained by disperse | distributing a polyolefin resin using an emulsifier or emulsion-polymerizing an olefinic monomer with another monomer suitably. Resin can be mentioned. In some cases, a so-called chlorinated polyolefin-modified resin in which the polyolefin resin is chlorinated may also be used.

As the olefin monomer, for example, ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-hexene, 1-decene Α-olefins such as 1-dodecene and the like; Conjugated dienes, such as butadiene, ethylidene norbornene, dicyclopentadiene, 1,5-hexadiene, styrene, or non-conjugated dienes, and the like, and the like. These monomers may be used alone or in combination. It may be.

As another monomer copolymerizable with an olefinic monomer, vinyl acetate, vinyl alcohol, maleic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, etc. are mentioned, for example, These monomers are mentioned. It may be used independently or may use multiple types together.

By containing a hardening | curing agent in the coating composition and coating composition of this invention, the water resistance of the coating film or multilayer coating film using a coating composition or coating composition, a coating film, etc. can be improved.

As a hardening | curing agent, amino resin, polyisocyanate, blocked polyisocyanate, melamine resin, carbodiimide, etc. can be used, for example. A hardening | curing agent may be used individually by 1 type, and may use multiple types together.

As an amino resin, the partial or fully methylolated amino resin obtained by reaction of an amino component and an aldehyde component is mentioned, for example. Examples of the amino component include melamine, urea, benzoguanamine, acetoguanamine, steroguanamine, spiroguanamine, and dicyandiamide. As an aldehyde component, formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, etc. are mentioned, for example.

As polyisocyanate, the compound which has two or more isocyanato groups in 1 molecule is mentioned, for example, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, etc. are mentioned, for example.

Examples of the blocked polyisocyanate include those obtained by adding a blocking agent to the polyisocyanato group of the polyisocyanate described above. Examples of the blocking agent include aliphatic alcohols such as phenol and cresol, aliphatic alcohols such as methanol and ethanol, dimethyl malonate and acetyl. Active methylenes such as acetone, mercaptans such as butyl mercaptan and dodecyl mercaptan, acid amides such as acetoanilide and amide acetate, lactams such as ε-caprolactam and δ-valerolactam, succinimide and male Blocking agents such as acid imides such as acid imides, oximes such as acetaldehyde oxime, acetone oxime and methyl ethyl keto oxime, and amines such as diphenylaniline, aniline, and ethyleneimine.

As a melamine resin, For example, methylol melamine, such as dimethylol melamine and trimethylol melamine; Alkyl etherified products or condensates of these methylolmelamines; And condensates of alkyl etherates of methylolmelamine.

A coloring pigment, an extender pigment, and a bright pigment can be added to the coating composition and coating composition of this invention.

Examples of the color pigments include titanium oxide, zinc oxide, carbon black, molybdenum red, prussian blue, cobalt blue, azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolin pigments, tren pigments, and perylene pigments. Can be mentioned. These may be used independently and may use multiple types together. In particular, it is preferable to use titanium oxide and / or carbon black as a coloring pigment.

As an extender pigment, clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, alumina white, etc. are mentioned, for example. These may be used independently and may use multiple types together. In particular, it is preferable to use barium sulfate and / or talc as an extender pigment, and it is more preferable to use barium sulfate.

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

The coating composition and coating composition of the present invention may contain conventional paint additives such as thickeners, curing catalysts, ultraviolet absorbers, light stabilizers, antifoaming agents, plasticizers, surface conditioners, and antisettling agents, as necessary. These may be used independently and may use multiple types together.

Although the manufacturing method of the coating composition and coating composition of this invention is not specifically limited, A well-known manufacturing method can be used. Generally, a coating composition and a coating composition are manufactured by mixing the said aqueous polyurethane resin dispersion with the various additives mentioned above, and adding to an aqueous medium and adjusting to the viscosity according to a coating method.

Examples of the coating material of the coating composition or the coating material of the coating composition include metals, plastics, inorganic materials, and wood.

As a coating method of a coating composition or a coating method of a coating composition, bell coating, spray coating, roll coating, shower coating, immersion coating, etc. are mentioned.

The aqueous polyurethane resin dispersion, the aqueous polyurethane resin dispersion composition, the coating composition, and the coating composition of the present invention are applied, coated, or coated onto a desired substrate, and then evaporated at least a portion of the aqueous medium under heating or non-heating. It is preferable to harden | cure by irradiating an active energy ray. Examples of the active energy rays include ionizing radiation such as electron beams, ultraviolet rays or gamma rays, and among them, ultraviolet rays are preferred.

The ultraviolet light source is not particularly limited as long as it is a light source that emits light in the ultraviolet region. For example, xenon lamp, low pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, carbon arc lamp, tungsten lamp and the like can be used. Irradiation time can be suitably fluctuated according to conditions, such as the kind of compound which has a polymerizable unsaturated bond, the kind of photoinitiator, film thickness, an ultraviolet-ray source, etc. It is preferable to irradiate for 1 to 60 second from the point of workability. Moreover, it can also heat-process after ultraviolet irradiation in order to complete hardening reaction.

As an irradiation amount of the ultraviolet-ray used when hardening the aqueous polyurethane resin dispersion, coating composition, coating composition, etc. of this invention, 300-3,000mJ / cm <^2> is preferable from a viewpoint of quick hardening property and workability.

An electron beam etc. can also be used in addition to an ultraviolet-ray for hardening. When hardening with an electron beam, the photoinitiator may not be added and it is preferable to use the electron beam accelerator which has an energy of 100-500 eV.

<Examples>

Next, an Example and a comparative example are given and this invention is demonstrated in detail.

Example 1

ETERNACOLL (registered trade mark) UM90 (3/1) (manufactured by Ubegosan; number average molecular weight 916; hydroxyl value 122 mgKOH / g; polyol component 1,4-cyclohexanedimethanol in a reaction apparatus equipped with a stirrer and a heater Polycarbonate diol obtained by reacting a polyol mixture in a molar ratio of 1: 1,6-hexanediol = 3: 1 with a carbonate ester, an alicyclic structure content of 39% by weight, 25.9 g), and 2,2-dimethylolpropionic acid (DMPA, 11.1 g) and isophorone diisocyanate (IPDI, 57.5 g) were heated at 80-90 ° C. for 2.5 hours in a nitrogen atmosphere in the presence of dibutyltin dilaurylate (0.1 g) in N-ethylpyrrolidone (43.9 g). It was. 2, 6- di-tert- butyl- 4-methyl phenol (0.2g) and 4-methoxy phenol (0.2g) were added, and atmosphere was made into air. In addition, the reaction product (1,6-HDL-EP-A, 12.6 g) of 2 molecules of acrylic acid and 1,6-hexanediol diglycidyl of 1 molecule, and pentaerythritol triacrylate (PETA, 19.7 g) ) Was heated at 90 ° C. for 6 hours. At the time of completion of the urethane-forming reaction, the NCO group content was 4.01 wt%. The reaction mixture was cooled to 70 ° C, and dipentaerythritol hexaacrylate (DPHA, 79.9 g) and triethylamine (8.9 g) were added and mixed thereto. The reaction mixture (226 g) was added in water (386 g) under strong stirring. Subsequently, 35 weight% of 2-methyl-1,5-pentanediamine aqueous solution (MPMD, 20.1 g) was added, and the aqueous polyurethane resin dispersion was obtained.

[Example 2]

Ethernacol (registered trade mark) UM90 (3/1) (manufactured by Ubegosan; number average molecular weight 916; hydroxyl value 122 mgKOH / g; polyol component 1,4-cyclohexanedimethanol) in a reactor equipped with a stirrer and a heater: Polycarbonate diol obtained by reacting a polyol mixture in a molar ratio of 6-hexanediol = 3: 1 with a carbonate ester, an alicyclic structure content of 39 wt%, 40.3 g), and 2,2-dimethylolpropionic acid (DMPA, 9.7 g) And isophorone diisocyanate (IPDI, 46.3 g) were heated at 80-90 ° C. for 2.5 hours under nitrogen atmosphere in the presence of dibutyltin dilaurylate (0.1 g) in N-ethylpyrrolidone (40.5 g). 2, 6- di-tert- butyl- 4-methyl phenol (0.2g) and 4-methoxy phenol (0.2g) were added, and atmosphere was made into air. Further, pentaerythritol triacrylate (PETA, 16.1 g) was added thereto, and the mixture was heated at 90 ° C. for 5 hours. At the time of completion of the urethane-forming reaction, the NCO group content was 3.51 wt%. The reaction mixture was cooled to 70 ° C, and trimethylolpropane triacrylate (TMPTA, 72.5 g) and triethylamine (7.8 g) were added and mixed thereto. The reaction mixture (210 g) was added in water (353 g) under strong stirring. Subsequently, 35 weight% of 2-methyl-1,5-pentanediamine aqueous solution (MPMD, 15.8g) was added, and the aqueous polyurethane resin dispersion was obtained.

[Example 3]

Ethernacol (registered trade mark) UM90 (3/1) (manufactured by Ubegosan; number average molecular weight 916; hydroxyl value 122 mgKOH / g; polyol component 1,4-cyclohexanedimethanol) in a reactor equipped with a stirrer and a heater: Polycarbonate diol obtained by reacting a polyol mixture in a molar ratio of 6-hexanediol = 3: 1 with a carbonate ester, an alicyclic structure content of 39% by weight, 56.1 g), and 2,2-dimethylolpropionic acid (DMPA, 23.5 g) And isophorone diisocyanate (IPDI, 124 g) were heated at 80-90 ° C. for 3 hours in a nitrogen atmosphere in the presence of dibutyltin dilaurylate (0.2 g) in N-ethylpyrrolidone (96.4 g). 2, 6- di-tert- butyl- 4-methyl phenol (0.5g) and 4-methoxy phenol (0.5g) were added, and atmosphere was made into air. In addition, the reaction product (1,6-HDL-EP-A, 27.7g) of 2 molecules of acrylic acid and 1,6-hexanediol diglycidyl of 1 molecule, and pentaerythritol triacrylate (PETA, 42.3g) ) Was heated at 90 ° C. for 5 hours. At the time of completion of the urethane-forming reaction, the NCO group content was 4.05 wt%. The reaction mixture was cooled to 70 ° C, and dipentaerythritol hexaacrylate (DPHA, 178 g) and triethylamine (19.5 g) were added and mixed thereto. The reaction mixture (251 g) was added in water (423 g) under strong stirring. Subsequently, 35 weight% of diethylenetriamine aqueous solution (DETA, 13.3 g) was added, and the aqueous polyurethane resin dispersion was obtained.

Example 4

Ethernacol (registered trade mark) UM90 (3/1) (manufactured by Ubegosan; number average molecular weight 916; hydroxyl value 122 mgKOH / g; polyol component 1,4-cyclohexanedimethanol) in a reactor equipped with a stirrer and a heater: Polycarbonate diol obtained by reacting a polyol mixture in a molar ratio of 6-hexanediol = 3: 1 with a carbonate ester, an alicyclic structure content of 39% by weight, 56.1 g), and 2,2-dimethylolpropionic acid (DMPA, 23.5 g) And isophorone diisocyanate (IPDI, 124 g) were heated at 80-90 ° C. for 3 hours in a nitrogen atmosphere in the presence of dibutyltin dilaurylate (0.2 g) in N-ethylpyrrolidone (96.4 g). 2, 6- di-tert- butyl- 4-methyl phenol (0.5g) and 4-methoxy phenol (0.5g) were added, and atmosphere was made into air. In addition, the reaction product (1,6-HDL-EP-A, 27.7g) of 2 molecules of acrylic acid and 1,6-hexanediol diglycidyl of 1 molecule, and pentaerythritol triacrylate (PETA, 42.3g) ) Was heated at 90 ° C. for 5 hours. At the time of completion of the urethane-forming reaction, the NCO group content was 4.05 wt%. The reaction mixture was cooled to 70 ° C, and dipentaerythritol hexaacrylate (DPHA, 178 g) and triethylamine (19.5 g) were added and mixed thereto. The reaction mixture (232 g) was added in water (391 g) under strong stirring. Subsequently, 35 weight% of diethylenetriamine aqueous solution (DETA, 6.1 g) and 35 weight% of 2-methyl-1,5-pentanediamine aqueous solution (MPMD, 10.4 g) were added to obtain an aqueous polyurethane resin dispersion. .

[Example 5]

Ethernacol (registered trade mark) UM90 (3/1) (manufactured by Ubegosan; number average molecular weight 916; hydroxyl value 122 mgKOH / g; polyol component 1,4-cyclohexanedimethanol) in a reactor equipped with a stirrer and a heater: Polycarbonate diol obtained by reacting a polyol mixture in a molar ratio of 6-hexanediol = 3: 1 with a carbonate ester, an alicyclic structure content of 39% by weight, 25.2 g), and 2,2-dimethylolpropionic acid (DMPA, 10.6 g) And isophorone diisocyanate (IPDI, 56.1 g) were heated at 80-90 ° C. for 2 hours in a nitrogen atmosphere in the presence of dibutyltin dilaurylate (0.1 g) in N-ethylpyrrolidone (42.9 g). 2, 6- di-tert- butyl- 4-methyl phenol (0.2g) and 4-methoxy phenol (0.2g) were added, and atmosphere was made into air. In addition, the reaction product (1,6-HDL-EP-A, 12.2 g) of 2 molecules of acrylic acid and 1 molecule of 1,6-hexanediol diglycidyl, and pentaerythritol triacrylate (PETA, 19.9 g) ) Was heated at 90 ° C. for 6 hours. At the time of completion of the urethane-forming reaction, the NCO group content was 3.95 wt%. The reaction mixture was cooled to 70 ° C, and trimethylolpropanetriacrylate (TMPTA, 79.1 g) and triethylamine (8.6 g) were added and mixed thereto. The reaction mixture (233 g) was added in water (401 g) under strong stirring. Subsequently, 35 weight% of 2-methyl-1,5-pentanediamine aqueous solution (MPMD, 19.7g) was added, and the aqueous polyurethane resin dispersion was obtained.

[Example 6]

Ethernacol (registered trade mark) UM90 (3/1) (manufactured by Ubegosan; number average molecular weight 916; hydroxyl value 122 mgKOH / g; polyol component 1,4-cyclohexanedimethanol) in a reactor equipped with a stirrer and a heater: Polycarbonate diol obtained by reacting a polyol mixture with a carbonate ester having a molar ratio of 6-hexanediol = 3: 1, alicyclic structure content of 39% by weight (121 g), 2,2-dimethylolpropionic acid (DMPA, 29.4 g) , Isophorone diisocyanate (IPDI, 139 g) was heated at 80-90 ° C. for 2 hours in a nitrogen atmosphere in the presence of dibutyltin dilaurylate (0.2 g) in N-ethylpyrrolidone (121 g). 2, 6- di-tert- butyl- 4-methyl phenol (0.8g) and 4-methoxy phenol (0.8g) were added, and atmosphere was made into air. Further, pentaerythritol triacrylate (PETA, 46.1 g) was added thereto and heated at 90 ° C. for 6 hours. At the time of completion of the urethane-forming reaction, the NCO group content was 3.83 wt%. The reaction mixture was cooled to 70 ° C, and trimethylolpropanetriacrylate (TMPTA, 221 g) and triethylamine (24.1 g) were added and mixed thereto. The reaction mixture (201 g) was added in water (332 g) under strong stirring. Next, adipic dihydrazide (AH, 8.5 g) was added to obtain an aqueous polyurethane resin dispersion.

[Example 7]

Ethernacol (registered trade mark) UM90 (3/1) (manufactured by Ubegosan; number average molecular weight 916; hydroxyl value 122 mgKOH / g; polyol component 1,4-cyclohexanedimethanol) in a reactor equipped with a stirrer and a heater: Polycarbonate diol obtained by reacting a polyol mixture with a carbonate ester having a molar ratio of 6-hexanediol = 3: 1, alicyclic structure content of 39% by weight (121 g), 2,2-dimethylolpropionic acid (DMPA, 29.4 g) , Isophorone diisocyanate (IPDI, 139 g) was heated at 80-90 ° C. for 2 hours in a nitrogen atmosphere in the presence of dibutyltin dilaurylate (0.2 g) in N-ethylpyrrolidone (121 g). 2, 6- di-tert- butyl- 4-methyl phenol (0.8g) and 4-methoxy phenol (0.8g) were added, and atmosphere was made into air. Further, pentaerythritol triacrylate (PETA, 46.1 g) was added thereto and heated at 90 ° C. for 6 hours. At the time of completion of the urethane-forming reaction, the NCO group content was 3.83 wt%. The reaction mixture was cooled to 70 ° C, and trimethylolpropanetriacrylate (TMPTA, 221 g) and triethylamine (24.1 g) were added and mixed thereto. The reaction mixture (199 g) was added in water (337 g) under strong stirring. Subsequently, 35 wt% aqueous hydrazine solution (4.8 g) was added to obtain an aqueous polyurethane resin dispersion.

[Example 8]

Ethernacol (registered trade mark) UM90 (3/1) (manufactured by Ubegosan; number average molecular weight 916; hydroxyl value 122 mgKOH / g; polyol component 1,4-cyclohexanedimethanol) in a reactor equipped with a stirrer and a heater: Polycarbonate diol obtained by reacting a polyol mixture with a carbonate ester having a molar ratio of 6-hexanediol = 3: 1, alicyclic structure content of 39% by weight (121 g), 2,2-dimethylolpropionic acid (DMPA, 29.4 g) , Isophorone diisocyanate (IPDI, 139 g) was heated at 80-90 ° C. for 2 hours in a nitrogen atmosphere in the presence of dibutyltin dilaurylate (0.2 g) in N-ethylpyrrolidone (121 g). 2, 6- di-tert- butyl- 4-methyl phenol (0.8g) and 4-methoxy phenol (0.8g) were added, and atmosphere was made into air. Further, pentaerythritol triacrylate (PETA, 46.1 g) was added thereto and heated at 90 ° C. for 6 hours. At the time of completion of the urethane-forming reaction, the NCO group content was 3.83 wt%. The reaction mixture was cooled to 70 ° C, and trimethylolpropanetriacrylate (TMPTA, 221 g) and triethylamine (24.1 g) were added and mixed thereto. The reaction mixture (253 g) was added in water (410 g) under strong stirring. Subsequently, 13 weight% of piperazine aqueous solution (4.8 g) was added, and the aqueous polyurethane resin dispersion was obtained.

[Example 9]

Ethernacol (registered trade mark) UM90 (3/1) (manufactured by Ubegosan; number average molecular weight 916; hydroxyl value 122 mgKOH / g; polyol component 1,4-cyclohexanedimethanol) in a reactor equipped with a stirrer and a heater: Polycarbonate diol obtained by reacting a polyol mixture in a molar ratio of 6-hexanediol = 3: 1 with a carbonate ester, an alicyclic structure content of 39% by weight, 100g), 2,2-dimethylolpropionic acid (DMPA, 36.7g) , Isophorone diisocyanate (IPDI, 144 g) was heated at 80-90 ° C. for 2.5 hours under nitrogen atmosphere in the presence of dibutyltin dilaurylate (0.2 g) in N-ethylpyrrolidone (114 g). 2, 6- di-tert- butyl- 4-methyl phenol (0.2g) and 4-methoxy phenol (0.2g) were added, and atmosphere was made into air. In addition, pentaerythritol triacrylate (PETA, 225 g) was added thereto and heated at 90 ° C. until the NCO group content became almost 0 wt%. The reaction mixture was cooled to 70 ° C, and trimethylolpropanetriacrylate (TMPTA, 219 g) and triethylamine (28.4 g) were added and mixed thereto. The reaction mixture (113 g) was added in water (202 g) under steel stirring to obtain an aqueous polyurethane resin dispersion.

Comparative Example 1

Ethernacol (registered trade mark) UM90 (3/1) (manufactured by Ubegosan; number average molecular weight 916; hydroxyl value 122 mgKOH / g; polyol component 1,4-cyclohexanedimethanol) in a reactor equipped with a stirrer and a heater: Polycarbonate diol obtained by reacting a polyol mixture in a molar ratio of 6-hexanediol = 3: 1 with carbonate ester, alicyclic structure content 39 wt%, 40.9 g), and 2,2-dimethylolpropionic acid (DMPA, 11.8 g) And isophorone diisocyanate (IPDI, 52.7 g) were heated at 80-90 ° C. for 4 hours in a nitrogen atmosphere in the presence of dibutyltin dilaurylate (0.1 g) in N-ethylpyrrolidone (44.3 g). At the time of completion of the urethane-forming reaction, the NCO group content was 0.42 wt%. 2, 6- di-tert- butyl- 4-methyl phenol (0.2g) and 4-methoxy phenol (0.2g) were added, and atmosphere was made into air. The reaction mixture was cooled to 70 ° C, and trimethylolpropanetriacrylate (TMPTA, 101 g) and triethylamine (8.7 g) were added and mixed thereto. The reaction mixture (222 g) was added in water (369 g) under strong stirring. Subsequently, 35% by weight aqueous 2-methyl-1,5-pentanediamine solution (MPMD, 24.8 g) was added to obtain an aqueous polyurethane resin dispersion.

Comparative Example 2

Ethernacol (registered trademark) UH100 (manufactured by Ubegosan; number average molecular weight 1004; hydroxyl value 112 mgKOH / g; polycarbonate diol obtained by reacting 1,6-hexanediol and carbonate ester, 40.8 in a reactor equipped with a stirrer and a heater g), 2,2-dimethylolpropionic acid (DMPA, 7.4 g) and isophorone diisocyanate (IPDI, 55.5 g) in dibutyltin dilaurylate (0.10 g) in N-ethylpyrrolidone (49.0 g). g) heated at 80-90 ° C. for 2.5 h under nitrogen atmosphere in the presence. 2, 6- di-tert- butyl- 4-methyl phenol (0.2g) and 4-methoxy phenol (0.2g) were added, and atmosphere was made into air. The reaction product (1,6-HDL-EP-A, 15.1 g) of two molecules of acrylic acid and one molecule of 1,6-hexanediol diglycidyl was added thereto, followed by heating at 90 ° C for 2 hours. At the time of completion of the urethane-forming reaction, the NCO group content was 5.47 wt%. The reaction mixture was cooled to 70 ° C, and trimethylolpropanetriacrylate (TMPTA, 78.7 g) and triethylamine (5.6 g) were added and mixed thereto. The reaction mixture (241 g) was added in water (390 g) under strong stirring. Subsequently, 35% by weight aqueous 2-methyl-1,5-pentanediamine solution (MPMD, 29.1 g) was added to obtain an aqueous polyurethane resin dispersion.

[Comparative Example 3]

Ethernacol (registered trademark) UH100 (manufactured by Ubegosan; number average molecular weight 1004; hydroxyl value 112 mgKOH / g; polycarbonate diol obtained by reacting 1,6-hexanediol and carbonate ester, 30.4 in a reactor equipped with a stirrer and a heater g), 2,2-dimethylolpropionic acid (DMPA, 8.6 g) and isophorone diisocyanate (IPDI, 50.9 g) in dibutyltin dilaurylate (0.1 g) in N-ethylpyrrolidone (43.2 g) g) heated at 80-90 ° C. under nitrogen atmosphere in the presence for 2 hours. 2, 6- di-tert- butyl- 4-methyl phenol (0.2g) and 4-methoxy phenol (0.2g) were added, and atmosphere was made into air. In addition, the reaction product (1,6-HDL-EP-A, 12.5 g) of 2 molecules of acrylic acid and 1 molecule of 1,6-hexanediol diglycidyl, and pentaerythritol triacrylate (PETA, 16.7 g) ) Was heated at 90 ° C. for 6 hours. At the time of completion of the urethane-forming reaction, the NCO group content was 3.59 wt%. The reaction mixture was cooled to 70 ° C, and trimethylolpropanetriacrylate (TMPTA, 75.0 g) and triethylamine (6.8 g) were added and mixed thereto. The reaction mixture (222 g) was added in water (375 g) under strong stirring. Subsequently, 35 weight% of 2-methyl-1,5-pentanediamine aqueous solution (MPMD, 16.5g) was added, and the aqueous polyurethane resin dispersion was obtained.

[Comparative Example 4]

Ethernacol (registered trade mark) UM90 (3/1) (manufactured by Ubegosan; number average molecular weight 916; hydroxyl value 122 mgKOH / g; polyol component 1,4-cyclohexanedimethanol) in a reactor equipped with a stirrer and a heater: Polycarbonate diol obtained by reacting a polyol mixture in a molar ratio of 6-hexanediol = 3: 1 with carbonate ester, alicyclic structure content 39 wt%, 41.1 g), and 2,2-dimethylolpropionic acid (DMPA, 17.6 g) And isophorone diisocyanate (IPDI, 91.3 g) were heated at 80-90 ° C. for 2.5 hours in a nitrogen atmosphere in the presence of dibutyltin dilaurylate (0.1 g) in N-ethylpyrrolidone (69.8 g). 2, 6- di-tert- butyl- 4-methyl phenol (0.2g) and 4-methoxy phenol (0.2g) were added, and atmosphere was made into air. In addition, the reaction product (1,6-HDL-EP-A, 21.6g) and pentaerythritol triacrylate (PETA, 29.3g) of 2 molecules of acrylic acid and 1 molecule of 1,6-hexanediol diglycidyl Was added, and it heated at 90 degreeC for 6 hours. At the time of completion of the urethane-forming reaction, the NCO group content was 3.96 wt%. The reaction mixture was cooled to 70 ° C, and triethylamine (14.3 g) was added and mixed. The reaction mixture (241 g) was added in water (334 g) under strong stirring. Subsequently, 35 wt% of 2-methyl-1,5-pentanediamine aqueous solution (MPMD, 29.5 g) was added to obtain an aqueous polyurethane resin dispersion.

[Sample Preparation of Pencil Hardness and Adhesiveness]

To each of the aqueous polyurethane resin dispersions of Examples 1 to 9 and Comparative Examples 1 to 4, 3 wt% / solid content of a polymerization initiator (IRGACURE 500, manufactured by Ciba Specialty Chemical Co., Ltd.) was added thereto, followed by stirring well. A coating agent was obtained. This was apply | coated uniformly to ABS resin, acrylic resin, and PC resin so that the film thickness after drying might be set to about 20 micrometers. Next, the coating film (before ultraviolet irradiation) was obtained by drying at 60 degreeC for 30 minutes. The obtained coating film was passed under a high pressure mercury lamp (once irradiation, ultraviolet irradiation amount 1000mJ / cm <^2> ). The obtained polyurethane resin coating film was used for pencil hardness measurement and adhesive evaluation.

(Evaluation of hardness)

It evaluated by measuring the pencil hardness of a polyurethane resin coating film.

[Measurement of Pencil Hardness]

In the polyurethane resin coating film obtained on the acrylic resin obtained above, the pencil hardness of the resin coating film was measured by the method based on JISK5600-5-4.

(Evaluation of adhesion)

In the polyurethane resin coating film obtained on the above ABS resin, acrylic resin, and PC resin, it evaluated by the checkerboard eye peeling method. That is, 25 4 mm ² checker eyes were produced on the test piece with the cutter, and peelability was investigated by the cellophane tape.

(Evaluation of Storage Stability)

The external appearance of each of the aqueous polyurethane resin dispersions of Examples 1 to 9 and Comparative Examples 1 to 4 was observed after one week after production to confirm storage stability. The evaluation criteria are as follows.

○: no change.

X: Aggregate is seen.

(Evaluation of tag-freeness)

To the aqueous polyurethane resin dispersions of Examples 1 to 9 and Comparative Examples 1 to 4, 3 wt% / solid content of a polymerization initiator (Irgacure 500, manufactured by Ciba Specialty Chemical Co., Ltd.) was added, followed by stirring well to obtain a coating agent. . This was apply | coated uniformly to acrylic resin so that the film thickness after drying might be set to about 20 micrometers. Next, the coating film (before ultraviolet irradiation) was obtained by drying at 60 degreeC for 30 minutes. The finger was applied to the coating film to evaluate tack-free properties. The evaluation criteria are as follows.

○: no change.

X: Traces of a finger or fingerprint remain.

The weight part in a table | surface shows the weight part of each compound when the total solid (including an acryl compound) in resin is 100 weight part.

Pencil hardness in a table shows that "H" does not have any scratches with the pencil of H, for example. "2H-3H" shows that a 3H pencil does not scratch or come out, and 2H does not show a scratch at all.

The adhesiveness in a table | surface shows the result of a peeling test. "25/25" shows that 25 eyes of 25 eyes adhere | attach after a test.

As shown in the above table, the aqueous polyurethane resin dispersion of Examples could form a coating film excellent in adhesion, and was excellent in storage stability.

In Comparative Example 1 in which the unsaturated compound (e) was not used in the production of the polyurethane resin (A), the storage stability was inferior.

Compounds (B) having a polymerizable unsaturated bond in Comparative Examples 2 and 3, and an aqueous polyurethane resin dispersion in which the polycarbonate diol (a) having an alicyclic structure was not used in the production of the polyurethane resin (A) were used. In Comparative Example 4 which was not blended, all had poor adhesion.

By comparing the result of the comparative example 2 and the comparative example 3, it turned out that the storage stability of an aqueous polyurethane resin dispersion improves by using the unsaturated compound (e ') which has one hydroxyl group in 1 molecule.

Moreover, by comparing the result of Example 5 and Example 6, it turns out that the hardness of the coating film obtained from an aqueous polyurethane resin dispersion becomes high by using the unsaturated compound (e ') which has two or more hydroxyl groups in 1 molecule. there was.

Moreover, by comparing the result of Example 1 and Example 9, it turned out that the tack free property of the dry coating film before ultraviolet irradiation is high by using a chain extender.

The aqueous polyurethane resin dispersion of the present invention can be widely used as raw materials for paints and coatings.

Claims (13)

It is an aqueous polyurethane resin dispersion formed by dispersing at least a polyurethane resin (A) having a polymerizable unsaturated bond and a compound (B) having a polymerizable unsaturated bond in an aqueous medium,
Polyurethane resin (A) which has a polymerizable unsaturated bond is a polycarbonate diol (a) which has an alicyclic structure at least in a principal chain, an acidic group containing polyol (b), a polyisocyanate (d), and one in 1 molecule An aqueous polyurethane resin dispersion, which is a polyurethane resin obtained by reacting a group capable of reacting with an isocyanato group and a compound (e) having at least one polymerizable unsaturated bond. The aqueous polyurethane resin dispersion according to claim 1, wherein the compound (B) having a polymerizable unsaturated bond comprises a compound having at least three (meth) acryloyl groups. The aqueous polyurethane resin dispersion according to claim 1 or 2, wherein the compound (B) having a polymerizable unsaturated bond comprises a compound having at least five (meth) acryloyl groups. The compound (e) according to any one of claims 1 to 3, wherein the compound (e) having a group capable of reacting with one isocyanato group and one or more polymerizable unsaturated bonds in one molecule is one isocyanato group An aqueous polyurethane resin dispersion comprising a compound having a group reactive with and at least one (meth) acryloyl group. The compound (e) according to any one of claims 1 to 4, wherein the compound (e) having one or more polymerizable unsaturated bonds with a group capable of reacting with one isocyanato group in one molecule is one isocyanato group. An aqueous polyurethane resin dispersion comprising a compound having a group capable of reacting with and three or more (meth) acryloyl groups. (delete) The polyurethane resin according to any one of claims 1 to 5, wherein the polyurethane resin having a polymerizable unsaturated bond includes at least a polycarbonate diol (a) having an alicyclic structure in the main chain, an acidic group-containing polyol (b), and a poly Aqueous polyurethane resin obtained by making isocyanate (d) react with the compound (e) which has one or more polymerizable unsaturated bonds which can react with one isocyanato group in 1 molecule, and a chain extender (C) Dispersion. The aqueous polyurethane resin dispersion according to claim 7, wherein the chain extender (C) is a primary polyamine compound. At least one polycarbonate diol (a) having an alicyclic structure in the main chain, an acidic group-containing polyol (b), a polyisocyanate (d) and a group capable of reacting with one isocyanato group in one molecule and at least one Reacting a compound (e) having a polymerizable unsaturated bond to obtain a polyurethane resin (A),
The manufacturing method of the aqueous polyurethane resin dispersion of any one of Claims 1-5 which disperse | distributes a polyurethane resin (A) and the compound (B) which has a polymerizable unsaturated bond in an aqueous medium. At least one polycarbonate polyol (a) having an alicyclic structure in the main chain, an acidic group-containing polyol (b), a polyisocyanate (d) and a group capable of reacting with one isocyanato group in one molecule and at least one Step (α1) of reacting a compound (e) having a polymerizable unsaturated bond to obtain a polyurethane prepolymer (A1),
Process (β) of neutralizing the acidic group of the polyurethane prepolymer (A1), and
Step (γ) of dispersing the compound (B) having a polyurethane prepolymer (A1) and a polymerizable unsaturated bond in an aqueous medium,
7th including the process ((delta)) which reacts a polyurethane prepolymer (A1) with the chain extender (C) which is reactive with the isocyanato group of a polyurethane prepolymer (A1), and obtains an aqueous polyurethane resin. The process for producing the aqueous polyurethane resin dispersion according to claim 8. The aqueous polyurethane resin dispersion according to any one of claims 1 to 5, 7 and 8, further comprising a photopolymerization initiator. The coating composition containing the aqueous polyurethane resin dispersion of any one of Claims 1-5, 7, 8, and 11. The coating composition containing the aqueous polyurethane resin dispersion of any one of Claims 1-5, 7, 8, and 11.