JPH0625377A - Production of aqueous dispersion of polyurethane resin - Google Patents

Abstract

PURPOSE:To obtain the subject dispersion having excellent resistance to waste water and waste oil, antifouling property, adhesivity, water-resistance, heat- resistance, etc., by using a specific single-terminal polyhydroxy macromonomer and a polyisocyanate as essential components and reacting the components with each other. CONSTITUTION:This dispersion is produced by reacting (A) a single-terminal polyhydroxy macromonomer produced by the radical polymerization of monomers containing a fluoroalkylcontaining (meth)acrylate (preferably perfluorooctylethyl acrylate, etc.) as essential monomer component in the presence of a mercaptan-based chain transfer agent having >=2 hydroxyl groups and one mercapto group (e.g. 1-mercapto-1,1-methanediol) with (B) a polyisocyanate as essential reaction components. Concretely, the component B is made to react with the component A, other compound having active hydrogen and a compound having hydrophilic group and mixing an organic solvent solution of the obtained polyurethane resin having hydrophilic group with an aqueous solution optionally containing a neutralizing agent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an aqueous polyurethane resin dispersion. More specifically, it relates to a method for producing a polyurethane resin aqueous dispersion having excellent water repellency, oil repellency, and antifouling property.

[0002]

2. Description of the Related Art Up to now, water-based polyurethane resins have a very low risk of fire and air pollution of solvent-based polyurethane resins, and have excellent mechanical properties, solvent resistance,
It is used in a wide range of fields such as water-based coating agents and adhesives by utilizing its properties such as durability such as water resistance and adhesion to various substrates.

However, when the conventional aqueous polyurethane resin is used as a coating agent, for example, the aqueous polyurethane resin alone has almost no surface properties such as surface lubricity, water repellency, oil repellency and stain resistance. In order to impart these functions, a silicone emulsion or an aqueous fluorine-based water / oil repellent or antifouling agent must always be blended.

[0004]

However, even if it is attempted to blend the above-mentioned fluorine-based water / oil repellent or antifouling agent into an aqueous polyurethane resin, there is usually a problem of miscibility, good stability over time, and uniformity. It was not possible to mix and there was nothing practical so far.

[0005]

Means for Solving the Problems The inventors of the present invention have made extensive studies in view of the above situation, and as a method for producing a polyurethane resin aqueous dispersion having a fluoroalkyl group in a side chain, a polyisocyanate and a fluoroalkyl group-containing ( A method of reacting with a polyhydroxy macromonomer having one terminal obtained by radical polymerization of (meth) acrylate as an essential component is suitable, and the polyurethane resin aqueous dispersion thus obtained can easily exhibit the surface characteristics. The present invention has been completed and the present invention has been completed.

That is, according to the present invention, one end obtained by radical polymerization of a fluoroalkyl group-containing (meth) acrylate as an essential component in the presence of a mercaptan chain transfer agent having two or more hydroxyl groups and one mercapto group. The present invention provides a method for producing a polyurethane resin aqueous dispersion, which comprises reacting a polyhydroxy macromonomer (A) and a polyisocyanate (B) as essential components. (Structure) In the present invention, the structure of the polyurethane resin having a fluoroalkyl group in the side chain, which is obtained by a specific production method, is a major feature.

Next, the structure of the polyurethane resin is schematically shown.

[0008]

[Chemical 1] (In the above schematic diagram, Rf is a fluoroalkyl group, Rh is a hydrocarbon group, and Si is an organosiloxyl group.) In the schematic diagram, the side chain (1) contains a fluoroalkyl group as a macromonomer (A). (Meth) acrylate, and shows a structure of a polyurethane resin in the case of using a one-end polyhydroxy macromonomer obtained by random radical polymerization of a hydrocarbon-based monomer such as (meth) acrylic acid alkyl ester, It can be seen that the fluoroalkyl group and the hydrocarbon group are located further on the side chain of the side chain (1) corresponding to the side chain of the polyurethane main chain. The length of the side chain (1) can be adjusted by the degree of polymerization of the fluoroalkyl group-containing (meth) acrylate and the other monomer, or the fluoroalkyl group-containing (meth) acrylate and the other hydrocarbon monomer. It is also possible to carry out block radical polymerization of and.

The side chain (2) has a fluoroalkyl group-containing (meth) acrylate as a macromonomer (A),
The structure of the polyurethane resin in the case of using a polyhydroxy macromonomer having one end obtained by radical polymerization of a (meth) acryloyl group-containing organopolysiloxane and a hydrocarbon-based monomer such as (meth) acrylic acid alkyl ester The side chain (2) corresponding to the side chain of the polyurethane main chain further has a fluoroalkyl group on the side chain,
It can be seen that the silicone chains and hydrocarbon groups are located.

The side chain (3) has two or more active hydrogen atoms at one end, which is not the macromonomer (A) of the present invention,
The structure of the polyurethane resin when an organic compound having a fluoroalkyl group is used is shown, and it can be seen that the side chain (3) of the fluoroalkyl group is located directly on the polyurethane main chain. Needless to say, the polyurethane resin having only the side chain (3) does not correspond to the polyurethane resin in the present invention.

In the conventional polyurethane resin, the distance of the fluoroalkyl group from the main chain of the polyurethane resin depends on the compound to be used, and therefore it could be located only a short distance from the main chain. Since the fluoroalkyl group can be located far from the main chain of the polyurethane resin, the physical functions of the fluoroalkyl group such as water repellency, oil repellency, and antifouling property are more easily exhibited on the surface.

The macromonomer (A) used in the present invention is
It can be obtained by radical polymerization using a fluoroalkyl group-containing (meth) acrylate as an essential component in the presence of a mercaptan-based chain transfer agent having two or more hydroxyl groups and one mercapto group.

Examples of the mercaptan chain transfer agent having two or more hydroxyl groups and one mercapto group used for producing the macromonomer (A) include 1-mercapto-1,1-methanediol and 1-mercapto. -1,1
-Ethanediol, 3-mercapto-1,2-propanediol (thioglycerin), 2-mercapto-1,2
-Propanediol, 2-mercapto-2-methyl-
1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,
2-Propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol and the like can be mentioned.

The fluoroalkyl group-containing (meth) acrylate used in the present invention is a (meth) acrylate having an alkyl group in which a hydrogen atom is replaced by a fluorine atom, and among them, all the hydrogen atoms of the alkyl group are preferably fluorine atoms. A perfluoroalkyl group-containing (meth) acrylate substituted with is used. Examples of the perfluoroalkyl group-containing (meth) acrylate include perfluorooctylethyl acrylate, perfluorooctylethyl methacrylate, perfluorohexylethyl acrylate, perfluorohexylethyl methacrylate, N-methylperfluorooctylsulfonamidoethyl acrylate, N- Methyl perfluorooctyl sulfonamide ethyl methacrylate, N-methyl perfluorohexyl sulfonamide ethyl acrylate, N-methyl perfluorohexyl sulfonamide ethyl methacrylate, N-propyl perfluorohexyl sulfonamide ethyl acrylate, N-propyl perfluorooctyl sulfonamide Ethyl acrylate, perfluoroheptyl carbon amide Le acrylate.

The macromonomer (A) of the present invention may be a macromonomer obtained by using only a fluoroalkyl group-containing monomer, but a (meth) acryloyl group-containing organopolysiloxane is added to the fluoroalkyl group-containing monomer. It may be used in combination. Polyurethane resin using macromonomer combined with (meth) acryloyl group-containing organopolysiloxane has new surface lubricity, abrasion resistance,
The blocking resistance becomes good, and the water repellency and oil repellency become more remarkable due to the interaction between the fluoroalkyl group and the siloxane chain. Another method is to use a macromonomer obtained by using a fluoroalkyl group-containing monomer as an essential component and a macromanomer obtained by using a (meth) acryloyl group-containing organopolysiloxane as an essential component.

Examples of the (meth) acryloyl group-containing organopolysiloxane used here include those having a structure represented by the following formula (I).

[0017]

[Chemical 2] (However, R _{1 to} R ₇ are an alkyl group or an aryl group, R ₈ is a C _{3 to} C ₁₀ alkylene group, R ₉ is H or a methyl group,
n is an integer of 10 to 200. ) In formula (I),
All of R _{1 to} R ₇ are preferably methyl groups, and R ₈ is preferably a propylene group.

Specific examples of the (meth) acryloyl group-containing organopolysiloxane of the present invention include methacryloxypropyl polydimethyl siloxane, acryloxy propyl polydimethyl siloxane, methacryloxy buter polydimethyl siloxane, and acryloxy buter poly dimethyl. Examples thereof include siloxane and methacryloxypropyl polymethylphenyl siloxane.

The (meth) acryloyl group-containing organopolysiloxane of the formula (I) is produced, for example, as follows. That is, the aryl methacrylate obtained by reacting methacrylic acid with an aryl alcohol is further reacted with chlorodimethylsilane to give methacryloxypropyldimethylchlorosilane, which is reacted with cyclic siloxane.

Radical-polymerizable unsaturated monomers other than the above-mentioned fluoroalkyl group-containing (meth) acrylate and (meth) acryloyl group-containing organopolysiloxane used in the present invention include, for example, methyl acrylate, ethyl acrylate and butyl acrylate. Alkyl (meth) acrylates such as octyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile,
Methacrylonitrile, styrene, vinyl acetate are mentioned, and of these, methyl methacrylate is preferable.

In addition to these, the following radically polymerizable unsaturated monomers having a functional group, for example, glycidyl group-containing monomers such as glycidyl (meth) acrylate and aryl glycidyl ether; (meth) acrylic acid , Itaconic acid, 2-methacryloyloxyethyl phthalic acid and salts thereof; methacryloyloxyethyl acid phosphate, methacryloyloxypropyl acid phosphate and phosphoric acid group-containing monomers such as esters or salts thereof; styrene sulfonic acid and their Sulfonic acid group-containing monomers such as salts; amino group-containing monomers such as dimethylaminomethyl (ethyl) (meth) acrylate and quaternary salts thereof; amide group-containing monomers such as (meth) acrylamide; methoxypolyethylene Glycol (meth) acrylate, etc. Oxyethylene group content monomers and the like can be used.

As a method for producing the fluoroalkyl group-containing macromonomer of the present invention, a conventionally known method can be applied, for example, in the presence of a mercaptan chain transfer agent having two or more hydroxyl groups and one mercapto group. The radical-polymerizable unsaturated monomer containing the perfluoroalkyl group-containing (meth) acrylate as an essential component is radical-polymerized by using a polymerization catalyst if necessary. Examples of the polymerization catalyst include acyl peroxides such as benzoyl peroxide, tertiary butyl hydroperoxides, alkyl hydroperoxides such as p-methane hydroperoxide, and dialkyl peroxides such as di-tertiary butyl peroxide. Examples thereof include peroxide compounds, azobisisobutyronitrile compounds, and the like.

The molecular weight of the macromonomer used in the present invention is 1,000 to 100,000, and usually 1.00.
0 to 50,000 is preferable. In the production method of the present invention, the perfluoroalkyl group macromonomer (A)
Can be used in any ratio, and it is necessary to use an amount sufficient to impart surface functionality to the solid content of the finally obtained polyurethane resin aqueous dispersion.

Examples of the polyisocyanate (B) used in the present invention include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate and 4,4'-diphenylmethane. Diisocyanate,
2,4'-diphenylmethane diisocyanate, 2,
2'-diphenylmethane diisocyanate, 3,3'-
Dimethyl-4,4'-biphenylene diisocyanate,
3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate , 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,
4-cyclohexylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,
4'-dicyclohexylmethane diisocyanate, 3,
3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate and the like can be mentioned.

The other active hydrogen-containing compound capable of reacting with the isocyanate group used in the production of the aqueous polyurethane resin dispersion of the present invention has an average molecular weight of 300 for convenience.
To 10,000, preferably 500 to 5,000, and high molecular weight compounds, and low molecular weight compounds having a molecular weight of 300 or less.

Examples of the high molecular weight compound include polyester polyol, polyether polyol, polycarbonate polyol, polyacetal polyol,
Examples thereof include polyacrylate polyol, polyester amide polyol, polythioether polyol and the like.

As the polyester polyol, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol,
1,6-hexanediol, neopentyl glycol,
Diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (molecular weight 300 to 6,000), dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, glycol components such as hydrogenated bisphenol A, hydroquinone and their alkylene oxide adducts, and succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid Acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4
Of naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p′-dicarboxylic acid and these dicarboxylic acids Anhydrides or ester-forming derivatives; polyesters obtained by dehydration condensation reaction with acid components such as p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid and ester-forming derivatives of these hydoxycarboxylic acids Other examples include polyesters obtained by a ring-opening polymerization reaction of a cyclic ester compound such as ε-caprolactone and copolymerized polyesters thereof.

As the polyether, ethylene glycol, diethylene glycol, triethylene glycol,
Propylene glycol, trimethylene glycol, 1,
3-butanediol, 1,4-butanediol, 1,6
-Hexanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, sorbitol, sucrose, aconit sugar, trimellitic acid, hemimellitic acid, phosphoric acid, ethylenediamine, diethylenetriamine, triisopropanolamine, pyrogallol, dihydroxybenzoic acid, hydroxy Ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin with one or more compounds having at least two active hydrogen atoms such as phthalic acid, 1,2,3-propanetrithiol and the like as an initiator. Examples thereof include those obtained by addition-polymerizing one or more monomers such as tetrahydrofuran and cyclohexylene by a conventional method.

As the polycarbonate polyol,
1,4-butanediol, 1,6-hexanediol,
Examples thereof include compounds obtained by reacting a glycol such as diethylene glycol with diphenyl carbonate or phosgene.

The low molecular weight compound has a molecular weight of 30.
A compound containing at least two active hydrogens in the molecule of 0 or less, for example, a glycol component used as a raw material for polyester polyol; a polyhydroxy compound such as glycerin, trimethylolethane, trimethylolpropane, sorbitol, pentaerythritol, and the like; Ethylenediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4′-dicyclohexylmethanediamine, 3,
3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, 1,2-propanediamine, hydrazine, diethylenetriamine,
Examples include amine compounds such as triethylenetetramine.

The method for producing the polyurethane resin aqueous dispersion of the present invention may be any of the methods well known in the art, such as the following method. A macromonomer (A), other active hydrogen-containing compound, and a hydrophilic group-containing compound, in an organic solvent solution or organic solvent dispersion of a hydrophilic group-containing polyurethane resin obtained by reacting the polyisocyanate (B), A method of obtaining an aqueous dispersion by optionally mixing an aqueous solution containing a neutralizing agent. A neutralizing agent is added to the hydrophilic group-containing terminal isocyanate group-containing urethane prepolymer obtained by reacting the macromonomer (A), other active hydrogen-containing compound, and the hydrophilic group-containing compound with the polyisocyanate (B). A method of obtaining an aqueous dispersion by mixing with an aqueous solution containing the same or by adding a neutralizing agent to a prepolymer in advance and then mixing and dispersing the water in water, followed by reacting with a polyamine. The hydrophilic group-containing terminal isocyanate group-containing urethane prepolymer obtained by reacting the macromonomer (A), other active hydrogen-containing compound, and the hydrophilic group-containing compound with the polyisocyanate (B), a neutralizing agent and A method of obtaining an aqueous dispersion by mixing with an aqueous solution containing a polyamine or by previously adding a neutralizing agent to a prepolymer and then mixing with an aqueous solution containing a polyamine.

The polyurethane resin in the aqueous polyurethane dispersion may or may not have a hydrophilic group in its molecule, but it is an emulsifier when the polyurethane resin is dispersed in an aqueous medium. It is preferable that it has a hydrophilic group because it is unnecessary separately, or if necessary, the amount thereof is small and the water resistance of the coating can be further improved.

The polyurethane resin preferably has a hydrophilic group which is a carboxylate group and / or an ethylene oxide unit. Examples of the raw material used for introducing a hydrophilic group into the polyurethane resin or the urethane prepolymer having a terminal isocyanate group of the present invention include, for example, a salt of a carboxylic acid having at least one active hydrogen atom in the molecule. , Sulfonic acid salt,
A compound having at least one functional group selected from the group consisting of a carboxylic acid group and a sulfonic acid group, which is basically ionic, or has at least one active hydrogen atom in the molecule, and has ethylene oxide of Examples thereof include nonionic compounds containing a group consisting of repeating units and a group consisting of ethylene oxide repeating units and other alkylene oxide repeating units. Among these hydrophilic groups, an anionic group consisting of a carboxylic acid group and a salt of a carboxylic acid and / or a nonionic group containing a repeating unit of ethylene oxide is particularly preferable.

Examples of the hydrophilic group-containing compound include 2-oxyethanesulfonic acid, phenolsulfonic acid,
Sulfobenzoic acid, sulfosuccinic acid, 5-sulfoisophthalic acid, sulfanilic acid, 1,3-phenylenediamine-
4,6-disulfonic acid, 2,4-diaminotoluene-5
-Sulfonic acid-containing compounds such as sulfonic acid and their derivatives or polyester polyols obtained by copolymerizing these; 2,2-dimethylolpropionic acid, 2,2-
Dimethylol butyric acid, 2,2-dimethylol valeric acid, dioxymaleic acid, 2,6-dioxybenzoic acid, 3,4-
Carboxylic acid-containing compounds such as diaminobenzoic acid and their derivatives or polyester polyols obtained by copolymerizing these; at least 30% by weight of repeating units of ethylene oxide, and at least 1 in the polymer.
Molecular weight 300 to 20,000 containing one or more active hydrogens
0, polyoxyethylene glycol or polyoxyethylene-polyoxypropylene copolymer glycol, polyoxyethylene-polyoxybutylene copolymer glycol, polyoxyethylene-polyoxyalkylene copolymer glycol or nonionics such as monoalkyl ethers thereof Examples thereof include group-containing compounds and polyester polyether polyols obtained by copolymerizing these, and these are used alone or in combination.

When the polyurethane resin used in the present invention is produced, the content of the hydrophilic group bonded in the molecule is the final content when the hydrophilic group is an ionic group such as a carboxyl group or a sulfonic acid group. At least 0.005 to 0.2 equivalents, preferably 0.01 to 0.1 equivalents are required per 100 parts by weight of the solid content of the polyurethane resin obtained in 1., but a hydrophilic group such as a carboxyl group is particularly preferable.

When a nonionic compound is used, it should be at least 20 parts by weight, preferably 10 parts by weight or less, per 100 parts by weight of the solid content of the polyurethane resin finally obtained.

In the present invention, an external emulsifier may be used in combination with the hydrophilic group-containing compound. Examples of such emulsifiers include nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styrenated phenyl ether, and polyoxyethylene sorbitol tetraoleate; fatty acid salts such as sodium oleate; Ester salt, alkylbenzene sulfonate,
Anionic emulsifiers such as alkyl sulfosuccinates, naphthalene sulfonates, sodium alkane sulfonates, sodium alkyl diphenyl ether sulfonates; nonionic anionic emulsifiers such as polyoxyethylene alkyl sulfates and polyoxyethylene alkylphenyl sulfates Can be mentioned.

The polyurethane resin and the urethane prepolymer containing a terminal isocyanate group according to the present invention are produced by a conventionally known method. For example, the polyisocyanate and the active hydrogen-containing compound (the macromonomer (A) and the hydrophilic group-containing compound are also included). In the case of polyurethane resin, the equivalent ratio of isocyanate group and active hydrogen group is 0.
8: 1 to 1.2: 1, preferably 0.9: 1 to 1.1: 1
In the case of urethane prepolymer containing terminal isocyanate group, the ratio is 1.1: 1 to 3: 1, preferably 1.
20 to 120 ° C., preferably 3 at a ratio of 2: 1 to 2: 1
Reacted at 0-100 ° C.

These reactions can be carried out without a solvent, but an organic solvent can be used for the purpose of controlling the reaction of the reaction system or reducing the viscosity. The organic solvent is not particularly limited, but examples thereof include aromatic hydrocarbons such as toluene and xylene; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; acetic acid esters such as ethyl acetate and butyl acetate; dimethylformamide, N Amides such as methylpyrrolidone. When such an organic solvent is removed by distillation from the finally obtained polyurethane resin aqueous dispersion, it is preferable to use an organic solvent having a relatively low boiling point, which is easily removed by distillation. Even when it is necessary to use an organic solvent having a boiling point of 100 ° C. or higher, it is preferable to keep the amount used to the minimum necessary.

Examples of the neutralizing agent that can be used in the production of the polyurethane aqueous dispersion of the present invention include non-volatile bases such as sodium hydroxide and potassium hydroxide; trimethylamine, triethylamine, dimethylethanolamine, methyldiethanolamine and triethylamine. Examples include tertiary amines such as ethanolamine and volatile bases such as ammonia. The time of neutralization may be before, during, or after the polymerization of the carboxyl group-containing unsaturated monomer, or during or after the urethanization reaction. Either is fine.

Examples of the polyamine which can be used in the production of the aqueous polyurethane dispersion of the present invention include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2-methylpiperazine and 2,5-. Dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,
3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, aminoethylethanolamine, aminopropylethanolamine, aminohexylethanolamine, aminoethylpropanolamine,
Examples thereof include diamines such as aminopropylpropanolamine and aminohexylpropanolamine; polyamines such as diethylenetriamine, dipropylenetriamine and triethylenetetramine; hydrazines; acid hydrazides, which may be used alone or in combination.

In the production of the aqueous polyurethane resin dispersion of the present invention, the macromonomer (A) may optionally have two or more active hydrogen atoms at one terminal organopolysiloxane and / or two active hydrogen atoms at one terminal. You may use together the organic compound which has the above and has a fluoroalkyl group.

Examples of these compounds include those having the following structures.

[0044]

[Chemical 3]

[0045]

[Chemical 4]

(In the formula, Ph represents a phenyl group, and n and m represent positive integers.)

[0047]

[Chemical 5]

[0048]

[Chemical 6]

(In the formula, Rf is a fluoroalkyl group, preferably a perfluoroalkyl group.) The polyurethane resin aqueous dispersion thus obtained may be used as it is, but the organic solvent is removed by distillation if necessary. Can also be used.

While various kinds of distillation apparatuses can be used for removing the organic solvent by distillation, a distillation apparatus which does not release the distilled solvent and the organic solvent which has been removed by distillation into the atmosphere is preferable, and a thin film evaporation apparatus is particularly preferable.

In addition, in the production methods 1 to 3 of the present invention,
If necessary, in addition to water, other aqueous dispersions or aqueous dispersions, for example, vinyl acetate-based, ethylene vinyl acetate-based, acrylic-based, acrylic styrene-based emulsions; styrene / butadiene-based, acrylonitrile-butadiene-based, acrylic -Butadiene-based latex; polyethylene-based or polyolefin-based ionomer; various aqueous dispersions of polyurethane, polyester, polyamide, epoxy resin, etc.
You may use together an aqueous dispersion.

The aqueous polyurethane resin thus obtained by removing the organic solvent is a substantially solvent-free aqueous dispersion having a solid content of about 10 to 60%, preferably 15 to 50%. However, even if it is unavoidable that an organic solvent having a boiling point of 100 ° C. or higher must be used for the production of the aqueous polyurethane resin, the amount of such an organic solvent should be stopped up to 20% based on the total weight of the aqueous dispersion. .

The thus obtained aqueous dispersion of the polyurethane resin of the present invention may be used as it is, or may be used in another aqueous dispersion such as a vinyl acetate type, ethylene vinyl acetate type, an acrylic type, an acrylic styrene type emulsion; styrene. Latex of butadiene type, acrylonitrile / butadiene type, acrylic / butadiene type, etc .; ionomer of polyethylene type, polyolefin type etc .; polyurethane, polyester, polyamide, epoxy type water dispersion blended at any ratio with the aqueous coating of the present invention It can be used as an agent. In addition to the above aqueous dispersion, an alkylene glycol derivative for the purpose of improving the film-forming property, or a film-forming auxiliary such as a dialkyl ester of an aliphatic dicarboxylic acid,
Further, for the purpose of improving coating suitability, a fluorine-based leveling agent, a dialkylsulfosuccinate-based emulsifying agent, and various leveling agents such as acetylene glycol derivatives may be added. Further, for the purpose of suppressing foaming of the compounded liquid, various defoaming agents such as mineral oil-based, amide-based, and silicone-based antifoaming agents or a small amount of alcohols such as ethanol and isopropyl alcohol may be added. More ink,
When used as a paint, various water-soluble or water-acidic inorganic or organic pigments can be added. Further, for the purpose of improving various durability such as light resistance, heat resistance, water resistance, solvent resistance and heat resistance of the above water dispersion, a stabilizer such as an antioxidant, an ultraviolet absorber and a hydrolysis inhibitor is added to the aqueous polyurethane. It may be added during or after the production process of the resin, or alternatively, a crosslinking agent such as an epoxy resin, a melamine resin, an isocyanate compound, an aziridine compound or a polycarbodiimide compound may be blended and used.

The aqueous polyurethane resin dispersion of the present invention thus obtained is made of polyester, nylon, vinyl chloride, AB.
As a primer coating agent for various plastic films and sheets such as S, OPP and CPP, as a top coating agent or as a base polymer for aqueous gravure ink, as a surface coating agent for various metal plates such as iron plates, steel plates and aluminum plates, thermal paper It is useful as a top coat agent for various functional papers, or as a coating material for various fiber knitted fabrics, non-woven fabrics, paper, natural leather, artificial leather, synthetic leather, wood, surface coating agents, adhesives, binders and the like.

[0055]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In the present invention, parts and% are based on weight unless otherwise specified.

<Water and oil repellency of film> Using the film prepared by the above method, water and n- at 23 ° C are used.
The contact angle of dodecane was measured. The larger the contact angle, the better the water and oil repellency, indicating that water-based or oil-based stains are less likely to adhere.

<Frictional coefficient> Using a surface property measuring device (Model 14 manufactured by Haydon Co., Ltd.), load 20 g, speed 130 mm /
Measured in minutes. Abrasion test, load 1kg, stroke 1
It was performed by a plane friction test (JIS M-403B) at 40 mm. Example 1 Polyester polyol having a molecular weight of 1,000 (ethylene glycol / neopentyl glycol / terephthalic acid / isophthalic acid / adipic acid) 1079 parts, average molecular weight 6,0
No. 00 of the present invention having a perfluoroalkyl group and a silicone chain-containing macromonomer [methylmethacrylate and perfluorooctylethyl acrylate in the presence of thioglycerin, methacryloxypropyl polydimethylsiloxane (Cilaplane FM-072 manufactured by Chisso Corporation).
1) Oligomers having one-end diol group copolymerized at a ratio of 3/5/2 by weight] 385 parts, dimethylolpropionic acid 115 parts, Coronate T-80 (manufactured by Nippon Polyurethane) 348 parts, methyl ethyl ketone 707 parts, N-methyl 578 parts of pyrrolidone were mixed and reacted at 75 ° C. for 20 hours to obtain a polyurethane resin solution. To this polyurethane resin solution, 58.4 parts of 25% ammonium hydroxide was added for neutralization, 5500 parts of water was slowly added dropwise with stirring to emulsify, and then methyl ethyl ketone was distilled off under reduced pressure to obtain a solid content concentration. A 25% aqueous polyurethane resin was obtained. This aqueous polyurethane resin was applied onto a PET film of 125 μm so that the film thickness when dried was 50 μm, and dried at 80 ° C. to obtain a urethane film. The contact angles of this film were 100 degrees (water) and 42 degrees (dodecane), respectively, and the friction coefficient was 0.05. Comparative Example 1 An aqueous urethane resin containing no perfluoroalkyl group and no silicone chain was synthesized in the same manner except that the macromer of Example 1 was omitted.

1246 parts of a polyester polyol having a molecular weight of 1,000 (ethylene glycol / neopentyl glycol / terephthalic acid / isophthalic acid / adipic acid), 101 parts of dimethylolpropionic acid, Coronate T-80
Mix 348 parts (manufactured by Nippon Polyurethane), 611 parts of methyl ethyl ketone, and 509 parts of N-methylpyrrolidone to prepare 7
A polyurethane resin solution was obtained by reacting at 5 ° C. for 20 hours. In this polyurethane resin solution, 25% ammonium hydroxide 58.
After neutralizing by adding 4 parts, 4820 parts of water was gradually added dropwise with stirring to emulsify, and then methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous polyurethane resin having a solid content concentration of 25%. This aqueous polyurethane resin was coated on a 125 μm PET film in the same manner as in Example 1 so that the film thickness when dried was 50 μm, and dried at 80 ° C. to obtain a urethane film. The contact angles of this film are 65 degrees (water) and 3 respectively.
And the coefficient of friction was 0.79. Example 2 3-Methylpentane Adipate 736 with a molecular weight of 2,000
Parts, a macromonomer having a molecular weight of 3,000 and containing a perfluoroalkyl group and a silicone chain of the present invention [in the presence of thioglycerin, methylmethacrylate and N-propylperfluorooctylsulfonamidoethylmethacrylate, methacryloxypropylpolydimethylsiloxane (Chisso stock Company-made sila plane FM-0721)
Oligomer having one terminal diol group copolymerized in a weight ratio of 5/3/2] 334 parts, dimethylolpropionic acid 1
09 parts, neopentyl glycol 21.5 parts, isophorone diisocyanate 466 parts, methyl ethyl ketone 11
75 parts by mixing 10 parts and 0.3 parts of stannous octoate
Was reacted for 8 hours to synthesize an isocyanate group-terminated prepolymer. Triethylamine (82.3 parts) was added to the prepolymer for neutralization, and 5520 parts of water was gradually added dropwise with stirring to emulsify, and then 24 parts of 100% hydrated hydrazine was added. The reaction is completed by stirring until no further absorption is observed. Subsequently, methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous polyurethane resin having a solid content concentration of 25%. This aqueous polyurethane resin was applied onto a PET film of 125 μm so that the film thickness when dried was 50 μm, and dried at 80 ° C. to obtain a urethane film. This waterborne polyurethane resin 1
A urethane film was obtained by coating on a PET film of 25 μm so that the film thickness when dried was 50 μm, and drying at 80 ° C. The contact angles of this film are 98 degrees (water) and 41, respectively.
And the coefficient of friction was 0.04. Example 3 772 parts of polyester diol having a molecular weight of 1,500 (ethylene glycol / neopentyl glycol / isophthalic acid / sebacic acid), a macromonomer containing a perfluoroalkyl group and a silicone chain of the present invention having a molecular weight of 4,000 [in the presence of thioglycerin Methyl methacrylate and N
-Ethyl perfluorooctyl sulfonamide ethyl acrylate, methacryloxypropyl polydimethyl siloxane (Cilaplane FM-0 manufactured by Chisso Corporation)
721) Oligomer having one-end diol group copolymerized at a ratio of 4/4/2] 319 parts, dimethylolpropionic acid 85.4 parts, 1,4-butanediol 24 parts,
4,4'-dicyclohexylmethane diisocyanate 3
93 parts, stannous octylate 0.8 parts, methyl ethyl ketone 743 parts and N-methylpyrrolidone 318 parts were mixed and reacted at 75 ° C. for 20 hours to obtain a polyurethane resin solution. 25% ammonium hydroxide 4 in this polyurethane resin solution
After 3.3 parts were added for neutralization, 5300 parts of water was gradually added dropwise with stirring to emulsify, and then methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous polyurethane resin having a solid content concentration of 25%. This waterborne polyurethane resin has a P of 125μ
A urethane film was obtained by coating on an ET film so that the film thickness when dried was 50 μm, and drying at 80 ° C. The contact angles of this film were 103 degrees (water) and 43 degrees (dodecane), respectively, and the friction coefficient was 0.06.

[0059]

According to the production method of the present invention, a polyurethane resin is produced by using a polyhydroxy macromonomer having a fluoroalkyl group at one end as a polyol. Therefore, a fluorocarbon is added to the side chain of the polyurethane skeleton. It is possible to obtain a polyurethane resin aqueous dispersion into which an alkyl group has been introduced, and conventional polyurethane resins having a fluoroalkyl group directly on the side chain have not been sufficient, and have higher surface properties such as oil repellency and antifouling property. It is possible to easily obtain the polyurethane resin film having the above.

In the polyurethane resin obtained by the production method of the present invention, since the fluoroalkyl group is localized in the side chain of the side chain of the polyurethane skeleton, a small amount of copolymerization can impart sufficient surface characteristics. Providing a water-based polyurethane resin that has a good balance and does not impair the properties inherent to polyurethane resins, such as adhesion to various substrates, transparency, film strength and elongation, water resistance, solvent resistance, heat resistance, etc. it can.

Claims (7)

[Claims] 1. One-terminal polyhydroxy macromolecule obtained by radical polymerization of a fluoroalkyl group-containing (meth) acrylate as an essential component in the presence of a mercaptan chain transfer agent having two or more hydroxyl groups and one mercapto group. A method for producing a polyurethane resin aqueous dispersion, which comprises reacting a monomer (A) with a polyisocyanate (B) as an essential component. 2. A macromonomer (A) containing a fluoroalkyl group-containing (meth) acrylate and a (meth) acryloyl group in the presence of a mercaptan chain transfer agent having two or more hydroxyl groups and one mercapto group. The production method according to claim 1, which is obtained by radical polymerization of an organopolysiloxane as an essential component. 3. One-terminal polyhydroxy obtained by radical polymerization of a (meth) acryloyl group-containing organopolysiloxane as an essential component in the presence of a mercaptan chain transfer agent having two or more hydroxyl groups and one mercapto group. The production method according to claim 1, wherein the macromonomer and the macromonomer (A) are used in combination. 4. An organopolysiloxane having two or more active hydrogen atoms at one end and / or two active hydrogen atoms at one end.
The production method according to claim 1, further comprising the organic compound having the above and having a fluoroalkyl group. 5. The method according to claim 1, wherein the hydrophilic group of the polyurethane resin is a carboxylate group and / or an ethylene oxide unit. 6. A mercaptan chain transfer agent having two hydroxyl groups and one mercapto group is 3-mercapto-
The method according to claim 1, which is 1,2-propanediol. 7. The production method according to claim 1, wherein the macromonomer (A) is a macromonomer obtained by further using methyl methacrylate.