JPS58179234A - Production of polyurethane aqueous dispersion - Google Patents

Abstract

PURPOSE:A blocked water-soluble urethane polymer with a special structure is dispersed, heated under stirring to dissociate the block and form a crosslinking structure by reaction of the regenerated NCO groups, thus producing the titled dispersion used as an adhesion for a variety of base materials. CONSTITUTION:Generally, polyols containing polyfunctional components and polyisocayanates are made to react to give a prepolymer and free isocyanates are blocked with a blocking agent such as a phenol. Further, the remaining free isocyanate groups are made to react with a corresponding amount of a compound bearing active hydrogens and ion-forming groups such as taurine to give a blocked water-soluble urethane compound of the formula (A is 3-6 functional organic residue containing urethane linkages; Z is compound containing ion- forming groups; Y is residue of blocking agent; n+m is 2, 3, 5). Then, the resultant compound is dispersed in water, then when necessary, a basic compound such as polyfunctional amine is added thereto, they are heated under stirring to dissociate the blocks and form a crosslinked structure.

Description

[Detailed description of the invention] The present invention relates to a method for producing an aqueous polyurethane dispersion.

More specifically, the general formula % formula % (1) (where A: the number of functionalities having a urethane bond in the molecule is 3
-6 organic group residue, Z: residue of a compound containing at least one ion-forming group in the molecule, Y containing at least one active hydrogen atom in two molecules, and isocyanate group formed by heat treatment. Blocking agent residue to be regenerated, n+m:2,
3 or 5) The branched blocked water-soluble urethane prepolymer shown in 3 or 5) is heated, adding a basic compound as necessary.
The present invention relates to a method for producing an aqueous polyurethane dispersion containing a crosslinked structure characterized by forced block dissociation under stirring.

As a conventional technique, Japanese Patent Publication No. 42-24192 and Japanese Patent Publication No. 43-9076 mainly involve adding a salt-type group or Wk capable of forming a salt to a linear polyurethane block and dispersing it in water. The weight proportion of the former salt type group is 1 to 15%, and the weight proportion of the latter salt type group is 0.02 to 1%.

Both of the former two patents are patents for adding a small amount of woody groups to mainly linear polyurethane blocks and making them water-dispersible. Due to its high molecular weight and high viscosity, it is extremely difficult to use conventional methods, and the manufacturing method, which involves complicated steps and uses special manufacturing equipment, is adopted, which reduces the cost of the finished product. It is also disadvantageous in terms of stabilization of quality.

In order to easily produce an aqueous dispersion of a polyurethane block having a crosslinked structure, the present invention first blocks free -NCO in the urethane prepolymer with a blocking agent2, and then adds a group capable of forming a salt. , a salt type base and an aqueous dispersion. The object of the present invention is to provide a method for easily producing a polyurethane aqueous dispersion of a crosslinked structure by forcibly dissociating the blocks and, if necessary, forming a crosslinked structure with a basic compound.

In order to add a small amount of hydrophilic groups to the polyurethane mass of the crosslinked structure and make it into an aqueous dispersion, it is necessary to It has drawbacks such as difficulty in uniformly imparting hydrophilicity, poor manufacturing stability, and the like. In addition, to improve product stability,
When a large amount of hydrophilic groups are added, water resistance deteriorates.

In the present invention, first, a polyol containing a polyfunctional component and a polyisocyanate are reacted in a solvent to synthesize a prepolymer having at least three free -NCOs remaining in one molecule.

After blocking the free -NCD groups with a blocking agent corresponding to two or more free -NCOs in one molecule, a compound corresponding to the remaining one or more free -NGOs is added and dispersed in water. let

Accordingly, if necessary, a basic compound is added to the block polyurethane aqueous dispersion and block dissociation is performed while heating and stirring, thereby making it possible to easily produce a polyurethane aqueous dispersion having a crosslinked structure.

By adding an inorganic base such as sodium bicarbonate, caustic soda, potassium chloride, or ammonia as a basic compound, or an aliphatic, cycloaliphatic, or aromatic polyfunctional amine, it is possible to more reliably form a crosslinked structure in polyurethane. Aqueous dispersions can be produced.

Polyfunctional amine and 1. Now, ethylenediamine.

Diamines such as hexamethylene diamine, l-4 cyclohexylene cyanine, benzidine, phenylene diamine, diethylene triamine.

triethylenetetramine, tetraethylenepentamine,
Polyurethane blocks of 79I:m structure can be prepared by diluting with a large amount of a suitable solvent with a highly viscous material to prevent reaction. It is very difficult to gel and apply a uniform salt product capable loading. Furthermore, since the polyurethane block of the crosslinked structure to which a small amount of woody group has been added has a high viscosity, it is impossible to disperse it in water without using a powerful high-speed stirring device.

The present invention makes it possible to prevent gelation with a smaller amount of solvent and to uniformly add wood-philic groups in a medium viscosity state when producing a polyurethane aqueous dispersion of a crosslinked structure. Become.

In addition, since a uniform aqueous dispersion is made by normal stirring and then forcibly dissociated, chain elongation and crosslinking are performed at the same time, it is easy to produce a polyurethane aqueous dispersion with a crosslinked structure with excellent product stability. I can do two things.

Highly crosslinked polyurethanes cannot be dissolved or dispersed in water by conventional methods.

In addition, polyurethane that is substantially linear and does not have a crosslinked structure can be easily made dispersible or 0% soluble by introducing a water-retaining compound or by using an emulsifier.
Physical properties include tensile strength, water resistance, solvent resistance, heat resistance, and deterioration.
].

In the present invention, in order to easily obtain a polyurethane main dispersion having a lock structure, as a result of intensive research, the present invention was completed by 1 dispersing it in water before the crosslinking structure and 2 crosslinking it. 1, that is, the present invention is based on the general formula % formula % (1) (where Δ: the functional number 3 that creates a urethane bond in the molecule)
-〇(+organic group residue, 2: residue IJ of compound rj containing at least one ion-forming group in the molecule, Y: at least one active water M I in the molecule): I Ki fjL,
If necessary, a basic compound is added to the branched blocked water-soluble urethane prepolymer represented by the blocking agent residue, n0rn: 2, 3 or 5), which produces +4 isocyanate-1 bales upon heat treatment. Add, heat,
This is a method for producing an aqueous polyurethane dispersion containing a crosslinked structure characterized by forced block dissociation under stirring.

・The branched blocked water-soluble urethane prepolymer represented by the general formula (+) has 2 to 4 t in the molecule.
At least two or more free ins of a trifunctional branched polyfunctional urethane prepolymer obtained from a compound A blocking agent that regenerates the isocyanate group by heat treatment that contains one or more -1- active hydrogen atom in the molecule is added to the cyanate group, and at least one active hydrogen atom in the molecule is added to one remaining free isocyanate group. A polyfunctional urethane prepolymer with a functional number of 3 to 6, which is added with a compound containing at least one ion-forming group, is described in detail below. 2. Polyols commonly used in polyurethane production include ethylene glycol-J.

Polyhydric alcohols such as petite/glycol, neopentyl glycol diethylene glycol, triethene glycol, glycerin, trimethylolpropane, pentaeryth 111-ol, monoethanolamine, jetanolamine, triethanolamine, propatoolamine, etc. Amino alcohols, the above polyhydric alcohols,
polyvalent amines, amino alcohols and catechol,
Alkylene oxides such as ethylene oxide, propylene oxide, etc. of III diphenyls such as hesorcin, hisphenol A, and hisphenol S. 1'dot](
Addition products and Alkire〉・1 hair IJ−
i light i. Adipic acid, succinic acid, phthalic acid, malic acid. Polyester polyols such as polycondensation products of saturated or unsaturated polycarboxylic acids such as 7-maric acid and saturated or unsaturated polyhydric alcohols such as ethylene glycol, butylene glycol, trimethylolpropane, and butynediol; Polybutadiene polyols such as denglycol or copolymerized polyols thereof with other vinyl monomers such as styrene, acrylonitrile, polychloroprene polyols or polyols used in the production of polychloroprene polyols and other vinyl monomers, polythioethers, polyacetal, polyesteramide,
Polyamides having a molecular weight of 2,000 or less can also be used.

The organic polyisocyanate is, for example, l.lis-(isocyanatehexyl)-puret isocyanate-1.
, triphenylmethane triisocyanate I, polymethylene polyphenyl polyisocyanate I, as well as hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate 1, and non-enyl 11-notane isocyanate. -Polyisonol/'r-1-, \renal methylene diisocyanate r-1 or 1-diisocyanate obtained by reaction with poly4-al of -bt
1. 3i1 incarnation -97J.1 toke I', +J.

1 piece F' per minute 1') f+': Plotter agent that produces both phenol, thalolphenol,
■) - Kekinbenzoic acid, 1) Okin Yasukuchi, butyl fragrant, 2L, Sol, etc. ()) Phenols, p-5ee butylbuenol, 11-1 (・r1 butylphenol-J[
.

1) -Tar/-hernoenol, p-nonylpheno-
71 tlI-ruphenols such as 11, isopropyl alcohol, l cr I-butyl alcohol, etc.
Class jiyo primary and tertiary alcohols, acetoxime, medicinal (
Rue-f Ii9 Toxim, Shi, Kuro・＼Xanone O M
Nmu', j't'l osym, ξ-vocal prolac, tam.

Lactano, such as δ-HaL, L:I '7ntano, etc.
active methylene compounds such as malonic acid mer\-11 varnish-i 11, aceto-acid-resistant-7' ItX-11 esteno L, 3-hydroxypyridine,
Examples include compounds that convert one active hydrogen atom into 3f), such as salt-capable nitrogen-containing compounds such as 8-hydroxyquinoline and 8-hydroxyquinoldine.

Examples of compounds containing at least one phosphorescent hydrogen atom and at least one ion-forming functional group in the molecule include amino acids such as taurine, N-methyltaurine, N-butyltaurine, and sulfamic acid. Sulfonic acids, aminocarboxylic acids such as glycine and alanine, 2-
Hydroxyethanol sulfonic acid, phenol 2.4-
Compounds containing anion-forming properties such as hydroxysulfonic acids such as disulfonic acid, hydroxycarboxylic acids such as glycolic acid, salicylic acid, p-oxygenated acid, and sulfuric acid, as well as N,N-dimethylethanolamine, N,N
-dimethylpropaturamine, N,N-dimethyl-β
- Alfquinol-based fatty alicyclic groups such as hydroxyethylaniline, α-hydroxyethylpyridine, β-hydroxyethylquinoline, N-hydroxyethylpiperidine, etc. -y5-Aromatic and heterocyclic groups, 'X class 7 ′
amines, N,N dimethylhydrazine-N, 14-dimethylethylenediamine-N.

Compounds which exhibit cationic monomerization, such as N-ance (root-robylenecyamine, 1-amino-pyridine, etc.) amines, are included.

Hydrophilicity is imparted to the formula (1) by converting it into a salt-like group by the well-known method, and it is then dissolved in water (for 3 minutes at IK).
Yes, it dissolves. In order to help the second time and first dispersion,
Current aqueous solvents may also be used.

After removing the solvent, the branched monocondensed wood-soluble urethane prepolymer uniformly dispersed or dissolved in water is heated and stirred in a solvent-containing state to forcibly dissociate the plotter. The aqueous polyurethane dispersion f1. is regenerated and becomes a crosslinked structure by the isoshi/゛゛〆-1・store()) reaction and finally forms a crosslinked structure. Rikiku IJ, ,, Neru.

Second, when performing iQi-controlled j rl no 9 dissociation, salt-filling compounds! When x'tA, IJI+, 1-toxolysis proceeds easily.

Therefore, when a polyfunctional amine is used as the pentavalent α product, crosslinking or chain elongation can be easily achieved.

The block reaction is carried out at a reaction temperature of 40 to 100°C in the presence or absence of a suitable inert solvent, optionally using a basic catalyst such as triethylamine or an organic group A catalyst such as dibutyltin dilaurate. .

The reaction of a partially blocked urethane prepolymer with a compound containing at least one active hydrogen atom and at least one ion-forming group in the molecule can be carried out by introducing the ion-forming group into a salt-like group in advance and using a suitable linkage. In the case of compounds containing anion-forming groups, for example, primary compounds such as ethylamine, triethylamine, dimethylamine, pyridine, etc.
class, secondary and tertiary amines, ethanolamine,
Organic bases such as alcohol amines such as jetanolamine and triethanolamine, and ammonia, and metal hydroxides and carbonates such as potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium bicarbonate. , 1 rare IA, % 1. on the phase 1],
In addition, cation formation (contains Ji, j, 5 (V'Fruf), hydrochloric acid, sulfuric acid.

Nitric acid, silicate) inorganic acids, moth acid, acetic acid, lactic acid, chlorine 11
Citric acid 1. ,・and-ノ)('acids or methyl iodide, Wa Chemical + I1. After converting into a masonry-like substance with an alkyl stopper such as dimethyl sulfate, it can be used as an aqueous solution or fJ organic solvent solution. It is preferable to add some charcoal.

The ion-forming group is added to the partially blocked urethane prepolymer in an aqueous solution or an organic solvent, and the ion-forming group is added to the urethane prepolymer. It is also possible to add as an Air-type gold compound solution or as a solution, which can be added as a solution of a branched fluorine or silica compound homogeneously dissolved in water. Stamp the penis and force the polymer
To remove ivy, the purpose can be achieved by heating the wet part at 85°C to 100°C with stirring.

Block dissociation can be easily achieved by adding a basic compound at 2σ).

Also, Naki 1. (Polyfunctional amines as bamboo compounds?
fj 1111 The isocyanate group regenerated by Suni + Ni and Ni 1 ribotuta dissociation reacts with polyfunctional amines,
It is possible to easily produce a polyurethane aqueous dispersion having a crosslinked structure with excellent physical properties.

The polyurethane aqueous dispersion obtained by the present invention is as follows.

It is easy to dilute with water, has excellent compatibility with other water-based resins, and has excellent storage stability.Secondly, since it forms a crosslinkable film, it can be used extremely effectively for adhesion of films, which has been considered difficult in the past. Therefore, in addition to adhesives for synthetic fibers such as nylon and polyester, adhesive processing for various base materials other than fibers,
Water-based resins for fibers such as polyepoxide compounds, ethylene urea compounds, SBR, MBR, etc., latex melamine formalin resins, phenol formalin resins, urea formalin resins, acrylic emulsions, starches, carboxymethylcellulose, polyvinyl alcohol, etc. It is possible.

Example 1 10.0 parts of polybutylene adipate (minute I' ¥20 + 50) (value 55.7) containing 1 terminating o+++M, 3 parts of trimethylropane, 3 parts of 1,4-butanediol
27 parts of hexamethylene diisocyanate (N+:0
10 il = 1.31), heated slowly in 50 parts of dioxane and reacted at 85-95°C for 60 minutes,
2% free isocyanate (183 parts based on urethane prepolymer) was obtained.

Next, add 35 parts of nitrogen, 5 parts of nitrogen,
IW, add 40 parts of the dissolved oil and 0.1 part of l-ethylamine as a catalyst at 50°C (step 2), heat gradually, and heat to 70°C.
80° ("[' Reacted for 120 minutes, free isocyanate 0.95° per person, (for urethane prepolymer)
223 parts of a dioxane solution of the partial pronone prepolymer was obtained.

Next, after diluting with 70 parts of 40% pure xane, 9 parts of 40% taurine solute solution was added at 40°C, and the mixture was heated at 40-50°C for 30 minutes. After this, 200 parts of water was slowly added to the mixture while stirring to obtain 493 parts of a milky white stable water dispersion with a solid content of 28%.

The solvent was removed under reduced pressure using an evaporator to obtain 338 parts of a blocked polyurethane aqueous dispersion.

Then after adding 1 part of ethylenediamine.

When stirring was continued for 120 minutes at 85° C. to 95 T, block dissociation occurred, the viscosity increased, and a highly stable aqueous polyurethane dispersion containing the desired crosslinked structure was obtained.

Example 2 Polytetramethylene glycol (M W 2000) 1
00 parts, 6 parts of 1.6 hexanediol, 2 parts of trimethylolpropane, 40 parts of hydrogenated MDI (NCOloH=
1°22) was added and reacted at 50-60°C for 120 minutes to obtain 198 parts of a urethane prepolymer with a free isocyanate group content of 1.62% (based on the urethane preformer).

Next, 5 parts of p-oxybenzoic acid was added to 35 parts of tetrahydrofuran.
40 parts of a solution in which 1 part was dissolved and 0.4 parts of triethylamine as a catalyst were gradually heated at 50°C, and 1 part was dissolved at 50 to 60°C.
8080 minutes reaction free incyane-1-j & 5fi0.
211 parts of a 97% (based on urethane prepolymer) partially flocked prepolymer solution in tetrahydrofuran was obtained.

Next, 11 parts of the solution was added to Tetrahuman 10% Taurinso Z/7 at 40°C.

, 10 to 30 minutes at SOC! After the reaction, water 200
%i:'. 'l: 4 (minutet) 438 parts of Kt body were obtained.

The solvent was removed from the two t1 under reduced pressure using an evaporator and a turret to obtain 282 parts of a blocked polyurethane aqueous dispersion. Next, 2 parts of diethyl chloride was added, and the mixture was heated at 85°C.
When stirring was continued for 120 minutes at ~95°C, block dissociation occurred. A stable polyurethane main dispersion which thickened and contained the desired crosslinked structure was obtained.J (Example 3 Polycaprola')tonpolyol (Mounshisha +000) 1
00 parts, after melting 4.5 parts of pentaerythritol.

"After dissolving in 150 parts of 1,N dimethylamide, 58 parts of diphenylmethane 4.4 diisocyanate (NCO10
1! = 1.40) and reacted at 85°C to 95°C for 60 minutes to obtain 312 parts of a urethane prepolymer with a free isocyanate base t of 3.50% (based on the urethane preformer).

Next, 22 parts of p-nonylphenol was dissolved in 35 parts of NN/dimethylformamide, and 0.0% of the triethylamine catalyst was dissolved.・
Add one part to the hair at 50°C and gradually heat it to 80-95°.
Reaction free isocyanate base 410.C for 12020 minutes.
369 parts of a 91% (based on urethane prepolymer) partially block prepolymer solution in NN/dimethylformamide was obtained.

Next, after diluting with 100 parts of NN/dimethylformamide, 8 parts of 40% glycine soda aqueous solution was added at 40°C.
After reacting at 0 to 50°C for 30 minutes, 285 parts of water was gradually added with stirring to obtain 762 parts of a milky white stable water dispersion with a solid content of 25%.

The solvent was removed under reduced pressure using an evaporator, and 470 parts of blocked polyurethane aqueous dispersion was obtained.
After adjusting the pH to 118-9 with aqueous soda solution, 85"
(When stirring is continued for 120 minutes at -05°C, block dissociation occurs, the viscosity increases, and a stable polyurethane aqueous dispersion containing an L1-like crosslinked structure becomes tr+ +:, , t+
Ta.

Example 1 100 parts of polypropylene glycol (molecule [500),
Trime 1,000 rono l propane 9 parts, pentaeris 1 river -
Part 1 of L.L. was heated and dissolved, and then cooled. Socialate (80/20) 105 parts (N(-0
/1111 = 1. :'18) and gradually heated in 200 parts of -methyl ethyl ketone at 75 to 85°C.
Reacted for 0 minutes, containing 6.30% free isocyanate groups (
Next, 40 parts of p-see-butylphenol was dissolved in 50 parts of methyl ethyl ketone, and 50 parts of the solution and 0.3 part of tetramethylpropylene diamine as a catalyst were obtained. °(j at ゛)11 and gradually heat to 12020 at 75-85℃
Separation reaction 512 parts of a methyl ethyl ketone solution of a partially block prepolymer having a free isocyanate group content of 1.33% (based on the urethane prepolymer) was obtained.

Next, dilute with 238 parts of methyl ethyl ketone, add 48 parts of 40% sodium sulfamate aqueous solution at 40°C,
After reacting at 50°C for 30 minutes, 423 parts of water was gradually added with stirring to obtain a milky white stable water dispersion 1 with a solid content of 24%.
220 copies were obtained.

The solvent was removed under reduced pressure using an evaporator to obtain 732 parts of a blocked polyurethane aqueous dispersion.

Next, when this aqueous dispersion was continued to be stirred at 85 DEG C. to 95 DEG C. for 180 minutes, block dissociation occurred, the viscosity increased, and a stable polyurethane aqueous dispersion containing the desired crosslinked structure was obtained.

applicant Daiichi Kogyo Seiyaku Co., Ltd.

Claims (1)

[Claims] General formula % Formula % (1) (where 2A: functional number 3 having a urethane bond in the molecule)
- 6, A 1° functional group residue, 2: residue μ of a compound containing at least one ion-forming group in the molecule, Y: containing at least ] active hydrogen atoms in the molecule If necessary, a basic compound is added to the branched blocked water-soluble urethane prepolymer which is bonded with a blocking agent residue that regenerates isocyanate groups by heat treatment, n: 2, 3 or 5). 1. A method for producing an aqueous polyurethane dispersion containing a crosslinked structure characterized by forced block dissociation under heating and stirring.