JPS58219213A - Aqueous dispersion of polyurethane - Google Patents

Abstract

PURPOSE:The titled dispersion, obtained from a compound having epoxy and hydroxyl groups, a polyol, a diisocyanate, a specific chain extender and a quaternizing agent, and having improved bonding strength and flexibility and further improved binding force and reinforcing effect as a binder for glass fibers. CONSTITUTION:A dispersion obtained by reacting (A) a compound having epoxy and hydroxyl groups, e.g. epoxidized polybutadienol with (B) a polyol, (C) a diisocyanate, (D) a chain extender having a tertiary amino group and plural Zerewitinoff activities, e.g. N-methyldiethanolamine, and (E) a quaternizing agent, e.g. dimethyl sulfate, preferably in 0.95-1.1 chemical equivalent ratio range between the groups having active hydrogen atoms in the components (A), (B) and (D) and the NCO groups in the component (C). EFFECT:The feeling of the adherend is not deteriorated, and the fine particles provide good finishing appearances.

Description

[Detailed description of the invention] The present invention relates to aqueous polyurethane 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 incyanate is used or urethane is crosslinked with formalin, but in the former case, the angle of 140°
If the C-position is not used, crosslinking may not occur or the blocking agent may remain and cause an adverse effect, and in the latter case, there are still problems of irritating odor and toxicity due to formalin.

On the other hand, polyurethane emulsion is used as a glass fiber sizing agent in glass fiber reinforced polypropylene, etc., but it has a drawback that although it has a strong sizing force, it lacks reinforcing effect.

An object of the present invention is to provide an aqueous polyurethane dispersion solution that has both high adhesive strength under normal conditions and high water-resistant adhesive strength, does not lose the flexibility characteristic of flexure, and does not impair the texture of objects to be adhered.

The object of the present invention is to provide an aqueous polyurethane dispersion solution that can simultaneously impart excellent focusing power and a high reinforcing effect when used as a glass fiber sizing agent.

It is an object of the present invention to provide an aqueous polyurethane dispersion having fine particles and thus an excellent finished appearance.

The present invention relates to compounds having at least one epoxy group and at least one hydroxyl group in the molecule, polyols, and diisocyanates 1-1-chains having at least one tertiary amino group and two or more Zelevitinoff activities in each molecule. The present invention relates to an aqueous cationic polyurethane dispersion obtained using an extender and a quaternizing agent.

Compounds having at least one epoxy group and at least one hydroxyl group in the molecule used in the present invention include epoxidized polydiolefinols such as epoxidized polybutadienol and epoxidized polypentadienol;
Examples include polyglycidyl ethers of polyols.

Specific examples of epoxidized polydiolefinols include azocabriol LPHX-31, LPHX-5
30, LPHX-2030, LPHX-2100, L
PH-2060 (manufactured by Adeka Argus Chemical Co., Ltd.),
Specific examples of the polyglycidyl ether of polyol include sorbitol polyglycidyl ether (trade name Tenacol EX-61.1, manufactured by Nagase Kasei Co., Ltd.). can be mentioned.

In addition, in the present invention, as compounds having at least one epoxy group and at least one hydroxyl group in the molecule, for example, compounds having two or more epoxy groups in the molecule include carboxylic acids, carboxylic acid anhydrides, Compounds obtained by reacting compounds selected from the group of amines and alkanolamines can be used.

In the present invention, various polyester polyols, polyether polyols, and other polyols can be used as the polyol. Specific examples of polyester polyols include adipate polyols such as polyethylene adipate polyol, polybutylene adipate polyol, and polyethylene propylene adipate polyol, terephthalic acid polyols (e.g., Toyobo Co., Ltd., trade names Vylon RUX, Vylon RV-20OL), and polyester polyols. Caprolactone polyol (e.g., Daicel Chemical, trade name Plaxel 2)
12, Plaxel 220), etc., and specific examples of polyether polyols include polyoxyethylene glycol, polyoxyethylene glycol, polyoxytetramethylene polyol, etc.

In addition, other polyols include polycarbonate polyols (e.g., West Germany, Baie, Shisha, trade name Desmofene 2020E), polybutadiene polyols (e.g., Nippon Soda, trade names G-1000, (, -2000, G
-3000, Idemitsu Petrochemical 1st School, product name Poly bd
R-45HT), castor oil-based polyols, and the like.

Various diisocyanates can be used in the present invention, such as diphenylmethane diisocyanate (MDI) and tolylene diisocyanate (TDl).
), toridine diisocyanate (TODI), xylylene diisocyanate (XD engineering), naphthylene diisocyanate L (NDI), isophorone diisocyanate)
(IPDI), hexamethylene diisocyanate (H
DI), dicyclohexylmethane diisocyanate (
HMDI) etc. are suitable. One of these incyanates
It is also possible to use one in which the part is blocked with a blocking agent.

The chain extender in the present invention includes at least one chain extender in the molecule.
A chain extender having two or more tertiary amine groups and two or more Zelevitinoff activities is used.

Examples of chain extenders having at least one tertiary amine group and two or more Zelevitinoff activities in the molecule mentioned above include N-methylgetanolamine, N-ethylgetanolamine, N-butylgetanol. amine,
Bis-hydroxyethylpiperazine, N-phenyldiethanolamine and the like can be mentioned.

Further, in the present invention, ordinary chain extenders can be used in addition to the above-mentioned chain extenders, and preferred examples thereof include the general formula % (R1 is a linear or branched alkylene group having 2 to IO carbon atoms, Connected by oxygen atoms, JP-A-58-
219213(3) May be. R2 is a linear or branched alkylene group or alicyclic group having 2 to 10 carbon atoms. A and B are groups having an aromatic ring. ), aliphatic diols, aliphatic diamines, aromatic diols, aromatic diamines, etc. can be mentioned.

Preferred examples of the aliphatic diol include ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, diethylene glycol, diethylene glycol, etc., and specific examples of the aliphatic diamine include ethylene diamine, 1,6- Examples include hexamethylene diamine and isophorone diamine.

Examples of the aromatic diol A include the following, and examples of the aromatic diamine B include the following.

In the present invention, a chain extender having at least one 8th amino group and two or more Tzelevitinoff activities in a molecule that can be converted into an ionic group is 94-nated with a quaternizing agent in advance. Alternatively, the resulting aqueous polyurethane dispersion can be cationized by neutralizing and copolymerizing the chain extender with polyurethane and then quaternizing it with a quaternizing agent.

In the present invention, examples of the quaternizing agent include dimethyl sulfate,
Dialkyl sulfates such as diethyl sulfate, alkyl halides such as ethyl bromide, methyl chloride, methyl iodide, and other benzyl chlorides may be appropriately determined from a wide range, but for example, at least one epoxy in the molecule The chemical equivalent ratio of the active hydrogen group contained in the compound having at least one hydroxyl group, the polyol, and the chain extender to the NCO group of the diisocyanate is 09 to 1.4, preferably 0.95 to 1.1. It is best to react within a certain range. Further, in the present invention, an inert solvent that does not react with NGO groups can be used, and can be recovered by distillation if necessary. Furthermore, a known urethanization catalyst, an aqueous antifoaming agent (for example, Toray Silicone, 5M-5512, etc.) to suppress foaming during emulsification, and a yellowing agent to improve weather resistance and heat discoloration resistance. It is also optional to use inhibitors (eg, hinodadophenol type, hindered amine type, etc.).

Examples of the above-mentioned solvents include acetone, ketos such as methyl ethyl ketone, esters such as ethyl acetate and methyl propionate, ethers such as dioxane and selonlube acetate, and dimethylformamide and dimethyl sulfoxide. These solvents may be used at any stage of the reaction of the present invention.

The aqueous polyurethane dispersion solution of the present invention can be produced by various methods, for example, by a one-shot method or a bleed polymer method. In the brepolymer method, for example, a compound having an epoxy group and a hydroxyl group, a polyol, and a diisocyanate are reacted to create an NCO-terminated prepolymer, then a chain extender is added and reacted, and a non-quaternized chain extender is used. When the polymer is mixed, a quaternizing agent is applied thereto, the resulting polymer is cooled, and water is added with vigorous stirring to obtain a milky white emulsion. Prepolymerization reaction is usually preferably carried out at about 60 to 180°C. Further, the quaternization reaction is usually preferably carried out at about 40 to 100°C.

In the present invention, other emulsions can also be blended into the obtained aqueous polyurethane dispersion. Examples of other emulsions include vinyl acetate/vinyl chloride copolymer emulsions (e.g., Denki Kagaku Kogyo, trade name Denkatex A)
C-20), ethylene/vinyl acetate copolymer emulsion (
Examples include Denka Kagaku Kogyo Co., Ltd. (trade name: Denka EVA Tex). Further, an aqueous solution of aliphatic polyamine such as ethylenediamine, diethylenetriamine, hexamethylenediamine, etc. may be used in combination with the aqueous polyurethane dispersion solution of the present invention.

The aqueous polyurethane dispersion obtained in the present invention can be used for various purposes, but when used as an adhesive, it has excellent both normal adhesive strength and water-resistant adhesive strength due to the presence of epoxy groups and its cationic nature, and is unique to urethane. □Does not damage the texture of the kimono.

Furthermore, when the urethane aqueous dispersion solution of the present invention is used as a glass fiber sizing agent, it has both excellent sizing power and a high reinforcing effect.

However, the aqueous urethane dispersion of the present invention has fine particles, so it has the advantage of giving a good appearance.

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

Example I (a) Pryol L, PH-206091f (
0.05 mol) (bl Plaxel 220
10 OF! (0,05 mol) (cl 4,4-diphenylmethane 5([(0,20 mol) diisocyanate (d) N-methyljetanol 11.9 g (0
, 10 mol) Amine (e) Dimethyl sulfate 12.6 f
(0', I 0 mol) In an Ioooml separable flask equipped with a stirrer, a thermometer, and a nitrogen inlet tube (a),
Add components (b) and (C) and react at 75 to 80°C for 60 minutes. After cooling to 50°C, methyl ethyl ketone (ME
K) Add 398 f and component (d) and heat to 75-80°C
Let it react for 3 hours. After cooling the liquid temperature to 50°C, (e
) Add a solution of the ingredients dissolved in 80f MEK,
Stir at 60°C for 1 hour. Then, after adding 564 g of water, MEK is distilled off to obtain an emulsion.

At this time, water may be added while MEK is distilled off.

The polymer content in the resulting emulsion is 35%, and the polymer contains 0.38% by weight of quaternary nitrogen atoms.

Example 2 An emulsion was obtained in the same manner as in Example I using the following components.

(a) Briall LPHX-20: (0136,
8g (0.04 mol) (b) polypterene adipe)
72 g (0.04 mol) Tuboran 4010 in polyol (C) m-xylylene diisocyanate 82.51
(0.17 mol) (d) N-methyljetanolamine 12 1NO, 10 mol) (e) Dimethyl sulfate 12.7 g (0.10 mol) M
EK fl+399f, +2180f water 50
6 g The polymer content in the emulsion obtained is 35% and the polymer contains 0.58% by weight of quaternary nitrogen atoms.

Example 3 An emulsion was obtained in the same manner as in Example I using the following components.

(a) Pryol LPH-206091y (0,
05mol) [Yes]) High07 RUX
l 00f (o, o5%le) (C) Inholonodiincyane-) 44.4IC0,20 mol) (
d) N-methyljetanolamine Il, 9 g (
0.10 mol) (e) dimethyl sulfate
11.3f (0.09 mol) MEK +11:(
88F! (2+78F! 562 g of water) The polymer content in the emulsion obtained is 35% and the polymer contains 0.47% by weight of quaternary nitrogen atoms.

Comparative Example 1 An emulsion was obtained in the same manner as in Example 1 using the following components.

(a) = Tuboran 4010 1 To, 4
g (0,0,85 mol) (b)') phenylmethane diisocyanate 639 r (o, 256 mol) -t (c) N-methyljetanolamine 20.3
g (0,170 mol) (d) dimethyl sulfate
12.9g (0,102mol) MEK+
1+401 g, +2+ 80 g water 5
62 f The polymer content in the resulting emulsion is 35% and the polymer contains 0.54% by weight of quaternary nitrogen atoms.

Next, the properties, film strength and adhesive strength of the obtained emulsion are shown in Table 1 below. In the table, the viscosity is 25℃
, is a value measured at 30 rpm using a BM type viscometer (No. 2 rotor), and the evaluation method for adhesive strength is as follows.

Adhesive base material Sufusef No. 4/soft vinyl chloride Application conditions Apply 2 of solids to the Sufu base and dry at 160℃ for 3 minutes Adhesion conditions Hot press at 120℃ with 61 pressures
0 second pressure bonding and peeling test Test specimens with a width of 25 were prepared and tested at 23°C with a peeling speed of 200 m7ftdn using Autograph IM-1.
00 (Shimadzu Corporation) Measured Water Resistant Adhesive Strength Peel strength of a sample immersed in room temperature water for 15 hours was measured under the above conditions while still wet Table 1 (above)

Claims (4)

[Claims] (1) Compounds, polyols, diisocyanates, having at least one epoxy group and at least one monohydroxyl group in the molecule, chain extensions having at least one tertiary amino group and two or more Zelevitinoff activities in the molecule A cationic polyurethane aqueous dispersion obtained from a quaternizing agent and a quaternizing agent. (2) The aqueous dispersion solution according to claim 1, wherein the chain extender is quaternized in advance with a quaternizing agent. (3) The aqueous dispersion solution according to claim 1, wherein the chain extender is copolymerized into polyurethane and then quaternized with a quaternizing agent. (4) The above-mentioned compound having at least one epoxy group and at least one hydroxyl group in the molecule may contain carboxylic acid, carboxylic acid anhydride, amine, or alkanolamine. The aqueous dispersion solution according to claim 1, which is a compound obtained by reacting compounds selected from the group.