JP2000230033A - Production of polyurethane emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a polyurethane emulsion improved in solvent resistance, water resistance, and miscibility with other aqueous emulsions by reacting an isocyanate-group-containing polyurethane prepolymer with an amine polymer and a specific low-mol.-wt. compound in an aqueous medium. SOLUTION: A high-mol.-wt. polyol having a number average mol.wt. of 500-10,000 and a hydroxyl functionality of 2.0 or higher but not higher than 4.0, an organic diisocyanate, and if necessary a chain extender are reacted in the absence of a solvent to give a polyurethane prepolymer having isocyanate groups. The prepolymer in an amount of 100 pts.wt., 0.2-20 pts.wt. amine polymer having a mol.wt. of 100 or higher, and a low-mol.-wt. compound having a mol.wt. of 300 or lower, containing active hydrogen groups selected from among prim-amino, sec-amino, prim-hydroxyl, and sec-hydroxyl groups, and in an equivalent ratio of active hydrogen atoms to isocyanate groups of the prepolymer of 0.70-1.20 are reacted in an aqueous medium.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a polyurethane emulsion, and more particularly, to a method for producing a polyurethane emulsion having good solvent resistance, water resistance, and good miscibility with other aqueous emulsions.

[0002]

2. Description of the Related Art Conventionally, polyurethane has been used as a resin to fill the boundary field between rubber and plastics by utilizing its excellent mechanical properties, abrasion resistance, chemical resistance, adhesiveness, etc. as a resin, a paint, an adhesive, It has penetrated a wide range of applications such as artificial leather. Among them, aqueous polyurethane has been rapidly developed to meet social needs such as environmental conservation, resource saving and safety. High-performance aqueous polyurethanes have emerged due to advances in the technology of emulsifying and dispersing urethane resins in water, the technology of self-emulsifying and dispersing by ionomerization, and the technology of increasing the molecular weight in water. It has reached a comparable level and has been put to practical use in various application fields.

[0003] However, as a problem of the aqueous polyurethane, an emulsifier or an ionic group necessary for making the aqueous polyurethane often impairs the inherent properties of the polyurethane resin, such as solvent resistance and water resistance. Furthermore, in the case of using a blend of an aqueous polyurethane and various aqueous emulsions, there is often a problem in miscibility. In order to solve these problems, for example, JP-A-53-79990 proposes using a water-soluble salt of a condensation product of an acidic amino acid and a fatty acid as an emulsifier.

[0004]

However, even in the method disclosed in JP-A-53-79990, the improvement in solvent resistance and water resistance is not sufficient, and the mixing stability with other aqueous emulsions is also insufficient. .

It is an object of the present invention to provide a polyurethane emulsion having improved solvent resistance, water resistance and miscibility with other aqueous emulsions, and a process for producing the same.

[0006]

The object of the present invention is to provide a polyurethane prepolymer having an isocyanate group in a molecule in an aqueous medium, an (a) amine-based polymer and (b) a primary amino group and a secondary This is achieved by providing a method for producing a polyurethane emulsion, which comprises reacting a low molecular weight compound having an active hydrogen atom selected from an amino group, a primary hydroxyl group and a secondary hydroxyl group.

Another object of the present invention is to provide an amine-based polymer,
This is more preferably achieved by providing a method for producing the above-mentioned polyurethane emulsion which is a hydrolyzate of a polymer of a monomer represented by the following (I). CH2 = CHNR1COR2 (I) (R1 and R2 represent a hydrogen atom or a methyl group.)

[0008] Another object of the present invention is to provide a polyurethane prepolymer having an anionic group bonded by a covalent bond,
It is more preferably achieved by providing a method for producing the above-mentioned polyurethane-based emulsion in which at least a part of the anionic group forms a salt with a cationic compound.

[0009] It is more preferably achieved by providing a method for producing the above-mentioned polyurethane-based emulsion using a nonionic surfactant when emulsifying the polyurethane prepolymer in an aqueous medium.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The polyurethane prepolymer used in the present invention is substantially an isocyanate in a molecule obtained by reacting a polymer polyol, an organic diisocyanate and, if necessary, a chain extender in the presence or absence of a solvent. It is a polyurethane having one or more groups.

The high molecular polyol which can be used for producing the polyurethane prepolymer includes polyester polyol, polycarbonate polyol, polyester polycarbonate polyol, polyether polyol and the like, and the polyurethane prepolymer is one of these high molecular polyols or It can be formed using two or more kinds.

The polyester polyol used in the production of the polyurethane prepolymer may be prepared, for example, by directly esterifying a polyol component with a polycarboxylic acid component such as a polycarboxylic acid, an ester thereof, or an ester-forming derivative such as an anhydride. Alternatively, it can be obtained by transesterification.

Examples of the polycarboxylic acid component which is a raw material for producing a polyester polyol used for producing a polyurethane prepolymer include succinic acid, glutaric acid, and the like.
Adipic acid, pimelic acid, suberic acid, azelaic acid,
Sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-
Aliphatic dicarboxylic acids such as methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecandioic acid, and 3,7-dimethyldecanedioic acid; isophthalic acid Dicarboxylic acids such as terephthalic acid, phthalic acid and naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; tricarboxylic acids such as trimellitic acid and trimesic acid; ester-forming derivatives thereof; And one or more of these can be used. Among them, the polyester polyol is mainly composed of an aliphatic carboxylic acid or an ester-forming derivative thereof as a polycarboxylic acid component, and optionally contains a small amount of a trifunctional or higher-functional polycarboxylic acid or an ester-forming derivative thereof. It is preferably manufactured.

Examples of the polyol component, which is a raw material for producing a polyester polyol used for producing a polyurethane prepolymer, include ethylene glycol, propylene glycol, 2-methyl-1,3-propanediol, 1,4-butanediol, , 5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-
Pentanediol, neopentyl glycol, 1,7-
Heptanediol, 1,8-octanediol, 1,9
Aliphatic diols such as nonanediol, 2-methyl-1,8-octanediol and 1,10-decanediol; alicyclic diols such as cyclohexanedimethanol and cyclohexanediol; glycerin, trimethylolpropane, butanetriol, hexane Triol,
Examples thereof include triols such as trimethylolbutane and trimethylolpentane, and tetraols such as pentaerythritol, and one or more of these can be used. Among them, the polyester polyol is preferably made of an aliphatic polyol as a polyol component, and is preferably produced using a polyol component containing a small amount of a trifunctional or higher polyol in some cases.

The polycarbonate polyol which can be used for producing the polyurethane prepolymer is obtained, for example, by reacting the polyol with a carbonate compound such as dialkyl carbonate, alkylene carbonate, diaryl carbonate and the like. As the polyol constituting the polycarbonate polyol, the polyol exemplified above as the constituent component of the polyester polyol can be used. Further, as the dialkyl carbonate, dimethyl carbonate, diethyl carbonate, and the like,
Examples of the alkylene carbonate include ethylene carbonate, and examples of the diaryl carbonate include diphenyl carbonate.

Polyester polycarbonate polyols that can be used in the production of polyurethane prepolymers include:
For example, a polyol, a product obtained by simultaneously reacting a polycarboxylic acid and a carbonate compound, a product obtained by reacting a polyester polyol and a carbonate compound which have been prepared in advance, a polycarbonate polyol and a polyol which have been prepared in advance And those obtained by reacting a polycarboxylic acid, and those obtained by reacting a polyester polyol and a polycarbonate polyol which have been produced in advance.

Examples of the polyether polyol which can be used for producing the polyurethane prepolymer include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like. One or more of these may be used. it can.

The number average molecular weight of the high molecular weight polyol component is 5
00 to 10000, and 700 to 5
000, more preferably 750-4000. Number average molecular weight of 500 to 10000
When a polyurethane prepolymer produced using a high molecular weight polyol out of the range is used, the resulting polyurethane composition tends to have reduced cold resistance, water resistance, solvent resistance and the like.

Further, in the high molecular polyol, the number f of hydroxyl groups per molecule is preferably in the range of 2.0 ≦ f ≦ 4.0. More preferably, the range is 2.0 ≦ f ≦ 3.0. The number of hydroxyl groups per molecule f is 2.0 as described above.
When a polyurethane prepolymer obtained by using a high molecular polyol in the range of ≦ f ≦ 4.0 is used in the polyurethane emulsion of the present invention, the obtained polyurethane composition has good water resistance and solvent resistance.

As the organic diisocyanate component, any of organic diisocyanates conventionally used in the production of ordinary polyurethane emulsions can be used. One of them
Species or two or more are preferably used. Examples of the organic diisocyanate include hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate,
Examples thereof include 4,4'-diphenylmethane diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, and 1,5-naphthylene diisocyanate, and one or more of these can be used.

In producing the polyurethane prepolymer of the present invention, a chain extender component can be used if necessary. As the chain extender component that can be used, any chain extender conventionally used in the production of ordinary polyurethane-based emulsions can be used, but two or more active hydrogen atoms capable of reacting with an isocyanate group in the molecule are used. It is preferable to use a low molecular compound having a molecular weight of 300 or less. For example, ethylene glycol, propylene glycol, 1,
4-butanediol, 1,6-hexanediol, 1,
4-bis (β-hydroxyethoxy) benzene, 1,4
Diols such as cyclohexanediol, bis- (β-hydroxyethyl) terephthalate, xylylene glycol; triols such as trimethylolpropane;
Pentaols such as pentaerythritol; diamines such as hydrazine, ethylenediamine, propylenediamine, xylylenediamine, isophoronediamine, piperazine and derivatives thereof, phenylenediamine, tolylenediamine, xylenediamine, adipic dihydrazide and isophthalic dihydrazide; amino Examples thereof include amino alcohols such as ethyl alcohol and aminopropyl alcohol, and one or more of these can be used.

The production of the polyurethane prepolymer can be carried out by a conventionally known method, and can be carried out at a temperature of 30 to 150 ° C. in the presence or absence of an organic solvent. Examples of the organic solvent that can be used in this case include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate and butyl acetate; amides such as dimethylformamide and N-methylpyrrolidone; And solvents having a boiling point of less than 100 ° C., such as acetone, methyl ethyl ketone, and ethyl acetate, in consideration of the easiness of solvent removal after emulsion production. Also, after prepolymer production,
The above organic solvent may be added or added for the purpose of lowering the viscosity or the like.

In the production of the polyurethane prepolymer, a reaction catalyst can be added as required. Examples of such a catalyst include tin octylate, monobutyltin triacetate, monobutyltin monooctylate, and monobutyltin. Organotin compounds such as monoacetate, monobutyltin maleate, dibutyltin diacetate, dibutyltin dioctoate, dibutyltin distearate, dibutyltin dilaurate and dibutyltin maleate; organic titanium compounds such as tetraisopropyl titanate and tetra-n-butyl titanate Compounds: tertiary amines such as triethylamine, N, N-diethylcyclohexylamine, N, N, N ′, N′-tetramethylethylenediamine and triethylenediamine.

In the production of the polyurethane prepolymer, the ratio (R) of isocyanate group equivalent per equivalent of active hydrogen atom is 1 based on the total amount of active hydrogen atoms contained in the polymer polyol and the chain extender. .05 ≦ R
It is preferably used in the range of ≦ 3.0, and 1.1 ≦ R ≦
More preferably, it is used in the range of 2.5. R is 1.0
If it is less than 5, the reactivity with the polyvinyl alcohol-based polymer described below decreases, heat resistance, solvent resistance, etc. are not sufficiently improved, and emulsification in water due to high viscosity of the prepolymer. Is difficult. When R exceeds 3.0, the emulsion becomes unstable during the reaction with a polyvinyl alcohol-based polymer or a low-molecular compound having an amino group or a hydroxyl group, which will be described later, and the emulsion tends to gel.

Next, the polyurethane prepolymer is emulsified in water. This method comprises (1) a method of introducing a hydrophilic group into the polyurethane prepolymer molecule to impart self-emulsifying properties to the prepolymer itself, and (2) A method of forcibly emulsifying a polyurethane prepolymer by using a surfactant is exemplified.

The introduction of a hydrophilic group into the polyurethane prepolymer molecule is achieved by using a compound containing an active hydrogen atom having a hydrophilic group in the above prepolymer reaction. Examples of the active hydrogen atom-containing compound having a hydrophilic group include one or more active hydrogen atoms such as a hydroxyl group or an amino group in a molecule, and a carboxylic acid group, a sulfonic acid group, a carboxylate, a sulfonate, or the like. An anionic group;
Nonionic groups such as polyoxyethylene groups; and compounds having one or more hydrophilic groups selected from cationic groups such as tertiary amino groups and quaternary ammonium salts. For example, carboxylic acid group-containing compounds such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, and 2,2-dimethylolvaleric acid, and derivatives thereof; 1,3-phenylenediamine-4,6-disulfonic acid Sulfonic acid group-containing compounds such as 2,4-diaminotoluene-5-sulfonic acid and derivatives thereof; molecular weight 200 to 10,000
A nonionic group-containing compound such as polyoxyethylene glycol 0 and its monoalkyl ether; a tertiary amino group-containing compound such as 3-dimethylaminopropanol; and derivatives thereof. Further, a polyester polyol or a polyester polycarbonate polyol obtained by copolymerizing the above active hydrogen atom-containing compound having a hydrophilic group can also be used. Among them, a polyurethane prepolymer is produced using 2,2-dimethylolpropionic acid, and after completion of the prepolymer reaction, a basic substance such as triethylamine, trimethylamine, sodium hydroxide or potassium hydroxide is added to the carboxylate. The conversion method is preferred.

When the polyurethane prepolymer is forcibly emulsified by using a surfactant, the polyurethane prepolymer may not have the above-mentioned hydrophilic group.
As the surfactant, for example, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene lauryl ether,
Nonionic surfactants such as polyoxyethylene stearyl ether and polyoxyethylene-polyoxypropylene block copolymer; sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium alkyldiphenylether disulfonate, di (2-ethylhexyl) ) Anionic surfactants such as sodium sulfosuccinate can be used. Among these, it is preferable to use a nonionic surfactant having an HLB value of 6 to 20.

Emulsification of the polyurethane prepolymer is carried out by using one or both of the above two methods and using an emulsifying and dispersing apparatus such as a homomixer and a homogenizer.
At this time, the emulsification temperature is preferably 40 ° C. or less, more preferably 30 ° C. or less, in order to suppress the reaction between the isocyanate group of the polyurethane prepolymer and water.

The polyurethane emulsion of the present invention comprises:
Simultaneously with or after emulsification of the polyurethane prepolymer, a low molecular weight compound having an active hydrogen atom selected from a primary amino group, a secondary amino group, a primary hydroxyl group and a secondary hydroxyl group in an amine polymer and a molecule is added and reacted. Obtained. The addition of the amine polymer and the active hydrogen atom-containing low molecular weight compound may be performed simultaneously or separately. It is presumed that the polyurethane emulsion of the present invention contains a polymer in which a polyurethane unit and a polyamine unit are bonded by a structural unit represented by the following general formula, and this contributes to the development of the characteristics of the polyurethane emulsion of the present invention. Thought to be

[0030]

Embedded image

As the amine-based polymer used in the present invention, a hydrolyzate of the polymer of the monomer represented by the above (I) is preferably mentioned. N- represented by (I)
Examples of the vinylamide-based monomer include N-vinylformamide, N-vinylacetamide, N-methyl-N-vinylformamide, and N-methyl-N-vinylacetamide. In addition, as long as the characteristics of the vinylamine-based polymer are not affected, in addition to the N-vinylamide-based monomer,
-An ethylenically unsaturated monomer other than vinylamide may be copolymerized.

The amine-based polymer used in the present invention comprises N
-Obtained by hydrolyzing a vinylamide polymer. In order to produce an N-vinylamide polymer, a precipitation polymerization method in which N-vinylamide is dissolved and the polymer is polymerized using a radical polymerization initiator in an organic solvent in which the polymer is not dissolved (precipitates) is particularly preferable. is there. As an organic solvent that can be used at this time, N-vinylamide such as ethyl acetate, butyl acetate, isopropyl acetate, benzene, toluene, xylene, ethylbenzene, acetone, methyl ethyl ketone, acetonitrile, and methylpyrrolidone are dissolved, and the N-vinylamide polymer is dissolved. Any solvent can be used as long as it is not an organic solvent. In addition, these organic solvents can be used by mixing and adjusting the molecular weight as necessary.
It is also possible to mix a small amount (for example, less than 10% by weight) of a solvent that dissolves the N-vinylamide polymer such as water, methanol, and ethanol. The concentration of N-vinylamide in the polymerization is usually 1 to 40% by weight, preferably 5 to 2%.
0% by weight.

The radical polymerization initiator may be any compound as long as it is soluble in the organic solvent. For example, azobisisobutyronitrile, 2,2'-azobis (4-methoxy-2,4- Dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylpropionitrile), 2,2'-azobis (2-methylbutyronitrile) , 1,1'-azobis (cyclohexane-1-carbonitrile), dimethyl 2,2'-azobis (2-methylpropionate), benzoyl peroxide, tertiary butyl hydroperoxide, di (2-ethylhexylperoxy) Dicarbonate). The amount of the polymerization initiator to be added is 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on N-vinylamide. Further, a chain transfer agent such as butyl mercaptan, dodecane thiol, bromotrichloromethane, isopropanol, thioglycolic acid, 2-ethylhexyl thioglycolate, etc. can be added in order to obtain the desired appropriate viscosity. The amount of the chain transfer agent to be added is 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on N-vinylamide. Cannot be obtained. The polymerization temperature is appropriately selected within a range from 30 ° C. or higher to the boiling point of the organic solvent used. If the polymerization temperature is too low, it has a long time to complete the polymerization, and it is not preferable because it may cause a decrease in the yield of the polymer, and is preferably 40 ° C. or higher, and particularly preferably around the boiling point of the organic solvent. Temperature. Further, if necessary, the polymerization can be carried out after degassing dissolved oxygen in the organic solvent,
When the polymerization is carried out near the boiling point of the organic solvent, the polymerization can be carried out without degassing.

The hydrolysis of the N-vinylamide polymer is
It can be performed using a basic catalyst or an acid catalyst. That is, using a basic catalyst such as sodium hydroxide, potassium hydroxide, sodium methylate, or an acidic catalyst such as p-toluenesulfonic acid, the alcohol or glycol such as methanol, ethanol, propanol, butanol, and ethylene glycol is used as a solvent. And a hydrolysis reaction is carried out. Further, in order to improve the solubility of the N-vinylamide polymer and the catalyst, tetrahydrofuran,
Solvents such as dioxane, dimethylsulfoxide, diethylene glycol dimethyl ether, toluene, acetone, and water are appropriately mixed and used. The conditions of the hydrolysis reaction are as follows:
Usually, catalyst concentration / N-vinylamide monomer unit concentration =
0.01 to 2.0 (molar ratio), reaction temperature 0 to 180 ° C,
The reaction time ranges from 0.1 to 20 hours.

The degree of hydrolysis of the N-vinylamide polymer is preferably 0.5 mol% or more, more preferably 1 mol% or more, and even more preferably 3 mol% or more. If the degree of hydrolysis is less than 0.5 mol%, the reactivity with the polyurethane prepolymer may be poor due to the low amine content of the resulting vinylamine-based polymer. The upper limit of the degree of hydrolysis is not particularly limited, but is preferably 100% or less, more preferably 95% or less.

Other amine-based polymers used in the present invention include allylamine-based polymers. Examples of the allylamine-based polymer include (1) a homopolymer of a mono- or diallylamine derivative; and (2) two or more types. And a copolymer of a mono- or diallylamine derivative.

The homopolymer of the mono- or diallylamine derivative (1) includes polyallylamine, polydiallylamine, poly (N-benzyldiallylamine),
Examples thereof include poly (N-alkylallylamine) and poly (N-alkyldiallylamine). However, the alkyl group of poly (N-alkylallylamine) or poly (N-alkyldiallylamine) is methyl, ethyl,
Hydroxyethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl,
Cyclohexyl groups are preferred.

Examples of the copolymer of the two or more mono- or diallylamine derivatives (2) include a copolymer of monoallylamine and diallylamine, and a copolymer of monoallylamine and N
-A copolymer of alkylallylamine, a copolymer of monoallylamine and N-alkyldiallylamine, a copolymer of diallylamine and N-alkyldiallylamine,
A copolymer of diallylamine and N-alkylallylamine, a copolymer of N-alkylallylamine and N-alkyldiallylamine, a copolymer of two or more N-alkylallylamines, and a copolymer of two or more N-alkyldiallylamines Can be exemplified. However, the term "alkyl" in the above copolymer is to be understood in a broad sense, and includes a chain alkyl group such as methyl, ethyl, propyl, isopropyl, sec-butyl and tert-butyl, a cycloalkyl group such as cyclohexyl, It includes an aralkyl group such as benzyl and an alkyl group having a functional group such as a hydroxyl group and a cyano group. In the present invention, other than the above-mentioned amine-based polymer, any polymer having a primary amine group or a secondary amine group can be used.

The molecular weight of the amine polymer is preferably 100 or more, more preferably 200 to 10,000,000.
0, more preferably 300 to 1,000,000
0, particularly preferably 500 to 1,000,000.

The addition amount of the amine polymer is 0.2 to 20 parts by weight, preferably 0.5 to 15 parts by weight, based on 100 parts by weight of the polyurethane prepolymer. When the addition amount is less than 0.2 parts by weight, the obtained polyurethane composition has insufficient water resistance, solvent resistance and the like, and the addition amount is 2 parts by weight.
If the amount exceeds 0 parts by weight, the emulsion becomes unstable during the reaction with the polyurethane prepolymer, and the system tends to gel. Also, the addition of vinylamine-based polymer,
The reaction is usually carried out in an aqueous solution, but ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate and butyl acetate;
It may be added by dissolving it in an organic solvent such as amides such as dimethylformamide and N-methylpyrrolidone or a mixed solvent thereof with water. In addition to the amine polymer, a vinyl alcohol polymer may be used at the same time as necessary.

As the low molecular weight compound having an active hydrogen atom selected from a primary amino group, a secondary amino group, a primary hydroxyl group and a secondary hydroxyl group in the molecule, an active hydrogen atom capable of reacting with an isocyanate group is used. It is preferable to use a low molecular weight compound having a molecular weight of 300 or less in a molecule. For example, triamines such as diethylenetriamine; diamines such as hydrazine, ethylenediamine, propylenediamine, xylylenediamine, isophoronediamine, piperazine and derivatives thereof, phenylenediamine, tolylenediamine, xylenediamine, adipic dihydrazide and isophthalic dihydrazide; ethylamine , Monoamines such as propylamine, butylamine, and morpholine; aminoalcohols such as aminoethyl alcohol and aminopropyl alcohol; ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, and 1,4-bis (Β
Diols such as (-hydroxyethoxy) benzene, 1,4-cyclohexanediol, bis- (β-hydroxyethyl) terephthalate, and xylylene glycol; and one or more of these can be used.

The amount of the low-molecular compound having an active hydrogen atom selected from a primary amino group, a secondary amino group, a primary hydroxyl group and a secondary hydroxyl group in the molecule is determined based on the amount of the active hydrogen atom in the low-molecular compound. It is preferably 0.70 to 1.20 equivalents, more preferably 0.75 to 1.15 equivalents, and more preferably 0.80 to 1.10 equivalents per isocyanate group equivalent of the polyurethane prepolymer. Is more preferred. If the amount of active hydrogen atoms is less than 0.70 equivalents or more than 1.20 equivalents, the degree of polymerization of the polyurethane composition will not be sufficiently increased, and water resistance and solvent resistance will be insufficient.

The polyurethane emulsion of the present invention comprises:
Usually, the solid content concentration is adjusted to about 20 to 65% by weight, but is not limited thereto. When an organic solvent is used in the production of the prepolymer, the organic solvent can be removed by distillation or stripping, if necessary.

The polyurethane emulsion of the present invention comprises:
If necessary, various conventionally known emulsions can be added and used as long as the effects of the present invention are not impaired.
Examples of emulsions that can be added include, for example,
Examples include a polyvinyl acetate emulsion, an ethylene-vinyl acetate copolymer emulsion, a (meth) acrylate (co) polymer emulsion, a styrene-butadiene copolymer emulsion, and an epoxy emulsion.

The polyurethane emulsion of the present invention may be used, if necessary, in order to adjust its drying property, setting property, viscosity, film-forming property, etc., by using N-methylpyrrolidone, toluene, perchrene, dichlorobenzene, trichlorobenzene, Various organic solvents such as chlorobenzene; starch, modified starch, oxidized starch, sodium alginate, carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, maleic anhydride / isobutylene copolymer, maleic anhydride / styrene copolymer, maleic anhydride / methyl vinyl ether Water-soluble polymers such as copolymers and polyvinyl alcohol; urea / formalin resin, urea / melamine /
Thermosetting resins such as formalin resin and phenol / formalin resin; fillers such as clay, kaolin, talc, calcium carbonate, and wood flour; bulking agents such as flour; reaction accelerators such as boric acid and aluminum sulfate; titanium oxide Various additives such as a pigment, an antioxidant, an ultraviolet absorber, an antifoaming agent, a leveling agent, an antifreezing agent, a preservative, and a rust preventive can be added.

The polyurethane emulsion of the present invention comprises
Excellent film solvent resistance, heat resistance, etc., and also excellent miscibility with various aqueous emulsions and brines. Therefore, industrial fibers, leather, interior decoration, apparel, floor materials (wood, concrete, floor polish), coating agents for plastic parts, etc., packages (wrapping paper, etc.), laminations (film / foil, fibers, etc.), general industry Adhesive (PVC sheet / wood, PVC sheet / metal, metal / wood), glass fiber sizing agent, ink, paint, etc.

[0047]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the following Examples and Comparative Examples, “parts” and “%” mean on a weight basis unless otherwise specified. [Production Example 1] N-vinylacetamide (100 parts) was dissolved in ethyl acetate (900 parts), and the mixture was boiled. As a radical polymerization initiator, azobisisobutyronitrile 0.00 was used.
Two parts were added and kept boiling. As the polymerization proceeds, the produced N-vinylamide polymer precipitates in ethyl acetate, and is kept for 3 hours. After allowing to cool, the polymer was suction-filtered, dried under vacuum at 50 ° C. for 24 hours, and crushed to obtain 98 parts of a fine powdery N-vinylacetamide polymer.

[Deionized aqueous solution viscosity measurement method] 200 mL
Then, 198 g of purified water is put into a tall beaker, and 2 g of the polymer obtained in Production Example 1 is dispersed and dissolved neatly without vigorous stirring so that no lump is formed. The viscosity of the 1% deionized aqueous solution thus obtained was measured using a BL type viscometer. The measurement was performed under the conditions of one rotor, 30 rpm and 20 ° C.

[Weight average molecular weight] The sample polymer was analyzed by gel permeation chromatography under the following measurement conditions, and the value in terms of pullulan was determined. The pull run used was a pull run for making a calibration curve manufactured by Showa Denko KK. Measurement conditions Column Shodex SB-805HQ + SB-802.5HQ + SB-
802HQ Measurement temperature 40 ℃ Mobile phase Deionized water Flow rate 1.
0ml / min Detector Differential Refractometer Shodex R
I-71 Sample concentration 400ppm Injection volume 100μl

10 parts of this N-vinylacetamide polymer was dissolved in 50 parts of methanol, and the temperature was raised to 60 ° C. To this solution, 20 parts of a 10% sodium hydroxide methanol solution was added, and the mixture was stirred for 2 hours to carry out hydrolysis. The degree of hydrolysis of the obtained vinylamine-based polymer (polyvinylamine-1) was measured by conductivity titration and found to be 83 mol%.

[Production Example 2] A polymer (polyvinylamine-2) was obtained in the same manner as in Production Example 1 except that N-vinylformamide was used instead of N-vinylacetamide. Table 1 also shows the measurement results of the aqueous solution viscosity, the weight average molecular weight, and the degree of hydrolysis.

Production Example 3 A vinylamine polymer (polyvinylamine-3) was obtained in the same manner as in Production Example 1, except that 10 parts of a 10% methanol solution of sodium hydroxide used for the hydrolysis reaction was used. Table 1 also shows the measurement results of the aqueous solution viscosity, the weight average molecular weight, and the degree of hydrolysis.

[0053]

[Table 1]

In Examples and Comparative Examples, the solvent resistance and water resistance of the polyurethane composition and the mixing stability of the polyurethane emulsion were measured by the following methods. Table 2 shows abbreviations used in the following Examples.

[0055]

[Table 2]

[Solvent Resistance of Polyurethane Composition] 50 ° C.
After heat-treating the film cast at a temperature of 120 ° C. for 10 minutes at a temperature of 90 ° C., the film was immersed in a solvent at 90 ° C. for 1 hour, and the elution rate and area swelling ratio of the film were obtained from the following formulas, whereby the solvent resistance was evaluated. . Elution rate (%) = {(weight before immersion−weight after immersion) / weight before immersion} × 100 Area swelling rate (%) = ｛(area after immersion−area before immersion)
/ Area before immersion｝ × 100

[Water Resistance of Polyurethane Composition] A film cast at a temperature of 50 ° C. was heat-treated at 120 ° C. for 10 minutes, and then immersed in water at 20 ° C. for 24 hours to determine the elution ratio and area swelling ratio of the film. The water resistance was evaluated from the equation. Elution rate (%) = {(weight before immersion−weight after immersion) / weight before immersion} × 100 Area swelling rate (%) = ｛(area after immersion−area before immersion)
/ Area before immersion｝ × 100

[Mutation stability of polyurethane emulsion] 80 g of a 1% aqueous sodium chloride solution and 80 g of an ethylene-vinyl acetate copolymer emulsion ("OM-4200" manufactured by Kuraray, solid content concentration 55%) were added to 20 g of the polyurethane emulsion. The stability in the case of addition and mixing was observed. Judgment: ○ No change (good stability) △ Slight aggregation or phase separation observed × Aggregation or phase separation was severe

<< Production of Polyurethane Emulsion >> [Example 1] PMPA2150 was placed in a 3 l three-necked flask.
537.5 g, IPDI 111.1 g, DMPA
6.71 g was weighed and dried at 90 ° C. for 2 hours under a dry nitrogen atmosphere.
With stirring, the hydroxyl groups in the system were quantitatively reacted to obtain an isocyanate-terminated prepolymer. This is MEK 20
After adding 2.9 g and uniformly stirring, the temperature in the flask was lowered to 40 ° C., and 5.06 g of TEA was added, followed by stirring for 10 minutes. Next, Emulgen 985 was used as an emulsifier.
An aqueous solution obtained by dissolving 14.5 g (manufactured by Kao, nonionic surfactant) in 420 g of distilled water was added to the above prepolymer, and the mixture was emulsified by stirring with a homomixer for 1 minute. An aqueous solution in which 58 g and 12.52 g of IPDA were dissolved in 652 g of distilled water was added, and the mixture was stirred for 1 minute with a homomixer to carry out a reaction. Thereafter, MEK was removed by a rotary evaporator to obtain a polyurethane emulsion having a solid content of 40% by weight (hereinafter referred to as PU emulsion). The elution rate in toluene of the film made by casting the PU emulsion is 5%, and the area swelling rate is 100%.
The elution rate in water was 3%, and the area swelling rate was 0%. The stability when 80 g of a 1% aqueous sodium chloride solution and 80 g of an ethylene-vinyl acetate copolymer emulsion (“OM-4200” manufactured by Kuraray, solid content concentration 55%) were added to 20 g of the PU emulsion and mixed, respectively, was as follows. As shown in Table 3.

Example 2 PM was placed in a 3 l three-necked flask.
PA3600 540.0 g, IPDI 80.0 g,
6.04 g of DMPA was weighed out and dried under an atmosphere of dry nitrogen.
The mixture was stirred at 0 ° C. for 2 hours to quantitatively react the hydroxyl groups in the system to obtain an isocyanate-terminated prepolymer. After adding 191.4 g of MEK thereto and uniformly stirring the mixture,
The temperature in the flask was lowered to ° C, 4.55 g of TEA was added, and the mixture was stirred for 10 minutes. Next, as an emulsifier, Emulgen 985 (manufactured by Kao, nonionic surfactant) 19.1.
g in 397 g of distilled water was added to the prepolymer, and the mixture was emulsified by stirring with a homomixer for 1 minute.
Immediately, 64.1 g of polyvinylamine-2 was added to distilled water 4
An aqueous solution dissolved in 20 g was added, and the mixture was stirred with a homomixer for 30 seconds.
An aqueous solution dissolved in 0 g was added, and the mixture was stirred with a homomixer for 1 minute to perform a reaction. Thereafter, MEK was removed by a rotary evaporator to obtain a polyurethane emulsion having a solid content of 40 wt% (hereinafter referred to as PU emulsion). The solvent resistance of the film obtained from the PU emulsion and the mixing stability of the PU emulsion are as follows:
As shown in Table 3 below.

[Example 3] PT was placed in a 3 l three-necked flask.
MG2000 250.0 g, PCL2000250.
0 g, HMDI 118.1 g, DMPA 6.71 g
Was weighed and stirred under a dry nitrogen atmosphere at 80 ° C. for 2 hours to quantitatively react hydroxyl groups in the system to obtain an isocyanate-terminated prepolymer. After 188.7 g of MEK was added thereto and uniformly stirred, the temperature in the flask was lowered to 40 ° C., 5.06 g of TEA was added, and the mixture was stirred for 10 minutes. Next, Emulgen 985 (manufactured by Kao,
Nonionic surfactant) 6.7 g and Emulgen 93
0 (manufactured by Kao, nonionic surfactant) in 392 g of distilled water was added to the prepolymer, and the mixture was stirred for 1 minute with a homomixer and emulsified. Then, 32.2 g of polyvinylamine-3 and DETA were immediately added. 6.81 g
Then, an aqueous solution in which 5.62 g of IPDA was dissolved in 620 g of distilled water was added, and the mixture was stirred with a homomixer for 1 minute to perform a reaction. Thereafter, MEK was removed by a rotary evaporator to obtain a polyurethane emulsion having a solid content of 40% by weight (hereinafter referred to as PU emulsion). The solvent resistance of the film obtained from the PU emulsion and the mixing stability of the PU emulsion are shown in Table 3 below.
Was as shown in FIG.

Example 4 PM was placed in a 3 l three-necked flask.
537.5 g of PA2150, 87.1 g of TDI, D
6.71 g of MPA was weighed, and dried under an atmosphere of dry nitrogen.
At 2 ° C. for 2 hours to quantitatively react hydroxyl groups in the system,
An isocyanate-terminated prepolymer was obtained. This is ME
After adding 194.6 g of K and stirring uniformly, the temperature in the flask was lowered to 40 ° C., and 5.06 g of TEA was added to add 1
Stirring was performed for 0 minutes. Next, 16.5 g of Emulgen 985 (a nonionic surfactant made by Kao) and 32.4 g of polyvinylamine-1 were used as emulsifiers in distilled water 52.
A 0 g aqueous solution was added to the prepolymer, and the mixture was emulsified by stirring with a homomixer for 1 minute.
7.59 g and 4.42 g of EDA were added to distilled water 49
An aqueous solution dissolved in 4 g was added, and the mixture was stirred with a homomixer for 1 minute to perform a reaction. Thereafter, MEK was removed by a rotary evaporator to obtain a polyurethane emulsion having a solid content of 40% by weight (hereinafter referred to as PU emulsion). The solvent resistance of the film obtained from the PU emulsion and the miscibility of the PU emulsion are as follows:
As shown in Table 3 below.

Example 5 PM was placed in a 3 l three-necked flask.
537.5 g of PA2150, 194.5 of IPDI
g, 33.53 g of DMPA and 249.1 g of MEK were weighed and stirred at 60 ° C. for 8 hours in a dry nitrogen atmosphere to quantitatively react hydroxyl groups in the system to obtain an isocyanate-terminated prepolymer. Thereafter, the temperature in the flask was lowered to 40 ° C., 25.30 g of TEA was added, and the mixture was stirred for 30 minutes. Then, after adding 720.0 g of distilled water and stirring to emulsify the polyurethane prepolymer in water,
Immediately 41.8 g of polyvinylamine-2, DETA
17.02 g and 14.05 g of IPDA were distilled water 5
An aqueous solution dissolved in 76 g was added, and the mixture was stirred with a homomixer for 1 minute to perform a reaction. Thereafter, MEK was removed by a rotary evaporator to obtain a polyurethane emulsion having a solid content of 40% by weight (hereinafter referred to as PU emulsion). The solvent resistance of the film obtained from the PU emulsion and the mixing stability of the PU emulsion were as shown in Table 3 below.

Example 6 PM was placed in a 3 l three-necked flask.
537.5 g of PA2150, 194.5 of IPDI
g, 33.53 g of DMPA and 249.1 g of MEK were weighed and stirred at 60 ° C. for 8 hours in a dry nitrogen atmosphere to quantitatively react hydroxyl groups in the system to obtain an isocyanate-terminated prepolymer. Thereafter, the temperature in the flask was lowered to 40 ° C., 25.30 g of TEA was added, and the mixture was stirred for 30 minutes. Then, after adding 720.0 g of distilled water and stirring to emulsify the polyurethane prepolymer in water,
Immediately, 41.8 g of polyallylamine (manufactured by Nitto Boseki Co., Ltd., molecular weight 10,000), 17.02 g of DETA
An aqueous solution in which 14.05 g of IPDA was dissolved in 576 g of distilled water was added, and the mixture was stirred for 1 minute with a homomixer to carry out a reaction. Thereafter, the MEK is removed by a rotary evaporator, and a polyurethane emulsion having a solid content of 40 wt% (hereinafter referred to as a PU emulsion).
I got The solvent resistance of the film obtained from the PU emulsion and the mixing stability of the PU emulsion were as shown in Table 3 below.

Comparative Example 1 A polyurethane emulsion was prepared in the same manner as in Example 1 except that polyvinylamine-1 was not used. When an aqueous solution of DETA and IPDA was added, In addition, the system gelled and a stable emulsion could not be produced.

[Comparative Example 2] In Example 1, 38.7 g of Emulgen 985 was used without using polyvinylamine-1.
Except for using, a polyurethane-based emulsion (hereinafter referred to as PU emulsion) in the same manner as in Example 1.
I got The solvent resistance of the film obtained from the PU emulsion and the mixing stability of the PU emulsion were as shown in Table 3 below.

Comparative Example 3 To the PU emulsion obtained in Comparative Example 2 was added 34.0 g of polyvinylamine-1 and dissolved by heating to obtain a polyurethane emulsion (hereinafter referred to as PU emulsion). The solvent resistance of the film obtained from the PU emulsion and the mixing stability of the PU emulsion were as shown in Table 3 below.

Comparative Example 4 The procedure of Example 1 was repeated, except that polyvinylacetamide not subjected to hydrolysis was used in place of polyvinylamine-1, and 38.7 g of Emulgen 985 was used. An emulsion (hereinafter, referred to as a PU emulsion) was obtained. The solvent resistance of the film obtained from the PU emulsion and the mixing stability of the PU emulsion were as shown in Table 3 below.

[0069]

[Table 3]

[0070]

The polyurethane emulsion of the present invention is excellent in solvent resistance, excellent in miscibility with various aqueous emulsions and brines, and also excellent in water resistance.
Therefore, industrial fibers, leather, upholstery, apparel,
Floor materials (wood, concrete, floor polish), coating agents for plastic parts, etc., packages (wrapping paper, etc.), laminations (film / foil, fiber, etc.), general industrial adhesives (PVC sheet / wood, PVC sheet / It can be widely and effectively used in application fields such as metal, metal / wood), glass fiber sizing agent, ink, and paint.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 CH052 CK031 CK041 CK051 EV186 EV236 EV256 FD010 FD312 FD316 GC00 GG02 GH00 GH01 GJ01 GK01 GK02 GL00 GT00 HA07 4J034 BA08 CA02 CA03 CA04 CA05 CA13 CBCB CB CB CB CB CB CB CB CB CB CB CB CC12 CC23 CC26 CC33 CC45 CC52 CC61 CC62 CC65 CD04 CD06 CE03 DA01 DB01 DB03 DB04 DB07 DF01 DF02 DF03 DF16 DF20 DF21 DF22 DG03 DG04 DG06 DP02 DP03 DP06 DP20 HA01 HA07 HC03 HC12 HC13 HC17 HC22 HC46 HC52 HC61 HC73 KC HC HC HC HC HC HC HC HC HC HC HC HC HC KD02 KD04 KD12 KE02 QC05 RA03 RA06 RA07 RA08 RA09 RA10

Claims (4)

[Claims] In an aqueous medium, a polyurethane prepolymer having an isocyanate group in a molecule is provided with (a)
A polyurethane emulsion characterized in that an amine polymer and (b) a low molecular compound having an active hydrogen atom selected from a primary amino group, a secondary amino group, a primary hydroxyl group and a secondary hydroxyl group in a molecule are reacted with each other. Production method. 2. The method for producing a polyurethane emulsion according to claim 1, wherein the amine polymer is a hydrolyzate of a polymer of a monomer represented by the following (I). CH2 = CHNR1COR2 (I) (R1 and R2 represent a hydrogen atom or a methyl group.) 3. The polyurethane according to claim 1, wherein the polyurethane prepolymer has an anionic group bonded by a covalent bond, and at least a part of the anionic group forms a salt with the cationic compound. A method for producing a system emulsion. 4. The method for producing a polyurethane emulsion according to claim 1, wherein a nonionic surfactant is used when the polyurethane prepolymer is emulsified in an aqueous medium.