JPH036929B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to aqueous polyurethane dispersions. Polyurethane emulsion is used for various purposes, but when it is used as an adhesive, for example, there is a problem in water-resistant adhesive strength, which has the drawback of being significantly lower than normal adhesive strength. In order to prevent this drawback, blocked isocyanates are used or urethane is cross-linked with formalin, but in the former case cross-linking does not occur unless the temperature is around 140°C, and the blocking agent remains and has an adverse effect. In the latter case, there are problems of pungent 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 strong sizing power, it lacks reinforcing effect. An object of the present invention is to provide an aqueous polyurethane dispersion solution that has both high normal adhesive strength and waterproof adhesive strength, does not lose the flexibility peculiar to urethane, and does not impair the texture of objects to be adhered. An 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 with fine particles and thus 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, diisocyanates, and chain extenders having at least one tertiary amino group and two or more Zelevitinoff activities in the molecule. and a cationic polyurethane aqueous dispersion obtained from 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 polybutadienol,
Examples include epoxidized polydiolefinols such as epoxidized polypentadienols, and polyglycidyl ethers of polyols. Specific examples of epoxidized polydiolefinols include Adekapriol LPHX-31,
LPHX-530, LPHX-2030, LPHX-2100,
LPH-2060 (manufactured by Adeka Argas Chemical Co., Ltd.),
Poly bd R-45 EPI (manufactured by Idemitsu Petrochemical Co., Ltd.) can be mentioned, and specific examples of polyglycidyl ethers of polyols include sorbitol polyglycidyl ether (trade name: Denacol EX-611, manufactured by Nagase Kasei Co., Ltd.). be able to. In addition, in the present invention, as the compound 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 acid, carboxylic acid anhydride, amine, alkanol. Compounds obtained by reacting compounds selected from the group of amines can be used. In the present invention, polyols include various polyester polyols, polyether polyols,
Other polyols can be used. Specific examples of polyester polyols include adipate polyols such as polyethylene adipate polyol, polybutylene adipate polyol, and polyethylene propylene adipate polyol, and terephthalic acid polyols (e.g., Toyobo Co., Ltd., trade name Byron).
RUX, Vylon RV-200L), polycaprolactone polyol (e.g., Daicel Chemical, trade name Plaxel 212, Plaxel 220), etc., and specific examples of polyether polyols include polyoxyethylene glycol, polyoxypropylene polyol, polyoxytetramethylene. Polyols and the like can be mentioned. In addition, other polyols include polycarbonate polyol (e.g., West Germany, Bayer AG, trade name: Desmofene 2020E), polybutadiene polyol (e.g., Nippon Soda, trade name: G-1000, G-
2000, G-3000, Idemitsu Petrochemical, product name Poly bd
R-45 HT), castor oil polyols, and the like. Various diisocyanates can be used in the present invention, such as diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), tolidine diisocyanate (TODI), xylylene diisocyanate (XDI),
Suitable examples include naphthylene diisocyanate (NDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), and the like.
It is also possible to use a part of these isocyanates blocked with a blocking agent. As the chain extender in the present invention, a chain extender having at least one tertiary amino group and two or more Zelevitinoff activities in the molecule is used. Examples of chain extenders having at least one tertiary amino group and two or more Tselevitinoff activities in the molecule mentioned above include N-methyldiethanolamine, N-ethyldiethanolamine, N-
Examples include butyldiethanolamine, bis-hydroxyethylpiperazine, N-phenyldiethanolamine, and the like. Further, in the present invention, ordinary chain extenders can be used in addition to the above-mentioned chain extenders, and preferable examples include those having the general formulas HO-R ¹ -OH, H ₂ NR ² -NH ₂ , A(-CH ₂ CH ₂ OH) ₂ , H ₂ N-B-NH ₂ , (R ¹ is a linear or branched alkylene group having 2 to 10 carbon atoms, and may be connected by an oxygen atom. R ² is a carbon number 2 to 10 linear or branched alkylene groups or alicyclic groups.A and B
is a group having an aromatic ring. ) Aliphatic diols, aliphatic diamines, aromatic diols,
Examples include aromatic diamines. Preferred examples of the aliphatic diol include ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, etc., and specific examples of the aliphatic diamine include ethylene diamine, 1,6
-Hexamethylene diamine, isophorone diamine, etc. can be mentioned. Further, as A of the above aromatic diol, for example,

【formula】

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【formula】 etc., and as the aromatic diamine B,

【formula】

【formula】

[Formula] etc. can be exemplified. In the present invention, a chain extender having at least one tertiary amino group and two or more having Tselevitinoff activity in a molecule that can be converted into an ionic group is quaternized in advance with a quaternizing agent, or the chain By copolymerizing the extender into polyurethane and then quaternizing it with a quaternizing agent, the resulting aqueous polyurethane dispersion can be cationized. In the present invention, as the quaternizing agent, various alkyl agents such as dialkyl sulfates such as dimethyl sulfate and diethyl sulfate, alkyl halides such as ethyl bromide, methyl chloride, and methyl iodide, and benzyl chloride can be used. . In the present invention, each component may be appropriately determined from a wide range depending on the intended aqueous dispersion solution.
For example, a compound having at least one epoxy group and at least one hydroxyl group in the molecule, a chemical equivalent ratio of the active hydrogen group contained in the polyol and chain extender to the NCO group of the diisocyanate of 0.9 to 1.4,
It is preferable to react within a range of 0.95 to 1.1. Furthermore, in the present invention, an inert solvent that does not react with CO groups can be used, and can be recovered by distillation if necessary. In addition, known urethanization catalysts and aqueous antifoaming agents (e.g., Toray Silicone, SM-
5512, etc.), it is also optional to use an anti-yellowing agent (eg, hindered phenol type, hindered amine type, etc.) to impart weather resistance and 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 dioxane and cellosolve acetate, and other solvents such as dimethylformamide and dimethyl sulfoxide. 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, such as a one-shot method or a prepolymer method. In the prepolymer 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. Next, a quaternizing agent is applied, and after the resulting polymer is cooled, water is added with vigorous stirring to obtain a milky white emulsion. Prepolymerization reaction is usually preferably carried out at about 60 to 130°C. In addition, the quaternization reaction is usually about 40~
Preferably it is carried out at 100°C. In the present invention, other emulsions can also be blended into the resulting aqueous polyurethane dispersion. Examples of other emulsions include vinyl acetate/vinyl chloride copolymer emulsions (e.g., Denki Kagaku Kogyo,
Product name Denkatex AC-20), ethylene/
Examples include acetic acid copolymer emulsion (eg, Denka Kagaku Kogyo, trade name: Denka EVA Techs). 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. without losing its flexibility and without damaging the texture of the adherend. 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. Furthermore, the aqueous urethane dispersion of the present invention has fine particles, so it has the advantage of providing a good finished appearance. The present invention will be explained below with reference to Examples. Example 1 (a) Pryol LPH-2060 91 g (0.05 mol) (b) Plaxel 220 100 g (0.05 mol) (c) 4,4'-diphenylmethane diisocyanate
50g (0.20mol) (d) N-methyldiethanolamine
11.9 g (0.10 mol) (e) Dimethyl sulfate 12.6 g (0.10 mol) 1000 ml with stirrer, thermometer and nitrogen inlet tube
Put components (a), (b) and (c) into a separable flask and react at 75-80°C for 60 minutes. After cooling to 50℃,
Add 398 g of methyl ethyl ketone (MEK) and component (d), and react at 75-80°C for 3 hours. Set the liquid temperature to 50
After cooling to .degree. C., a solution of component (e) dissolved in 80 g of MEK is added and stirred at 50 to 60.degree. 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 emulsion obtained was 35%, and the polymer content was 0.38
Contains % by weight of quaternary nitrogen atoms. Example 2 An emulsion was obtained in the same manner as in Example 1 using the following components. (a) Plyall LPHX−2030
136.8g (0.04mol) (b) Polybutylene adipate polyol (Nituporan 4010) 72g (0.04mol) (c) m-xylylene diisocyanate
32.5g (0.17mol) (d) N-methyldiethanolamine
12g (0.10mol) (e) Dimethyl sulfate 12.7g (0.10mol) MEK (1) 399g, (2) 80g Water 506g The polymer content in the obtained emulsion was 35
% and the polymer contains 0.53% by weight of quaternary nitrogen atoms. Example 3 An emulsion was obtained in the same manner as in Example 1 using the following components. (a) Pryol LPH-2060 91g (0.05mol) (b) Vylon RUX 100g (0.05mol) (c) Isophorone diisocyanate
44.4g (0.20mol) (d) N-methyldiethanolamine
11.9 g (0.10 mol) (e) Dimethyl sulfate 11.3 g (0.09 mol) MEK (1) 388 g, (2) 78 g Water 562 g The polymer content in the obtained emulsion was 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) Nituporan 4010 170.4g (0.85mol) (b) Diphenylmethane diisocyanate
63.9g (0.256g) (c) N-methyldiethanolamine
20.3g (0.170mol) (d) Dimethyl sulfate 12.9g (0.102mol) MEK (1) 401g, (2) 80g Water 562g The polymer content in the obtained emulsion was 35
% and the polymer contains 0.54% by weight of quaternary nitrogen atoms. Next, the properties, film strength and deposition strength of the obtained emulsion are shown in Table 1 below. In the table, the viscosity is the value measured at 25°C and 30 rpm using a BM type viscometer (No. 2 rotor), and the evaluation method for adhesive strength is as follows. Adhesive base material SFUMOS No. 4/soft vinyl chloride Application conditions: Apply 20g/ ^m2 of solid content to the SFU base and dry at 160℃ for 3 minutes.Adhesive conditions: Hot press at 120℃ for 30 seconds at a pressure of 6Kg/ ^cm2 Peeling test A test piece with a width of 25 mm was prepared, and it was peeled off at 23°C with a peeling speed of 200 mm/min using Autograph IM-100 (Shimadzu Corporation).
Measured by 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】

Claims (1)

[Scope of Claims] 1. A compound having at least one epoxy group and at least one hydroxyl group in the molecule, a polyol, and a diisocyanate are reacted to create an NCO-terminated prepolymer, and then at least one A cationic polyurethane aqueous dispersion solution obtained by adding water under stirring to a polymer obtained by the action of a chain extender and a quaternizing agent having a tertiary amino group and two or more Zerewitinoff activities. 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 compound having at least one epoxy group and at least one hydroxyl group in the molecule is a compound having two or more epoxy groups in the molecule from the group of carboxylic acids, carboxylic acid anhydrides, amines, and alkanolamines. The aqueous dispersion solution according to claim 1, which is a compound obtained by reacting selected compounds. 5 Compounds having at least one epoxy group and at least one hydroxyl group in the molecule, polyols, diisocyanates, and optionally chain extenders having at least one tertiary amino group and two or more Zelevitinoff activities in the molecule An aqueous cationic polyurethane dispersion solution obtained by reacting a polymer with a quaternizing agent, then adding water to the resulting polymer while stirring. 6. The aqueous dispersion solution according to claim 5, wherein the chain extender is quaternized in advance with a quaternizing agent. 7. The aqueous dispersion solution according to claim 5, wherein the chain extender is copolymerized into polyurethane and then quaternized with a quaternizing agent. 8 The above compound having at least one epoxy group and at least one hydroxyl group in the molecule is a compound having two or more epoxy groups in the molecule from the group of carboxylic acids, carboxylic acid anhydrides, amines, and alkanolamines. The aqueous dispersion solution according to claim 5, which is a compound obtained by reacting selected compounds.