JP2003292567A - Method for producing aqueous acrylic-polyurethane- based resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an aqueous acrylic-polyurethane- based resin, capable of shortening a time required for producing the resin, simultaneously capable of saving its production cost by controlling warming of the aqueous resin at a low temperature, capable of giving good appearance to the aqueous resin, and further capable giving stable viscosity to the aqueous resin by reducing an amount of a residual solvent. <P>SOLUTION: This method for producing the aqueous acrylic-polyurethane- based resin comprises dispersing a hydrophilic acrylic-polyurethane-based copolymer which is synthesized in a hydrophilic organic solvent having a boiling point of <100°C in water to form an aqueous dispersion, and finally removing the hydrophilic organic solvent in the aqueous dispersion, wherein the hydrophilic organic solvent is removed from the aqueous dispersion by setting degrees of constant vacuum to three or more stages, while keeping a temperature of the aqueous dispersion at 50°C or lower. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an aqueous acrylic-polyurethane-based resin, and more specifically, a mild heating condition at the time of solvent removal and a reduction in production time to reduce production cost. The present invention relates to a method for producing an aqueous acrylic-polyurethane-based resin in which the resulting aqueous acrylic-polyurethane-based resin has a good appearance and which can be obtained with a stable viscosity.

[0002]

2. Description of the Related Art Aqueous acrylic-polyurethane resins are
Since it has a hydrophilic group in the molecule, it has good dispersibility without the use of a surfactant, and has excellent strength of the film after drying,
Widely used as paints, adhesives, adhesives, coatings, etc.

So far, in the presence of hydrophilic organic solvents,
A self-dispersing urethane blepolymer having at least one of a carboxyl group and a sulfonic acid group is continuously mixed with a modifier in a pipeline, and then the mixture of the urethane prepolymer and the modifier is immersed in water. There has been proposed a method for producing a urethane emulsion, which comprises dispersing, followed by chain extension reaction and solvent removal (see, for example, Patent Document 1). According to this manufacturing method, as a method for shortening the time required for manufacturing, a method of carrying out a polymerization reaction at a high temperature of 50 to 150 ° C. is adopted.

However, using this method, water-based acrylic
When trying to obtain a polyurethane-based resin, it is necessary to react at a high temperature at the time of production, and thus the production cost required for heating is required, and the aqueous acrylic-polyurethane-based resin obtained by this production method tends to be cloudy in appearance. Further, there is a problem that it is difficult to obtain a uniform viscosity for the obtained water-based acrylic-polyurethane resin.

[0005]

[Patent Document 1] Japanese Patent Application Laid-Open No. 10-176062 (second
~ Page 6)

[0006]

SUMMARY OF THE INVENTION In view of the above problems, the present invention can shorten the time required for manufacturing, and at the same time suppress the heating to reduce the manufacturing cost.
Moreover, it is an object of the present invention to provide a method for producing an aqueous acrylic-polyurethane resin having a good appearance and a stable viscosity while reducing residual solvent.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found an epoch-making manufacturing method that solves these problems. That is, the present invention is a method for producing an aqueous acrylic-polyurethane resin,
A hydrophilic acrylic-polyurethane-based copolymer synthesized in a hydrophilic organic solvent (A) having a boiling point of less than 100 ° C. is dispersed in water to give an aqueous dispersion, and finally, the hydrophilic organic solvent (A ), While maintaining the temperature of the aqueous dispersion below 50 ° C., and (1) maintaining a constant degree of vacuum, azeotropic distillation of the hydrophilic organic solvent (A) and water during the removal. The outflow rate of the substance was measured, and (2) it was confirmed that the outflow rate of the azeotrope of the hydrophilic organic solvent (A) and water per minute was less than a certain amount, and (3) the degree of vacuum was adjusted. The removal method is performed by interlocking with the measurement of the outflow amount of the azeotrope of the hydrophilic organic solvent (A) and water by the raising method, and the removal is performed by passing the constant vacuum degree through three or more steps. Which is a method for producing the above water-based acrylic-polyurethane resin.

In the present invention, the above-mentioned outflow amount per minute is 0.001 to 1.5% with respect to the total charged amount of the hydrophilic organic solvent (A) having a boiling point of less than 100 ° C. and water before the removal.
The method for producing an aqueous acrylic-polyurethane-based resin according to claim 1, wherein the amount is equivalent to.

The present invention is characterized in that the hydrophilic organic solvent (A) having a boiling point of less than 100 ° C. is composed of two kinds, a ketone solvent and an alcohol solvent, and the above-mentioned aqueous acrylic-polyurethane system. Resin manufacturing method.

According to the present invention, the above-mentioned constant degree of vacuum is in the range of the first stage: 34.0 to 13.2 (kPa), the second stage: the range of 13.1 to 9.2 (kPa), and the third stage: The above-mentioned water-based acrylic resin, which is in the range of 9.1 to 3.9 (kPa).
It is a method for producing a polyurethane resin.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The present invention is a method for producing an aqueous acrylic-polyurethane resin, which is a hydrophilic organic solvent (A) having a boiling point of less than 100 ° C.
When the hydrophilic acrylic-polyurethane-based copolymer synthesized in (1) is dispersed in water to form an aqueous dispersion, and finally the hydrophilic organic solvent (A) in the aqueous dispersion is removed, the aqueous dispersion While maintaining the temperature below 50 ° C., (1) measuring the azeotrope flow rate of the hydrophilic organic solvent (A) and water during the removal while maintaining a constant degree of vacuum, (2) By confirming that the outflow amount of the azeotrope of the hydrophilic organic solvent (A) and water per minute is less than a certain amount, (3) increasing the degree of vacuum, and repeating the method, the hydrophilic organic solvent The water-based acrylic resin is characterized in that the removal is performed by interlocking the measurement of the outflow amount of the azeotrope of the solvent (A) and water and the degree of vacuum in conjunction with the constant degree of vacuum through three or more stages. It is a method for producing a polyurethane resin.

In the present invention, a hydrophilic organic solvent having a boiling point of less than 100 ° C. is selected so that it can be efficiently removed from the system during solvent removal. Here, the hydrophilic organic solvent, a solvent having a solubility in water, specifically,
A solvent having a molecular weight of 32 or more and a solubility in water at 20 ° C. of 2% or more. Examples of the hydrophilic organic solvent having a boiling point of less than 100 ° C. include ketone solvents such as acetone, methyl ethyl ketone, methyl isopropyl ketone, cyclohexanone, methanol, ethanol, n-propanol, isopropanol, sec-butanol, and the like.
Examples thereof include alcohol solvents such as t-butanol and allyl alcohol, ester solvents such as methyl acetate and ethyl acetate, ether solvents such as tetrahydrofuran. In the present invention, these hydrophilic organic solvents having a boiling point of less than 100 ° C. can be used alone or as a mixture of two or more thereof, but when considering the solubility in the target resin and the solubility in water. It is preferable to use a mixture of two types of a ketone solvent and an alcohol solvent, and it is more preferable to use a mixture of two types of methyl ethyl ketone and isopropanol.

The above-mentioned hydrophilic acrylic-polyurethane copolymer, which is synthesized in a hydrophilic organic solvent (A) having a boiling point of less than 100 ° C. and then dispersed in water to form an aqueous dispersion, is a hydrophilic group. It is an acrylic-polyurethane-based copolymer having, and its structure is not particularly limited.

As a preferred specific example in the present invention, the synthesis of an acrylic-polyurethane copolymer having a hydrophilic anionic group as a hydrophilic acrylic-polyurethane copolymer will be described in detail below.

As a method for obtaining the above-mentioned acrylic-polyurethane-based copolymer having a hydrophilic anionic group, for example, an acrylic-polyurethane-based copolymer having a carboxylic acid group is preliminarily synthesized, and then the carboxylic acid group is added. A method of neutralizing a carboxylic acid group with a basic neutralizing agent to give a function as a hydrophilic anionic group to obtain an acrylic-polyurethane-based copolymer having a hydrophilic anionic group can be mentioned.

The above acrylic-polyurethane-based copolymer having a carboxylic acid group is (a) an ethylenically unsaturated monomer (b) a radical polymerization initiator used for radical polymerization of an ethylenically unsaturated monomer, and (c) Organic polyisocyanate, (d) a compound containing a mercapto group and an active hydrogen group, (f) a compound containing an active hydrogen group other than a mercapto group, (f) a hydrophilic anionic group-forming group and an active hydrogen group A composition comprising a compound is charged into a reaction device such as a reaction vessel equipped with a stirring device and capable of heating and cooling,
It can be obtained by a urethanization reaction and a radical copolymerization reaction. (A) Charge amount and (c)
The ratio of (d), (e), and (f) to the total amount charged is 5 / 95-
It is preferably 95/5, particularly preferably 10/90 to 90/10. In this case, in order to accelerate the urethanization reaction, if necessary, use an organometallic compound such as dibutyltin dilaurate or dioctyltin dilaurate, or an urethanization catalyst such as an organic amine such as triethylenediamine or triethylamine or a salt thereof. You can The acrylic-polyurethane-based copolymer having a carboxylic acid group obtained by synthesis is dispersed in water together with a hydrophilic organic solvent having a boiling point of less than 100 ° C.

The above-mentioned (a) ethylenically unsaturated monomer is not particularly limited, and examples thereof include hydrophilic polar group-containing ethylenically unsaturated monomer, keto group- or aldehyde group-containing ethylenically unsaturated monomer, and other ethylenic unsaturated monomers. Unsaturated monomers are mentioned.

Examples of the hydrophilic polar group-containing ethylenically unsaturated monomer include poly (oxyalkylene) ether glycol monoacrylate, poly (oxyalkylene) ether glycol monomethacrylate, poly (oxyalkylene) ether glycol monoalkyl ether acrylate, poly ( (Oxyalkylene) ether glycol monoalkyl ether methacrylate, glycidyl acrylate, glycidyl methacrylate, and other compounds having an alkylene oxide added to a compound having an ethylenically unsaturated double bond and an epoxy group, poly (oxyethylene) chain-containing ethylenically unsaturated Oxyethylene group-containing ethylenically unsaturated monomers such as monomers, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, maleic acid monoester , Fumaric acid, fumaric acid monoesters, itaconic acid, itaconic acid monoesters and other carboxylic acid-containing ethylenically unsaturated monomers, sulfonated styrene, sulfonated α-methylstyrene, sulfonic acid-containing ethylenically unsaturated monomers Acid-containing ethylenically unsaturated monomers such as allylamine, allylamine, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl acrylate, N, N-diethylaminoethyl methacrylate,
Examples thereof include those obtained by adding alkylene oxide, and base-containing ethylenically unsaturated monomers such as primary, secondary or tertiary amino group-containing ethylenically unsaturated monomers.

Examples of the ethylenically unsaturated monomer containing a keto group or an aldehyde group include acrolein, diacetone acrylamide, diacetone methacrylamide, formyl styrene, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone, vinyl acetophenone, vinyl benzophenone, acryl. Oxypropenal, diacetone acrylate, acetonitrile acrylate,
2-hydroxypropyl acrylate acetyl acetate, butanediol-1,4-acrylate acetyl acetate, methacryloxypropenal, diacetone methacrylate, acetonitrile methacrylate, 2
-Hydroxypropyl methacrylate acetyl acetate, butanediol-1,4-methacrylate acetyl acetate and the like can be mentioned.

Other ethylenically unsaturated monomers include alkyl acrylate, cycloalkyl acrylate,
Acrylic esters such as phenyl acrylate, benzyl acrylate, glycidyl acrylate, etc., Methacrylic acid esters such as alkyl methacrylate, cycloalkyl methacrylate, phenyl methacrylate, benzyl methacrylate, glycidyl methacrylate, vinyl acetate, propionic acid Vinyl ester compounds such as vinyl, vinyl alkyl ethers such as vinyl methyl ether, vinyl cyclohexyl ether, vinyl phenyl ether, vinyl benzyl ether, vinyl glycidyl ether and other vinyl ether compounds, acrylonitrile, methacrylonitrile and other vinyl cyanide compounds , Styrene, vinyltoluene, α-methylstyrene and other ethylenically unsaturated double bond-containing aromatic compounds, vinyl chloride, vinyl bromide and other halogenated vinyl compounds. , Vinylidene chloride, vinylidene bromide, and other vinylidene halides, maleic acid diesters, such as dialkyl maleates, fumaric acid diesters, such as dialkyl fumarate, itaconic acid diesters, such as dimethyl itaconate, N, N- Dialkylacrylamides such as dimethylacrylamide, heterocyclic vinyl compounds such as N-vinylpyrrolidone and 2-vinylpyridine,
2-hydroxyethyl acrylate, hydroxypropyl acrylate, polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, 2
-Ethyl-caprolactone adduct of hydroxyethyl acrylate, β-methyl-γ-valerolactone adduct of 2-hydroxyethyl acrylate, acrylates such as glycerol monoacrylate and glycerol diacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, Polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, 2-hydroxyethyl methacrylate ε
-Caprolactone adduct, β-methyl-γ-valerolactone adduct of 2-hydroxyethyl methacrylate, methacrylates such as glycerol monomethacrylate and glycerol dimethacrylate, allyl compounds such as allyl alcohol, glycerol monoallyl ether and glycerol diallyl ether Etc.

These ethylenically unsaturated monomers may be used alone or in admixture of two or more.

The radical polymerization initiator used in the radical polymerization of the above-mentioned (b) ethylenically unsaturated monomer is not particularly limited, and examples thereof include 2,2'-azobisisobutyronitrile and 2,2'-. Azobis-2-methylbutyronitrile, dimethyl 2,2'-azobisisobutyrate, azobiscyanovaleric acid, 1,1'-azobis- (cyclohexane-1-carbonitrile), 2,2'-azobis- (2,2
4-dimethylvaleronitrile), 2,2'-azobis-
Azo compounds such as (4-methoxy-2,4-dimethylvaleronitrile), 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1
-Bis (t-hexylperoxy) cyclohexane,
1,1-bis (t-hexylperoxy) -3,3,5
-Trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, n-butyl-4,4
-Bis (t-butylperoxy) valerate, 2,2-
Bis (t-butylperoxy) butane, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, t-hexyl peroxide, 1,1,3,3-tetramethylbutyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, di-t-butyl peroxide, isobutyroyl peroxide,
3,5,5-trimethylhexanoyl peroxide,
Octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide, benzoyl peroxide, toluyl benzoyl peroxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, bis (4-t-butyl) Cyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-methoxybutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) Peroxydicarbonate, α, α'-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanate, 1,1,3,3-tetramethylbutylperoxyneodecane , 1-cyclohexyl-1-methylethylperoxyneodecanate, t-hexylperoxyneodecanate, t-butylperoxyneodecanate, t-hexylperoxypivalate, t-butylperoxypivalate , 2,5-dimethyl-2,5
-Bis (2-ethylhexylperoxy) hexane,
1,1,3,3-tetramethylbutylperoxy-2-
Ethyl hexanate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanate, t-hexylperoxy-2-ethylhexanate, t-butylperoxy-2-ethylhexanate, t-butylperoxy Isobutyrate, t-butylperoxylaurate, t-butylperoxy-3,5,5-trimethylhexanate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxyisopropyl monocarbonate, t-butylperoxide Oxy-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, 2,5-dimethyl-2,5-bis (m-toluoylperoxy) hexane, t-butyl Peroxyacetate, t-hexyl peroxybenzoe DOO, t- butyl peroxy -m- toluoyl benzoate, t- butyl peroxybenzoate, and a bis (t-butylperoxy) organic peroxides such as isophthalate. The radical polymerization initiators used for radical polymerization of these ethylenically unsaturated monomers may be used alone or in combination of two or more.

The above (c) organic polyisocyanate is not particularly limited and includes, for example, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate and 2,4-toluene diisocyanate. , 2, 6
-Toluene diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,
4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,
4'-diphenylpropane diisocyanate, 1,2-
Phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate,
Aromatic diisocyanates such as 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate, 1,6-hexamethylene diisocyanate,
Aliphatic diisocyanates such as 1,4-tetramethylene diisocyanate and lysine diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate,
Aroaliphatic diisocyanates such as p-xylene diisocyanate and tetramethyl xylene diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, alicyclic diisocyanates such as hydrogenated tetramethyl xylene diisocyanate, and the like. . Further, so-called modified polyisocyanates such as adduct modified products, buret modified products, isocyanurate modified products, uretonimine modified products, uretdione modified products and carbodiimide modified products of these organic diisocyanates can also be used. Further, polyisocyanates called so-called polymeric bodies such as polyphenylene polymethylene polyisocyanate and crude toluene diisocyanate can also be used. These organic polyisocyanates can be used alone or in admixture of two or more.

The compound containing the (d) mercapto group and the active hydrogen group is not particularly limited, and examples thereof include polythiol, hydroxythiol, aminothiol and the like.

Examples of the polythiol include methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-
Propanedithiol, 2,2-propanedithiol,
1,6-hexanedithiol, 1,2,3-propanetrithiol, tetrakis (mercaptomethyl) methane,
1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3
-Dithiol, 3,4-dimethoxybutane-1,2-dithiol, 3,6-dioxaoctane-1,8-dimercaptan, 2-methylcyclohexane-2,3-dithiol, bicyclo [2,2,1] Hepta-exo-cis
-2,3-Dithiol, 1,1-bis (mercaptomethyl) cyclohexane, thiomalic acid bis (2-mercaptoethyl ester), 2,3-dimercaptosuccinic acid (2-mercaptoethyl ester), 2,3-dimercapto -1-Propanol (2-mercaptoacetate), 2,3-dimercapto-1-propanol (3-
Mercaptoacetate), diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, 2,2-bis ( Mercaptomethyl) -1,3-propanedithiol, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (2-mercapto) Acetate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3
-Mercaptopropionate), 1- (1'-mercaptomethylthio) -2,3-dimercaptopropane, 1-
(2'-mercaptoethylthio) -2,3-dimercaptopropane, 1- (3'-mercaptopropylthio)-
2,3-dimercaptopropane, 1- (4'-mercaptobutylthio) -2,3-dimercaptopropane, 1-
(5'-mercaptopentylthio) -2,3-dimercaptopropane, 1- (6'-mercaptohexylthio)-
2,3-dimercaptopropane, 1,2-bis (1'-
Mercaptomethylthio) -3-mercaptopropane,
1,2-bis (2'-mercaptoethylthio) -3-mercaptopropane, 1,2-bis (3'-mercaptopropylthio) -3-mercaptopropane, 1,2-bis (4'-mercaptobutylthio) ) -3-Mercaptopropane, 1,2-bis (5'-mercaptopentylthio)
-3-mercaptopropane, 1,2-bis (6'-mercaptohexylthio) -3-mercaptopropane, 1,
2,3-tris (1'-mercaptomethylthio) propane, 1,2,3-tris (2'-mercaptoethylthio) propane, 1,2,3-tris (3'-mercaptopropylthio) propane, 1, 2,3-Tris (4'-
Mercaptobutylthio) propane, 1,2,3-tris (5'-mercaptopentylthio) propane, 1,2,
Aliphatic polythiols such as 3-tris (6'-mercaptohexylthio) propane, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercapto) Methyl) benzene, 1,3-bis (mercaptomethyl) benzene,
1,4-bis (mercaptomethyl) benzene, 1,2-
Bis (mercaptoethyl) benzene, 1,3-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene, 1,2-bis (mercaptomethyloxy) benzene, 1,3-bis (mercaptomethyl) benzene (Oxy) benzene, 1,4-bis (mercaptomethyloxy) benzene, 1,2-bis (mercaptoethyloxy) benzene, 1,3-bis (mercaptoethyloxy) benzene, 1,4-bis (mercaptoethyloxy) Benzene, 1,2,3-trimercaptobenzene,
1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3 , 5-Tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, 1,3,5-tris (mercaptoethyl) benzene, 1 , 2,3-Tris (mercaptomethyloxy) benzene, 1,2,4-tris (mercaptomethyloxy) benzene, 1,3,5-tris (mercaptomethyloxy) benzene, 1,2,3-tris (mercapto) Ethyloxy) benzene, 1,2,4-tris (mercaptoethyloxy) benzene, 1,3,5-tris (mercaptoethyl) Carboxymethyl) benzene, 1,2,
3,4-tetramercaptobenzene, 1,2,3,5-
Tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1,2,3,4-tetrakis (mercaptomethyl) benzene, 1,2,3,5-tetrakis (mercaptomethyl) benzene, 1,2, 4,5-Tetrakis (mercaptomethyl) benzene, 1,2,3,4
-Tetrakis (mercaptoethyl) benzene, 1,2,
3,5-tetrakis (mercaptoethyl) benzene,
1,2,4,5-tetrakis (mercaptoethyl) benzene, 1,2,3,4-tetrakis (mercaptoethyl) benzene, 1,2,3,5-tetrakis (mercaptomethyloxy) benzene, 1,2,2 4,5-Tetrakis (mercaptomethyloxy) benzene, 1,2,3
4-tetrakis (mercaptoethyloxy) benzene,
1,2,3,5-tetrakis (mercaptoethyloxy) benzene, 1,2,4,5-tetrakis (mercaptoethyloxy) benzene, 2,2′-dimercaptobiphenyl, 4,4′-dimercaptobiphenyl, 4,
4'-dimercaptodibenzyl, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,
6-naphthalenedithiol, 2,7-naphthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene-1,3-dithiol,
9,10-anthracene dimethanethiol, 1,3-di (4'-methoxyphenyl) propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol Aromatic polythiols such as 2,4-di (4'-mercaptophenyl) pentane, and 2,5-dichlorobenzene-1,3-
Dithiol, 1,3-di (4'-chlorophenyl) propane-2,2-dithiol, 3,4,5-tribromo-
1,2-Dimercaptobenzene, 2,3,4,6-tetrachloro-1,5-bis (mercaptomethyl) benzene and other chlorine-substituted compounds, bromine-substituted and other halogen-substituted aromatic polythiols, and 2-methyl Amino-4,6-dithiol-sym-triazine, 2-ethylamino-4,6
-Dithiol-sym-triazine, 2-amino-4,
6-dithiol-sym-triazine, 2-morpholino-4,6-dithiol-sym-triazine, 2-cyclohexylamino-4,6dithiol-sym-triazine, 2-methoxy-4,6-dithiol-sym-triazine, 2-phenoxy-4,6-dithiol-sy
Polythiols containing a heterocycle such as m-triazine, 2-thiobenzeneoxy-4,6-dithiol-sym-triazine, and 2-thiobutyloxy-4,6-dithiol-sym-triazine, and 1,2 -Bis (mercaptomethylthio) benzene, 1,3-bis (mercaptomethylthio) benzene, 1,4-bis (mercaptomethylthio) benzene, 1,2-bis (mercaptoethylthio) benzene, 1,3-bis (mercapto) Ethylthio) benzene, 1,4-bis (mercaptoethylthio)
Benzene, 1,2,3-tris (mercaptomethylthio) benzene, 1,2,4-tris (mercaptomethylthio) benzene, 1,3,5-tris (mercaptomethylthio) benzene, 1,2,3-tris (mercapto) Ethylthio) benzene, 1,2,4-tris (mercaptoethylthio) benzene, 1,3,5-tris (mercaptoethylthio) benzene, 1,2,3,4-tetrakis (mercaptomethylthio) benzene, 1 , 2, 3, 5-
Tetrakis (mercaptomethylthio) benzene, 1,
2,4,5-Tetrakis (mercaptomethylthio) benzene, 1,2,3,4-tetrakis (mercaptoethylthio) benzene, 1,2,3,5-tetrakis (mercaptoethylthio) benzene, 1,2,4 , 5-Tetrakis (mercaptoethylthio) benzene, bis (4-mercaptophenyl) sulfide, etc., or aromatic polythiols containing a sulfur atom in addition to the mercapto group such as alkylated products thereof, bis (mercaptomethyl) sulfide, bis (Mercaptoethyl) sulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropyl) methane, 1,2-
Bis (mercaptomethylthio) ethane, 1,2- (2-
Mercaptoethylthio) ethane, 1,2- (3-mercaptopropyl) ethane, 1,3-bis (mercaptomethylthio) propane, 1,3-bis (2-mercaptoethylthio) propane, 1,3-bis (3 -Mercaptopropylthio) propane, 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane, 2-mercaptoethylthio-1,3-propanedithiol, 1,2,3
-Tris (mercaptomethylthio) propane, 1,2,
3-tris (2-mercaptoethylthio) propane,
1,2,3-Tris (3-mercaptopropylthio) propane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl)
Methane, tetrakis (3-mercaptopropylthiomethyl) methane, bis (2,3-dimercaptopropyl) sulfide, 2,5-dimercapto-1,4-dithiane,
Bis (mercaptomethyl) disulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) disulfide, etc., or their thioglycolic acid or mercaptopropionic acid esters, hydroxymethylsulfide-bis (2-mercaptoacetate), hydroxymethylsulfide -Bis (3-mercaptopropionate), hydroxyethyl sulfide-
Bis (2-mercaptoacetate), hydroxyethyl sulfide-bis (3-mercaptopropionate),
Hydroxypropyl sulfide-bis (2-mercaptoacetate), hydroxypropyl sulfide-bis (3-mercaptopropionate), hydroxymethyldisulfide-bis (2-mercaptoacetate), hydroxymethyldisulfide-bis (3-mercaptopropionate) ), Hydroxyethyldisulfide-bis (2-mercaptoacetate), hydroxyethyldisulfide-bis (3-mercaptopropionate), hydroxypropyldisulfide-bis (2-mercaptoacetate), hydroxypropyldisulfide-bis (3- Mercaptopropionate), 2-mercaptoethyl ether-bis (2-mercaptoacetate), 2
-Mercaptoethyl ether-bis (3-mercaptopropionate), 1,4-dithian-2,5-diol-bis (2-mercaptoacetate), 1,4-dithian-2,5-diol-bis (3 -Mercaptopropionate), thioglycolic acid-bis (2-mercaptoethyl ester), thiodipropionic acid-bis (2-mercaptoethyl ester), 4,4-thiodibutyric acid-bis (2-mercaptoethyl ester), Dithiodiglycolic acid-bis (2-mercaptoethyl ester), dithiodipropionic acid-bis (2-mercaptoethyl ester), 4,4-dithiodibutyric acid-bis (2-mercaptoethyl ester), thiodiglycolic acid- Screw (2,
3-dimercaptopropyl ester), thiodipropionic acid-bis (2,3-dimercaptopropyl ester), dithioglycolic acid-bis (2,3-dimercaptopropyl ester), dithiodibropionic acid (2,3
An aliphatic polythiol containing a sulfur atom in addition to a mercapto group such as (dimercaptopropyl ester), 3,4-
Thiophenedithiol, 2,5-bis (mercaptomethyl) tetrahydrothiophene, bis (mercaptomethyl) -1,3-dithiolane, 2,5-dimercapto-
1,3,4-thiadiazole, 2,5-dimercapto-
1,4-dithiane, 2,5-dimercaptomethyl-1,
Examples thereof include heterocyclic compounds containing a sulfur atom in addition to the mercapto group such as 4-dithiane.

Examples of the hydroxy thiol include 2-mercapto-1-hydroxyethane, 2-mercapto-1-hydroxypropane, 1-mercapto-2-hydroxypropane, 3-mercapto-1-hydroxypropane, 2
-Mercapto-1-hydroxybutane, 3-mercapto-1-hydroxybutane, 4-mercapto-1-hydroxybutane and other monomercaptomonool compounds, thioglycerol, 2,3-dihydroxy-1-mercaptobutane, 2,3 -Dihydroxy-1-mercaptopentane, 3,4-dihydroxy-1-mercaptobutane,
3,4-dihydroxy-1-mercaptopentane, 3,
Monomercaptodiol compounds such as 4-dihydroxy-1-mercaptohexane, 2-hydroxy-1,3-dimercaptopropane, 1-hydroxy-2,3-dimercaptopropane, 2-hydroxy-1,3-dimercaptobutane , 1-hydroxy-2,3-dimercaptobutane, 2-hydroxy-1,3-dimercaptopentane,
2-hydroxy-1,3-dimercaptohexane, 3-
Examples thereof include dimercaptomonool compounds such as hydroxy-1,4-dimercaptobutane, 3-hydroxy-1,4-dimercaptopentane, and 3-hydroxy-1,4-dimercaptohexane.

Examples of aminothiols include β-mercaptoethylamine, β-mercaptopropylamine, γ-mercaptopropylamine, 2-aminothiophenol,
3-aminothiophenol, 4-aminothiophenol, etc. are mentioned.

These compounds containing a mercapto group and an active hydrogen group can be used alone or in admixture of two or more.

The compound containing an active hydrogen group other than the above (f) mercapto group is not particularly limited, and those referred to as long-chain polyols in the polyurethane industry and those referred to as chain extenders are mentioned. Can be mentioned.

Examples of the long-chain polyols include polyester polyols, polycarbonate polyols, polyether polyols, polyolefin polyols, animal / vegetable polyols, and copolyols thereof.

Known polyester polyols include succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydroorthophthalic acid and naphthalenedicarboxylic acid. , One or more of polycarboxylic acids such as trimellitic acid, acid esters, or acid anhydrides, and ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-
Butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8- Octanediol, 1,9-nonanediol, diethylene glycol,
Dipropylene glycol, 1,4-cyclohexanedimethanol, or ethylene oxide or propylene oxide adduct of bisphenol A, low molecular weight polyols such as trimethylolpropane, glycerin, pentaerythritol, hexamethylenediamine, xylylenediamine, isophoronediamine, etc. Polyester polyols or polyester amide polyols obtained by dehydration condensation reaction with one or more low molecular weight amino alcohols such as low molecular weight polyamines, monoethanolamine, and diethanolamine. Further, a lactone polyester polyol obtained by ring-opening polymerization of a cyclic ester (lactone) monomer such as ε-caprolactone or γ-valerolactone using a low molecular weight polyol, a low molecular weight polyamine or a low molecular weight amino alcohol as an initiator can be mentioned.

Examples of the polycarbonate polyol include those obtained by dealcoholation reaction and dephenolation reaction of the low molecular weight polyol used in the synthesis of the above polyester polyol with diethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate and the like. To be

As the polyether polyol, a polyethylene glycol obtained by ring-opening polymerization of ethylene oxide, propylene oxide, tetrahydrofuran or the like with a low molecular weight polyol, a low molecular weight polyamine or a low molecular weight amino alcohol used as the above-mentioned polyester polyol as an initiator, Examples thereof include polypropylene glycol, polytetramethylene ether glycol, and the like, and polyether polyols obtained by copolymerizing these, and further, the above-mentioned polyester polyols and polyester ether polyols using the polycarbonate polyol as an initiator.

Examples of the polyolefin polyols include hydroxyl group-containing polybutadiene, hydrogenated hydroxyl group-containing polybutadiene, hydroxyl group-containing polyisoprene, hydrogenated hydroxyl group-containing polyisoprene, hydroxyl group-containing chlorinated polypropylene and hydroxyl group-containing chlorinated polyethylene.

Examples of animal and plant polyols include castor oil-based polyols and silk fibroin.

In addition to dimer acid type polyols and hydrogenated dimer acid type polyols, epoxy resins, polyamide resins,
Resins such as polyester resin, acrylic resin, rosin resin, urea resin, melamine resin, phenol resin, coumarone resin and positive vinyl alcohol can also be preferably used as the long chain polyol.

The number average molecular weight of these long chain polyols is preferably 500 to 10,000.

As the chain extender, a compound having two or more active hydrogen groups in the molecule having a number average molecular weight of less than 500,
Specific examples thereof include the aforementioned low molecular weight polyols, low molecular weight polyamines, and low molecular weight amino alcohols.

These compounds containing an active hydrogen group other than the mercapto group can be used alone or in admixture of two or more.

The compound containing the above-mentioned (f) hydrophilic anionic group-forming group and active hydrogen group is not particularly limited, and examples thereof include α-hydroxypropionic acid, hydroxysuccinic acid, dihydroxysuccinic acid and ε-hydroxypropane. -1,2,3-tricarboxylic acid, hydroxyacetic acid,
α-hydroxybutyric acid, hydroxystearic acid, ricinoleic acid, ricinoelaidic acid, ricinostearolic acid,
Hydroxy fatty acid obtained by hydroxylating unsaturated fatty acid such as salicylic acid, mandelic acid, etc., oleic acid, ricinoleic acid, linoleic acid, glutamine, asparagine, lysine, diaminopropionic acid, ornithine, diaminobenzoic acid, diamine type of diaminobenzenesulfonic acid, etc. Amino acids, glycine, alanine, glutamic acid, taurine,
Aminocaproic acid, aminobenzoic acid, aminoisophthalic acid, monoamine type amino acids such as sulfamic acid, or
Carboxylic acid-containing polyols such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid and 2,2-dimethylolvaleric acid; 1: 1 of iminodiacetic acid and glycidol.
(Molar ratio) Chelate type such as adduct, polyester polyol introduced with 5-sulfoisophthalic acid skeleton,
Examples thereof include polycaprolactone having water or a carboxyl group-containing alcohol as an initiator, a transesterification product of an active hydrogen group-containing polyester and a carboxyl group-containing alcohol, and a transesterification product of an active hydrogen group-containing polycarbonate and a carboxyl group-containing alcohol. Further, the long-chain polyols and low-molecular-weight glycols, trimethylolpropane, low-molecular-weight polyols such as glycerin and polyamines, and a half ester mixture containing a carboxyl group obtained by reacting a polycarboxylic acid anhydride, Half amide mixtures can also be used. When a polyol is added to dianhydride such as pyromellitic dianhydride, 2
Since one carboxylic acid is produced, a hydrophilic anionic group can be introduced into the molecular chain of the polyester polyol. These compounds containing a hydrophilic anionic group-forming group and an active hydrogen group can be used alone or in admixture of two or more.

Next, in order to impart a function as a hydrophilic polar group, specifically a hydrophilic anion group, to the carboxylic acid group in the acrylic-polyurethane type copolymer having a carboxylic acid group, an acrylic resin having a carboxylic acid group is provided. After synthesizing the polyurethane copolymer, the carboxylic acid group is neutralized using amino alcohol as the basic neutralizing agent.

The above amino alcohol is not particularly limited, and examples thereof include triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine,
Monoethanolamine, dimethylethanolamine, diethylethanolamine, 2-amino-2-ethyl-1
-Propanol and the like. These amino alcohols can be used alone or in combination of two or more.

As the basic neutralizing agent, in addition to the above amino alcohols, organic amines such as ethylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, morpholine, N-methylmorpholine and pyridine, lithium, potassium, Examples include alkali metals such as sodium, inorganic alkalis such as sodium hydroxide and potassium hydroxide, ammonia, etc. However, when considering both efficient neutralization and dispersibility in water, use amino alcohol. Is preferred.

An acrylic-polyurethane copolymer having a carboxylic acid group present in a hydrophilic organic solvent having a boiling point of less than 100 ° C., the above amino alcohol, a compound having two or more hydrazide groups in one molecule, And, if necessary, it is preferable that additives and auxiliaries commonly used in an aqueous system are dispersed in water and mixed by stirring to form an aqueous dispersion. A compound having two or more hydrazide groups in one molecule,
Also, additives and auxiliaries commonly used in water-based systems need not necessarily be dispersed in water together with the above amino alcohol.

The above compound having two or more hydrazide groups in one molecule is not particularly limited, and examples thereof include 4,
4'-bisbenzenedihydrazide, 2,6-pyridinedihydrazide, 1,4-cyclohexanedihydrazide,
Dihydrazide compounds such as N, N′-hexamethylenebissemicarbazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, hydrazide dihydrazide, azelaic dihydrazide Dodecanedicarboxylic acid dihydrazide, hexadecanedicarboxylic acid dihydrazide,
Maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide, terephthalic acid dihydrazide, isophthalic acid dihydrazide, phthalic acid dihydrazide, 2,6
-Naphthoic acid dihydrazide, 1,4-naphthoic acid dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide,
Dicarboxylic acid dihydrazides such as iminodiacetic acid dihydrazide, citric acid trihydrazide, 1,2,4-benzenetricarboxylic acid trihydrazide, nitrilotriacetic acid trihydrazide, cyclohexanetricarboxylic acid trihydrazide, trimellitic acid trihydrazide and other tricarboxylic acid trihydrazides , Tetracarboxylic acid tetrahydrazides such as ethylenediaminetetraacetic acid tetrahydrazide, 1,4,5,8-naphthoic acid tetrahydrazide, pyromellitic acid tetrahydrazide, carbonic acid dihydrazide, carbohydrazide, thiocarbodihydrazide, bissemicarbazide, acid Examples thereof include hydrazide polymers. These compounds having two or more hydrazide groups in one molecule can be used alone or in combination of two or more.

Examples of the additives and auxiliaries commonly used in the water-based system as required above include pigments, dyes, preservatives, fungicides, antibacterial agents, thixotropic agents, antiblocking agents,
Dispersion stabilizer, viscosity modifier, film forming aid, leveling agent, gelation inhibitor, light stabilizer, antioxidant, ultraviolet absorber, inorganic and organic filler, plasticizer, lubricant, antistatic agent, reinforcing material. , Catalysts and the like.

Further, as additives and auxiliaries commonly used in the water-based system according to the above-mentioned need, JP-A-6-22031 is used.
Glycol ether compounds as described in JP-A-9 may be added.

The method for obtaining the acrylic-polyurethane-based copolymer having a hydrophilic anionic group has been described above in detail. As the water-based acrylic-polyurethane-based copolymer to be used in the present invention, this hydrophilic Examples of the acrylic-polyurethane-based copolymer having a hydrophilic nonionic group, a hydrophilic cationic group, and a hydrophilic amphoteric group in addition to the anionic group. For example, the method of the present invention is
It can also be applied as a method for producing an aqueous emulsion as described in JP-A No. 11-269247.

Next, a method for removing a hydrophilic organic solvent having a boiling point of less than 100 ° C. from the above water dispersion will be described.

In the present invention, when the hydrophilic organic solvent having a boiling point of less than 100 ° C. contained in the above water dispersion is removed, the removal operation is performed while maintaining the temperature of the water dispersion below 50 ° C. When the removal operation is performed with the temperature of the aqueous dispersion at 50 ° C. or higher, the appearance of the desired aqueous acrylic-polyurethane resin is remarkably clouded, which is not preferable.

The greatest feature of the manufacturing method of the present invention is that
It is a method of removing a hydrophilic organic solvent having a boiling point of less than 100 ° C. contained in the above aqueous dispersion. That is, in the present invention, while maintaining the temperature of the aqueous dispersion below 50 ° C,
(1) The amount of azeotrope of the hydrophilic organic solvent (A) and water is measured during the removal while maintaining a constant degree of vacuum, (2)
By confirming that the amount of the azeotrope of the hydrophilic organic solvent (A) and water per minute is less than a certain amount, (3) increasing the degree of vacuum, repeating the method When performing the removal by interlocking the measurement of the outflow amount of the azeotrope of the organic solvent (A) and water and the degree of vacuum, a method is adopted in which the removal is carried out after the constant degree of vacuum is passed through three or more stages.

In the present invention, as a general rule, batch distillation is premised as the solvent removal method. Other solvent removal methods include continuous film distillation and the like.
In principle, it is not desirable for the method according to the invention.

While maintaining the above (1) constant vacuum degree,
The method for measuring the outflow amount of the azeotrope of the hydrophilic organic solvent (A) having a boiling point of less than 100 ° C. and water during the removal is not particularly limited, and a method of actually measuring the outflow amount or an outflow amount Such as a method to automatically measure the amount using some kind of device,
It is possible to use a known method.

Although water may azeotropically evaporate under the reduced pressure atmosphere conditions as described above, in the present invention, the solid content desired for the target resin is obtained as necessary after the completion of solvent removal. Since it is possible to perform correction by adding water as described above, water may azeotrope during solvent removal.

The above boiling point of 100 in (2) above
In the present invention, the amount of the azeotrope of the hydrophilic organic solvent (A) and water azeotrope per minute below 0 ° C. is, in the present invention, 0.1 with respect to the total charged amount of the hydrophilic organic solvent (A) and water. 001-
The amount is preferably 1.5%, and more preferably 0.003 to 1.4% with respect to the total charged amount of the hydrophilic organic solvent (A) and water. More preferable.

Regarding the above preferable outflow amount,
Although it depends on the fractional distillation capacity in the equipment used, the larger the total amount of charge, the more the amount of outflow per minute is the above with respect to the total amount of the hydrophilic organic solvent (A) having a boiling point of less than 100 ° C and water. The% value of is preferably smaller.

In the present invention, when it is confirmed that the outflow amount per minute is less than a certain amount, the solvent is removed by a method of increasing the degree of vacuum. In this case, the degree of vacuum does not gradually increase, but the degree of vacuum is maintained at a constant level, and when it is confirmed that the above-mentioned outflow amount is less than a certain amount, the degree of vacuum is increased and the degree of vacuum is increased again. Take a method to keep the degree constant. When a method of gradually increasing the degree of vacuum is adopted, the viscosity of the aqueous acrylic-polyurethane-based resin, which is the target product obtained in each batch, becomes non-uniform, and a resin with a stable viscosity desired in the present invention is obtained. I can't.

In the present invention, the constant vacuum degree is set in three stages or more to remove the solvent. If the constant degree of vacuum is two steps or less, sufficient solvent removal cannot be performed.

In the present invention, this constant degree of vacuum is in the range of 34.0 to 13.2 (kPa) as the first step,
In the range of 13.1-9.2 (kPa) as the second stage,
And, it is preferable to set in the range of 9.1 to 3.9 (kPa) as the third stage. With such a setting, a desired water-based acrylic-polyurethane resin can be obtained.

As described above, when the hydrophilic organic solvent (A) having a boiling point of less than 100 ° C. is removed, by setting such multistage constant depressurization conditions, the desired aqueous acrylic-polyurethane resin is obtained. It is possible to obtain the aqueous acrylic-polyurethane-based resin which enables the hydrophilic organic solvent (A) remaining therein to be further reduced and has a stable viscosity.

[0061]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

Production Example: Acrylic having a carboxylic acid group
Polyurethane-based copolymer synthesis Stirrer, thermometer, condenser, capacity with dropping funnel: 10
In a reaction container of 00 ml, 118.5 g of polyester polyol having a number average molecular weight of 2000 (Nipporan 4070: manufactured by Nippon Polyurethane Industry Co., Ltd.), 2.7 g of hydroxyethyl methacrylate (2-HEMA), 3.0 g of thioglycol, and dimethylol. Butanoic acid (DMBA) 4.4 g, methyl ethyl ketone (MEK) 16.5 g
Each was charged and heated with stirring, and when the temperature reached 70 ° C., 19.9 g of hexamethylene diisocyanate (HDI) and 0.03 g of dioctyltin dilaurate (DOTDL) as a catalyst were charged, and the mixture was stirred at 80
Urethane reaction was carried out at ℃ for 7 hours. The reaction solution was subjected to IR measurement to confirm that the isocyanate group had disappeared, then 57.8 g of methyl ethyl ketone (MEK) and 74.3 g of isopropanol (IPA) were added, and the mixture was stirred until uniform. At the time of homogenization, 246.5 g of methyl methacrylate (MMA), 62.9 g of butyl acrylate (n-BA), 12.4 g of acrylic acid (AA) and diacetone acrylamide ( DAAM)
24.8 g of each was charged and heated with stirring,
The temperature was raised to 8 ° C. Next, 5.0 g of t-butylperoxy-2-ethylhexanoate and 175.7 of methyl ethyl ketone (MEK) were added to the dropping funnel as polymerization initiators.
g and 175.7 g of isopropanol (IPA) were charged, respectively, and this was added dropwise to the reaction vessel heated to 78 ° C. over 5 hours. After completion of dropping, the mixture was further stirred at 78 ° C. for 7 hours and then cooled to 30 ° C. to obtain an acrylic-polyurethane copolymer.

Using this acrylic-polyurethane type copolymer, aqueous dispersions of aqueous acrylic-polyurethane type resin were obtained in the following examples and comparative examples. Regarding the obtained water dispersion of the aqueous acrylic-polyurethane-based resin, the appearance of the water dispersion, the particle size of the resin, the viscosity of the water dispersion, the amount of MEK remaining in the water dispersion, and the IPA remaining in the water dispersion. The amount of each was measured by the following method. Appearance of water dispersion: visually confirmed. Resin particle size: Laser zeta electrometer (Otsuka Electronics Co., Ltd.)
Manufactured). Viscosity of water dispersion: Measured using a Vismetron viscometer VSA-L type (manufactured by Shibaura System Co., Ltd.). MEK residual amount in water dispersion: measured using gas chromatography. IPA residual amount in water dispersion: measured using gas chromatography.

Example 1 200.0 g of the above-obtained acrylic-polyurethane copolymer was charged into a 500 ml reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a vacuum distillation apparatus, and dimethyl ethanol was added. 2.9 g of amine (DMEA) was added,
The mixture was stirred at 200 rpm for 15 minutes. Next, 181.0 g of water
What dissolved 2.5 g of adipic acid hydrazide (ADH) was prepared in the dropping funnel, and it stirred at 200 rpm, making it dripped in the reaction container over 10 minutes. Then, after reducing the pressure to 14.6 kPa, the liquid temperature was set to 45.
While keeping the temperature below ℃, confirm that the outflow amount of solvent etc. per minute has become less than 1.0 g (= equivalent to 0.4% of the total amount of MEK / IPA / water charged). The solvent was removed up to. The amount of the solvent and the like removed in this first stage is as follows. MEK: 40.7 g IPA: 19.9 g Water: 4.0 g After that, the pressure was set to 11.3 kPa and the outflow amount of the solvent per minute was 1.0 g while keeping the liquid temperature at 45 ° C. or lower. The solvent was removed until it was confirmed that the amount was less than (= the amount corresponding to 0.4% with respect to the total amount of MEK / IPA / water charged). The amounts of the solvent and the like removed in the second stage are as follows. MEK: 8.5 g IPA: 20.8 g Water: 7.1 g After that, the pressure was further increased to 9.0 kPa, and the outflow amount of the solvent or the like per minute was 1. while maintaining the liquid temperature at 45 ° C. or lower. The solvent was removed until it was confirmed that the amount was less than 0 g (= the amount corresponding to 0.4% with respect to the total amount of MEK / IPA / water charged). The amounts of the solvent and the like removed in this third stage are as follows. MEK: 0.7 g IPA: 9.2 g Water: 21.8 g In the third stage, the outflow amount of the solvent etc. was 1.
When it was confirmed that the amount became less than 0 g, the solvent removal was completed (time required for solvent removal: 82 minutes). Finally, the solid content was corrected to 40% with water to obtain the following water-based acrylic-polyurethane resin water dispersion (1). Appearance: Good (translucent) Resin particle size (nm): 55 Viscosity (mPa · s at 25 ° C.): 151 MEK residual amount (%): 0.1 IPA residual amount (%): 0.4

Example 2 Example 1 was reproduced by using the same apparatus, the same raw materials, the same charging amount, and the same method as in Example 1. First,
After reducing the pressure to 14.6 kPa, the amount of the solvent or the like flowing out per minute was 1.0 g while keeping the liquid temperature at 45 ° C or lower.
The solvent was removed until it was confirmed that the amount was less than (= the amount corresponding to 0.4% with respect to the total amount of MEK / IPA / water charged). The amount of solvent etc. removed in this first stage is
It is as follows. MEK: 40.9 g IPA: 20.0 g Water: 4.1 g After that, the pressure was set to 11.3 kPa, and while keeping the liquid temperature at 45 ° C. or lower, the outflow amount of the solvent or the like per minute was 1.0 g. The solvent was removed until it was confirmed that the amount was less than (= the amount corresponding to 0.4% with respect to the total amount of MEK / IPA / water charged). The amounts of the solvent and the like removed in the second stage are as follows. MEK: 8.4 g IPA: 20.9 g Water: 7.1 g After this, the pressure was further increased to 9.0 kPa, and the outflow amount of the solvent or the like per minute was 1. while maintaining the liquid temperature at 45 ° C. or lower. The solvent was removed until it was confirmed that the amount was less than 0 g (= the amount corresponding to 0.4% with respect to the total amount of MEK / IPA / water charged). The amounts of the solvent and the like removed in this third stage are as follows. MEK: 0.6 g IPA: 9.0 g Water: 21.8 g In the third stage, the outflow amount of the solvent etc. per minute is 1.
When it was confirmed that the amount was less than 0 g, the solvent removal was completed (time required for solvent removal: 79 minutes). Finally, the solid content was corrected to 40% with water to obtain an aqueous dispersion (2) of the following aqueous acrylic-polyurethane resin. Appearance: Good (translucent) Resin particle size (nm): 54 Viscosity (mPa · s at 25 ° C.): 150 MEK residual amount (%): 0.1 IPA residual amount (%): 0.3

Example 3 Example 1 was reproduced again using the same apparatus, the same raw materials, the same charging amount, and the same method as those in Example 1. First, after reducing the pressure to 14.6 kPa, the outflow amount of the solvent etc. per minute was 1.0 while keeping the liquid temperature at 45 ° C. or lower.
g (= 0.4% to the total amount of MEK / IPA / water charged)
The solvent was removed until it was confirmed that the amount was less than The amount of the solvent and the like removed in this first stage is as follows. MEK: 40.6 g IPA: 19.8 g Water: 4.0 g After that, the pressure was set to 11.3 kPa, and while keeping the liquid temperature at 45 ° C. or lower, the outflow amount of the solvent or the like per minute was 1.0 g. The solvent was removed until it was confirmed that the amount was less than (= the amount corresponding to 0.4% with respect to the total amount of MEK / IPA / water charged). The amounts of the solvent and the like removed in the second stage are as follows. MEK: 8.0 g IPA: 20.5 g Water: 7.1 g After that, the pressure was further increased to 9.0 kPa, and the outflow amount of the solvent or the like per minute was 1. while maintaining the liquid temperature at 45 ° C. or lower. The solvent was removed until it was confirmed that the amount was less than 0 g (= the amount corresponding to 0.4% with respect to the total amount of MEK / IPA / water charged). The amounts of the solvent and the like removed in this third stage are as follows. MEK: 1.3 g IPA: 9.6 g Water: 22.2 g In the third stage, the outflow amount of the solvent etc. per minute is 1.
When it was confirmed that the amount became less than 0 g, the solvent removal was completed (time required for solvent removal: 83 minutes). Finally, the solid content was corrected to 40% with water to obtain an aqueous dispersion (3) of the following aqueous acrylic-polyurethane resin. Appearance: Good (translucent) Resin particle size (nm): 55 Viscosity (mPa · s at 25 ° C.): 151 MEK residual amount (%): 0.1 IPA residual amount (%): 0.3

In Examples 1 to 3, the water-based acrylic-polyurethane type resins obtained by the exactly same method were obtained at very stable values in terms of resin particle size, viscosity and residual solvent amount.

Comparative Example 1 200.0 g of the above-obtained acrylic-polyurethane copolymer was charged into a 500 ml reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a vacuum distillation apparatus, and dimethyl ethanol was added. 2.9 g of amine (DMEA) was added,
The mixture was stirred at 200 rpm for 15 minutes. Next, 181.0 g of water
What dissolved 2.5 g of adipic acid hydrazide (ADH) was prepared in the dropping funnel, and it stirred at 200 rpm, making it dripped in the reaction container over 10 minutes. Then, after reducing the pressure to 14.6 kPa, the liquid temperature was set to 45.
While keeping the temperature below ℃, confirm that the outflow amount of solvent etc. per minute has become less than 1.0 g (= equivalent to 0.4% of the total amount of MEK / IPA / water charged). The solvent was removed up to. The amount of the solvent and the like removed in this first stage is as follows. MEK: 40.4 g IPA: 20.1 g Water: 4.1 g After this, the pressure was set to 9.0 kPa and the liquid temperature was kept at 4
While keeping the temperature below 5 ° C, confirm that the outflow rate of solvent, etc. per minute was less than 1.0g (= equivalent to 0.4% of the total amount of MEK / IPA / water charged). The solvent was removed until. The amounts of the solvent and the like removed in the second stage are as follows. MEK: 9.4 g IPA: 28.9 g Water: 31.2 g In the second stage, the outflow rate of the solvent etc. per minute is 1.
When it was confirmed that the amount became less than 0 g, the solvent removal was terminated (time required for solvent removal: 73 minutes). Finally, the solid content was corrected to 40% with water to obtain an aqueous dispersion (4) of the following aqueous acrylic-polyurethane resin. Appearance: Good (translucent) Resin particle size (nm): 55 Viscosity (mPa · s at 25 ° C.): 251 MEK residual amount (%): 0.2 IPA residual amount (%): 1.0

When the example and the above comparative example 1 are compared, the viscosity of the obtained aqueous acrylic-polyurethane resin is high. This is because isopropanol (I
This is due to the increase in the remaining amount of PA).

Comparative Example 2 200.0 g of the above-obtained acrylic-polyurethane copolymer was charged into a 500 ml reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a vacuum distillation apparatus, and dimethyl ethanol was added. 2.9 g of amine (DMEA) was added,
The mixture was stirred at 200 rpm for 15 minutes. Next, 181.0 g of water
What dissolved 2.5 g of adipic acid hydrazide (ADH) was prepared in the dropping funnel, and it stirred at 200 rpm, making it dripped in the reaction container over 10 minutes. Then, after reducing the pressure to 9.0 kPa, the liquid temperature was changed to 45 ° C.
Until it is confirmed that the amount of solvent outflow per minute is less than 1.0g (= equivalent to 0.4% of the total amount of MEK / IPA / water) while keeping the following. The solvent was removed. The amount of the solvent and the like removed in this first stage is as follows. MEK: 49.5 g IPA: 47.8 g Water: 40.0 g In the first stage, the outflow amount of the solvent etc. per minute is 1.
When it was confirmed that the amount became less than 0 g, the solvent removal was completed (time required for solvent removal: 34 minutes). Finally, the solid content was corrected to 40% with water to obtain the following water-based acrylic-polyurethane resin water dispersion (5). Appearance: Good (translucent) Resin particle size (nm): 53 Viscosity (mPa · s at 25 ° C.): 456 MEK residual amount (%): 0.5 IPA residual amount (%): 1.9

When the example is compared with the above-mentioned comparative example 2, the viscosity of the obtained aqueous acrylic-polyurethane type resin is high. Moreover, the viscosity is higher than that of Comparative Example 1. This is because isopropanol used as a solvent (IP
This is because the remaining amount of A) is further increased.

Comparative Example 3 200.0 g of the above-obtained acrylic-polyurethane copolymer was charged into a 500 ml reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a vacuum distillation apparatus, and dimethyl ethanol was added. 2.9 g of amine (DMEA) was added,
The mixture was stirred at 200 rpm for 15 minutes. Next, 181.0 g of water
What dissolved 2.5 g of adipic acid hydrazide (ADH) was prepared in the dropping funnel, and it stirred at 200 rpm, making it dripped in the reaction container over 10 minutes. Then, after reducing the pressure to 14.6 kPa, the liquid temperature was adjusted to 65
While keeping the temperature below ℃, confirm that the outflow amount of solvent etc. per minute has become less than 1.0 g (= equivalent to 0.4% of the total amount of MEK / IPA / water charged). The solvent was removed up to. The amount of the solvent and the like removed in this first stage is as follows. MEK: 49.8 g IPA: 49.4 g Water: 33.4 g In the first stage, the outflow amount of the solvent per minute is 1.
When it was confirmed that the amount was less than 0 g, the solvent removal was completed (time required for solvent removal: 114 minutes). Finally, the solid content was corrected to 40% with water to obtain an aqueous dispersion (6) of the following aqueous acrylic-polyurethane resin. Appearance: Poor (cloudy) Resin particle size (nm): 71 Viscosity (mPa · s at 25 ° C.): 131 MEK residual amount (%): 0.1 IPA residual amount (%): 0.5

When the example and the above-mentioned comparative example 3 are compared, the appearance of the obtained aqueous acrylic-polyurethane type resin is deteriorated. This is due to the fact that the heating temperature was set high in order to bring the desolvation to the same level as in the example, while the constant depressurization condition was set to one step. In addition, since the depressurization condition is set to be mild, the time required for desolvation is prolonged.

Comparative Example 4 200.0 g of the above-obtained acrylic-polyurethane copolymer was charged into a reaction vessel having a capacity of 500 ml equipped with a stirrer, a thermometer, a dropping funnel and a vacuum distillation apparatus, and dimethyl ethanol was added. 2.9 g of amine (DMEA) was added,
The mixture was stirred at 200 rpm for 15 minutes. Next, 181.0 g of water
What dissolved 2.5 g of adipic acid hydrazide (ADH) was prepared in the dropping funnel, and it stirred at 200 rpm, making it dripped in the reaction container over 10 minutes. After that, in order to reduce the time required for solvent removal, the liquid temperature was raised to 70 ° C. before depressurization, and then depressurized to 9.0 kPa, and the outflow amount of the solvent, etc. per minute was 1.0 g. (= M
The solvent was removed until it was confirmed that the amount was less than 0.4% of the total amount of EK / IPA / water charged. The amount of the solvent and the like removed in this first stage is as follows. MEK: 49.8 g IPA: 49.2 g Water: 38.1 g In the first stage, the outflow amount of the solvent, etc. per minute is 1.
When it was confirmed that the amount became less than 0 g, the solvent removal was completed (time required for solvent removal: 21 minutes). Finally, the solid content was corrected to 40% with water to obtain an aqueous dispersion (7) of the following aqueous acrylic-polyurethane resin. Appearance: Poor (cloudy) Resin particle size (nm): 75 Viscosity (mPa · s at 25 ° C.): 353 MEK residual amount (%): 0.3 IPA residual amount (%): 1.1

When the example and the above-mentioned comparative example 4 are compared, the appearance of the obtained aqueous acrylic-polyurethane resin is deteriorated. This is due to the same cause as in Comparative Example 3. Further, since the solvent was removed under a constant depressurization condition in one step, it is also possible to increase the viscosity due to the increase in the residual amount of isopropanol (IPA) used as the solvent, as in Comparative Example 2.

[0076]

The production method according to the present invention shortens the time required for producing an aqueous acrylic-polyurethane resin,
In addition, it is possible to suppress heating in the solvent removal treatment, and it is possible to reduce the manufacturing cost. Further, the aqueous acrylic-polyurethane resin obtained by the production method can have a better appearance. Furthermore, for the solvent removal, which is the greatest feature of the production method according to the present invention, the solvent remaining in the resin can be reduced by setting a constant degree of vacuum in multiple stages, regardless of the method of gradually reducing the pressure. It is possible to obtain an aqueous acrylic-polyurethane-based resin having a stable viscosity.

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Claims (4)

[Claims] 1. A method for producing an aqueous acrylic-polyurethane resin, which comprises dispersing a hydrophilic acrylic-polyurethane copolymer synthesized in a hydrophilic organic solvent (A) having a boiling point of less than 100 ° C. in water to prepare water. As a dispersion, and finally when removing the hydrophilic organic solvent (A) in the aqueous dispersion, while maintaining the temperature of the aqueous dispersion below 50 ° C.,
(1) While maintaining a constant degree of vacuum, the amount of azeotrope of the hydrophilic organic solvent (A) and water is measured during the removal, (2)
By confirming that the amount of the azeotrope of the hydrophilic organic solvent (A) and water per minute is less than a certain amount, (3) increasing the degree of vacuum, repeating the method The above-mentioned water-based acrylic resin, characterized in that when measuring the outflow amount of the azeotrope of the organic solvent (A) and water in conjunction with the degree of vacuum, the degree of vacuum is removed in three or more stages. -Method for producing polyurethane resin. 2. The outflow rate per minute of (2) in claim 1 is 0.001 to 1.% of the total charged amount of the hydrophilic organic solvent (A) having a boiling point of less than 100 ° C. and water before removal. 5%
The method for producing an aqueous acrylic-polyurethane-based resin according to claim 1, wherein the amount is equivalent to. 3. The aqueous solution according to claim 1, wherein the hydrophilic organic solvent (A) having a boiling point of less than 100 ° C. according to claim 1 is composed of two kinds of a ketone solvent and an alcohol solvent. Method for producing acrylic-polyurethane resin. 4. The constant vacuum degree according to claim 1, the first stage: in the range of 34.0 to 13.2 (kPa), the second stage: in the range of 13.1 to 9.2 (kPa), the third stage: The method for producing an aqueous acrylic-polyurethane resin according to any one of claims 1 to 3, characterized in that it is in the range of 9.1 to 3.9 (kPa).