JPS60120751A - Aqueous resin dispersion - Google Patents

Abstract

PURPOSE:To provide an aqueous polyurethane resin dispersion capable of forming films excellent in water resistance, by dissolving a high-molecular resin in an org. solvent soln. of polyurethane resin having quat. nitrogen atoms and then mixing water with the soln. CONSTITUTION:A polyol (e.g., polyethylene adipate glycol) and a diisocyanate (e.g., 2,4-tolylene diisocyanate) are allowed to react to form a polyurethane. An org. solvent (e.g., acetone, ethyl acetate, or N-methylpyrrolidone) is added to dissolve the polyurethane, which is then allowed to react by the addn. of a diol having tert. amino groups (e.g., N-methydiethanolamine). The reaction product is further allowed to react by the addn. of a quaternizing agent (e.g., dimethyl sulfate). A high-molecular resin soluble in the above solvents (e.g., vinyl chloride/ vinyl acetate/vinyl alcohol copolymer) is dissolved in the resulting org. solvent soln. of polyurethane resin having quat. nitrogen atoms, and then water is added with stirring to the above soln., yielding an aqueous resin dispersion.

Description

[Detailed description of the invention] The present invention relates to polyurethane aqueous fil (fat dispersions).

Polyurethane emulsions are used for various purposes, but when used as adhesives, for example, there is a problem with water-resistant adhesive strength, which is significantly lower than normal adhesive strength. In order to prevent this drawback, blocked isocyanates are used or urethane is crosslinked with melamine, but in the former case, crosslinking does not occur unless the temperature is about 140°C, or the blocking agent remains and has an adverse effect. In the latter case, there are problems of pungent odor and toxicity due to formalin.

An object of the present invention is to provide a polyurethane aqueous resin dispersion that provides a film with excellent water resistance.

The present invention is an aqueous tilt fat obtained by adding water under stirring to an organic solvent solution of a polyurethane resin having a quaternized nitrogen atom, after dissolving a high molecular weight O (fat) that is soluble in this organic solvent. Concerning dispersion.

The polyurethane resin having a quaternized nitrogen atom of the present invention can be obtained, for example, from a polyol, a diisocyanate, a nool having at least one tertiary amino group, and a quaternizing agent.

In the present invention, various polyester polyols, polyether polyols, and various polyols can be used as the polyol. Examples of polyester polyols include aliphatic dicarboxylic acids having 4 to 20 carbon atoms such as 7-dipic acid, suberic acid, sebacic acid, and brassylic acid, terephthalic acid, and isophthalic acid as acid components, and ethylene glycol, propylene glycol, and neopentyl. R”Jktlt of glycol, hexamethylene glycol, etc.
1 to 6 aliphatic diols, ether glycols such as diethylene glycol and dipropylene glycol, spiroglycol L, N- such as N-methyljetanolamine, etc.
Polyester polyols or polycaprolactone polyols containing flukylnoalkanolamine or the like as a polyol component can be used, and specific examples include adipate polyols such as polyethylene adipate polyol, polybutylene anovate polyol, and polyethylene propylene anopate polyol. , terephthalic acid polyol (e.g., Toyobo Co., Ltd., trade name: Vylon R)
UX, Vylon RV-20OL>, polycaprolactone polyol (e.g., Daicel Chemical, trade name Plaxel 21
2, Praxel 220), etc.

Specific examples of polyether polyols include polyoxyethylene polyol, polyoxypropylene polyol, polyoxytetramethylene polyol, and the like.

In addition, other polyols include polycarbonate polyol (e.g., Bayer AG, West Germany, trade name Desmoreene 2020E), polybutadiene polyol (e.g., Nippon Soda, trade name G-1000, G-2000, G-:
(000, Idemitsu Petrochemical, trade name Poly bd R-
4511T), polypentanoene polyol, castor oil polyol, etc. These polyols can be used alone or in combination of two or more.

As the diisocyanate of the present invention, various difunctional well-known aliphatic, alicyclic and aromatic incyanates in the field of polyurethane production can be used, such as hexamethylene diisocyanate (II D I ), inphorone diisocyanate, etc. ) (+1101), 4,4-dicyclohexylmethane diisocyanate) (IIMDI), 2.
4-Tolylene diisocyanate (2,4-TDI), 2
．． 6-) Lylene diisocyanate (2,6-TDI)
, 4,4-diphenylmethane diisocyanate (MI)
I), orthotoluinone diisocyanate) (TOII
+), naphthylene diisocyanate (NDI), xylylene diisocyanate (XI) I), lJ9:zshi4soshi74-) (LDI).

Examples of diols having at least one tertiary amino group in the present invention include N-methylgetanolamine, N-methylgetanolamine, N-butylgetanolamine, N-phenyldiethanolamine, N,N
-dihydroxyethylpiperazine, N,NE/methylamino-2,2-bishydroxymethylethylamine, and the like.

Examples of quaternizing agents include dialkyl sulfates such as dimethyl sulfate and diethyl sulfate, methyl chloride, methyl iodide,
Various quaternary acids such as halogenated hydrocarbons such as ethyl bromide and benol chloride, organic acids such as acetic acid, propionic acid, and monochloroacetic acid, and inorganic acids such as hydroiodic acid, hydrobromic acid, hydrochloric acid, and perchloric acid. A curing agent can be used.

Furthermore, in the present invention, if necessary, ordinary chain fil
Agent II can also be used. Examples of the chain extender include di- to hexafunctional polyols with a molecular weight of 500 or less and diamines having 7 primary or secondary terminal amide groups with a molecular weight of 500 or less. Suitable chain extenders include, for example: (a) ethylene glycol, diethylene glycol,
Polyols (b) such as propylene glycol, dipropylene glycol, butanediol, hexanediol, glycerin, trinotyrolpropane, pentaerythritol, sorbitol, 1,4-cyclohexanediol, 1°4-cyclohexane dimetatool, xylylene glycol, etc. Diamines such as hydrazine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, and 1,4-cyclohexanoamine (C) Alkanolamines such as ethanolamine, jetanolamine, and triethanolamine (d) Hydroquinone, pyrogallol, 4. 4-inpropylidene di7er/-
Molecular weight 50 obtained by adding propylene oxide and/or ethylene oxide to aniline and the above polyols, diamines, and alkanolamines in any order
Examples include polyols having 0 or less.

In the present invention, each component may be appropriately determined from a wide range depending on the desired aqueous dispersion, but for example, the components contained in the polyol, the diol having at least one tertiary amine 7 group, and the chain extender. It is preferable to carry out the reaction in such a range that the chemical equivalent ratio between the active hydrogen groups in the diisocyanate and the NCO groups in the diisocyanate is from 0.9 to 1.4, preferably from 0.95 to 1.1. Further, in the present invention, an inert solvent that does not react with NGO groups is used, and recovery can be carried out by distillation if necessary. Furthermore, a known urethanization catalyst, an aqueous antifoaming agent to suppress foaming during emulsification (for example, Toray Silicone, 5M-5512, 'f://7' Nia,
SN7”7oh7v-113,432 etc.), creativity,
It is also optional to use an anti-yellowing agent (eg, hindered phenol type, hindered/mino type, etc.) to impart heat discoloration resistance. - Examples of the above-mentioned solvents include ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and methyl propionate, ethers such as nooxane, tetrahydro7rane, and cellosolve acetate; Examples include methyl sulfoxide, hexamethylphosphoric triamide, and N-methylpyrrolidone, and these solvents may be used at any stage of the reaction of the present invention.

The polyurethane resin of the present invention can be produced by various methods, such as a one-shot method or a prepolymer method. In the prepolymer method, for example, a polyol and a diisocyanate are reacted to form an NCO-terminated prepolymer, and then a diol having at least one tertiary amine 7 group and, if necessary, a chain extender are added and reacted. The quaternization reaction can be carried out during or after the polymerization of the polyurethane. The reaction of prepolymerization is usually 60~
Preferably, it is carried out at 130°C. Further, the quaternization reaction is generally preferably carried out at a temperature of 40 to 100°C.

The aqueous resin dispersion of the present invention is obtained by dissolving a high molecular weight resin soluble in the organic solvent in the obtained organic solvent solution of the polyurethane resin, and then adding water while stirring to emulsify. 1 ↑h (As the fat, for example, polyvinyl chloride, vinyl chloride/vinyl acetate copolymer, polyester resin (e.g., Toyobo Co., Ltd., Byron 200, Byron 3)
00 etc., manufactured by Fuji Photo Film Co., Ltd., Stafix, etc.),
Vinyl chloride/vinyl acetate/vinyl alcohol copolymer (
Examples include Union Carbide Co., Ltd., V to Gl1, etc.). After emulsification, the solvent is distilled off under normal pressure or reduced pressure to obtain an aqueous dispersion of polyurethane resin containing no solvent.

The aqueous polyurethane dispersion of the present invention can be used in various fields in which conventional aqueous polyurethane dispersions are used, such as adhesives, paints, fiber sizing agents, textile treatment agents, etc. I take it.

The present invention will be explained below with reference to Examples.

Example 1 In a 2-liter separable 7-glass tank equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a reflux condenser, 4 liters of polyethylene adipate glycol and Tubolan 4040) were added.
00g (1,,0 mol) and 76.6g (2,2 mol) of T
mol) and reacted for 1 hour at 70±10°C. After cooling, A7Tone 5358 was added and dissolved well. Then N
- 28.6 g (1.2 mol) of methylnoethanolamine
was added, and the mixture was allowed to react under refluxing acetone until the absorption of NGO at 2250 cm −1 disappeared according to an infrared absorption spectrum.

After cooling to 50°C, 30.2 g (1.2 mol) of dimethyl sulfate was added and reacted at 60°C for 1 hour. Further to V CI+
(4078) was added and dissolved by heating, 95 g of water (1) was added under stirring, and then acetone was distilled off to obtain a milky white emulsion. The resulting emulsion had a solid content of 35
%, viscosity at 25° C. 85 cps, 1+ll 6.1.

Comparative Example I V A solution of polyurethane resin was prepared in the same manner as in Example 1 except that I+ was not added. To this was added 994° of water with stirring, and then the acetone was distilled off to give a solid content of 35% and a viscosity of 55 cps at 25°C, p, lI
A 6.0 emulsion was obtained.

Adhesion Test Hydroxyethyl cellulose was added to each of the emulsions of Example 1 and Comparative Example 1, and the emulsions were stirred to thicken.

The obtained emulsion was coated on a soft vinyl chloride sheet with a thickness of 1111111 with a bar coater at 60 B/
+n 2 coated, +(i) immediately laminated with polyester woven fabric, crimped with a hand roller, and heated in an oven at 80°C for 2
Dry for an hour, 1! (The obtained sample was cut to a width of 2.5 cm, and the 180 degree peel strength was measured using a Shimadzu Autograph 1M-100 at a crosshead speed of 200 mm/min. The 180 degree peel strength after 24 hour immersion was also measured.The results are shown in Table 1.

Table 1 Peel strength (k8/2.5cm) Normal condition after immersion in water Example 1 3.3 2.4 Comparative example]' 2, 8 1.2 (that's all) Patent applicant: Toyo Rubber Industries, Ltd. Representative Attorney ± []1 Iwao Mura

Claims (2)

[Claims] (1) An aqueous resin dispersion obtained by dissolving a high molecular weight resin soluble in an organic solvent in an organic solvent solution of a polyurethane resin having a quaternized nitrogen atom, and then adding water with stirring. (2) Claim 1 obtained by distilling off the organic solvent
Dispersion as described in Section.