JPS6145614B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a glyoxal-amide adduct by reacting glyoxal with an amide, and aims to provide a fiber treatment agent with high commercial value. It has been known to obtain non-formalin-based fiber treatment agents by reacting various amide compounds with glyoxal (for example, Senzo Kogyo Vol. 22,
No. 12, pp. 10-28). Although these known glyoxal-amide adducts have the great advantage of not generating formalin during their production or use, first of all, the amine by-produced during amide production is not removed even after the reaction with glyoxal. This is a cause of unpleasant odors such as fishy odor during fiber processing. In addition, when using more than this equivalent amount of amide in the reaction with glyoxal, unreacted amide remains, causing side reactions due to heating during fiber processing, causing unpleasant odors and discoloration of the treated fibers, and even causing skin damage to the human body. cause trouble. Second, it has many drawbacks, such as variations in performance due to amines and amides, and third, it cannot provide a variety of satisfactory performances to the fibers to be treated. Furthermore, especially when producing glyoxal-amide adducts in neutral to weak alkaline conditions, amines produced as by-products due to partial decomposition of the amide during the addition reaction cause unpleasant odors and discoloration. The present inventors have conducted intensive research to solve the drawbacks of conventional fiber treatment agents made of glyoxal-amide adducts as described above, and have found that by adding a certain compound during or after the production, glyoxal-amide adducts can be produced. The present invention was completed based on the finding that many of the above-mentioned drawbacks can be solved at the same time. That is, the present invention provides a method for producing a glyoxal-amide adduct, which comprises adding a polyurethane containing a terminal isocyanate group during or after the production of the glyoxal-amide adduct by reacting glyoxal with an amide. be. To explain the present invention in detail, the method of reacting glyoxal and amide itself is well known, so the details thereof will not be described. Amides used in the present invention include, for example, urea, dimethylurea,
Urea-based compounds such as diphenyl urea; formamide-based compounds such as formamide, N-methylformamide, and acetamide; bisamide-based compounds such as methylene bisformamide and ethylene bisformamide; carbamate-based compounds such as methyl carbamate, isopropyl carbamate, and hydroxyethyl carbamate; Other acrylamide,
Among these amide compounds, urea compounds are preferred, and dimethylurea is most suitable for the purpose of the present invention. Such urea-based compounds are usually mixed with an aqueous glyoxal solution,
The reaction is usually carried out at an elevated temperature, preferably in a weakly acidic to weakly alkaline environment for several to several tens of hours. The ratio of amide and glyoxal used varies depending on the type of amide used, reaction conditions, etc., but it is usually 0.4 to 1.5 mol of glyoxal per 1 mol of amide, especially in the case of urea-based compounds, 1 mol of the compound. 0.8 to 1.2 mol of glyoxal is preferable. The main feature of the present invention is that in the above-mentioned production method, polyurethane having isocyanate groups at the terminals (hereinafter referred to as polyurethane including polyurethane prepolymers) is added during or after production. By adding such a compound, the malodorous components in the reaction product of glyoxal and amide are removed, and the problems of unpleasant odor and discoloration during textile processing are solved. When using the product as a fiber treatment agent, it exhibits various treatment effects that are significantly superior to that of a fiber treatment agent that simply adds water-soluble polyurethane to a glyoxal amide adduct (Japanese Patent Application Laid-open No. 75898/1983). It was found that the effect is comparable to that of conventional formalin-based fiber treatment agents. The disappearance of the unpleasant odor and the various disadvantages after fiber treatment are probably due to the fact that the impurities present in the glyoxal amide adduct that cause the unpleasant odor and discoloration are eliminated by reacting with the isocyanate group. However, the reason for the unexpected improvement in effectiveness as a fiber treatment agent is not necessarily clear. The terminal isocyanate group-containing polyurethane used in the present invention can be easily obtained by a conventionally known method. That is, the desired polyurethane prepolymer can be obtained by reacting a polyol component and a polyisocyanate component in an excess equivalent proportion of the latter, and a polyurethane can be obtained by further reacting with an appropriate amount of a chain extender. . In the method of the present invention, it has been found that polyurethanes containing terminal isocyanate groups that are automatically dispersible in water (self-emulsifying) or water-soluble are most effective. In order to obtain a self-emulsifying, preferably water-soluble polyurethane, highly water-soluble polyethylene glycol, a random or block copolymer of ethylene oxide and propylene oxide, or a polyester polyol obtained from these polyols and polycarboxylic acid is used as the polyol component. It is preferable to use In order to make polyurethane self-emulsifying in this way,
When the hydrophilic moiety is an oxyethylene group, this group must account for approximately 50% by weight in the polyurethane, and in order to make the polyurethane water-soluble, the oxyethylene group must account for approximately 70% by weight. preferable.
However, it goes without saying that this ratio varies to some extent depending on the type of polyol component and polyisocyanate component used. The proportion of terminal isocyanate groups in such polyurethanes is usually about 0.05 to 5% by weight. It is well known in the art to obtain polyurethane itself having the above properties, and the polyol components used include polyhydric alcohols (ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.), ethylene oxide and ( or) polyether polyol obtained by reacting propylene oxide, polyester polyol obtained from this polyether polyol and polycarboxylic acid, caprolactone polyol, polytetramethylene glycol, or a mixture thereof. isocyanate, diphenylmethane diisocyanate, diphenyl diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, triphenylmethane triisocyanate, isophorone diisocyanate, and other polyisocyanate compounds known in the polyurethane industry. As the chain extender, which is used as necessary, various conventionally known polyamines are mainly used. The polyurethane containing terminal isocyanate groups as described above may have a portion of the terminal isocyanate groups masked with a conventionally known masking agent. In this case, the masked isocyanate groups remain masked even after the process of the present invention is completed, and are regenerated during heating during fiber processing, forming fibers and/or glyoxal amide adducts. It reacts and exhibits excellent treatment effects on fibers. The terminal isocyanate group-containing polyurethane as described above is added during or after the production of the glyoxal-amide adduct, but if it is added during the production, it is preferably added when the reaction between glyoxal and the amide is substantially completed. The amount of polyurethane containing terminal isocyanate groups is
It is necessary that the amount of polyurethane with terminal isocyanate groups is equal to or greater than the equivalent of the amine and excess amide contained in the amide adduct, and usually the amount of NH ₂ in the NCO/amine + the amount of
Particularly preferred are amounts such that _NH2 and NH are 1.0 to 1.1. After adding in this way, it may be heated, but
The object of the present invention can be achieved simply by stirring the reaction mixture without special heating.
The amount of polyurethane to glyoxal amide adduct is usually about 2 parts by weight of the latter per 100 parts by weight of the former.
~20 parts by weight. The method of the present invention as described above is mainly carried out in an aqueous medium, preferably water, and a known reaction catalyst or the like is used as necessary. The reaction product of the present invention obtained as described above is very effective as a fiber treatment agent, and its amine and amide odors are completely eliminated when compared with conventional fiber treatment agents made of glyoxal amide adducts. In addition, various drawbacks caused by residual amines and amides have been completely resolved, and in addition, various performances as a fiber treatment agent, such as wrinkle resistance, shrink-proofing rate, impact resilience, volume feel, and texture, have been completely resolved. It was completely unexpected that the properties of the present invention were improved to the extent that they were comparable to conventional formalin-based fiber treatment agents. Next, the present invention will be specifically explained with reference to Examples. Note that parts and percentages in the text are based on weight. Example 1 1.01 mol of dimethylurea and 1.0 mol of glyoxal were added to pure water so that the solid content was 40%, and the pH was adjusted.
was adjusted to 6.7 and reacted at a temperature of about 70-80°C for 20 hours, and then cooled to obtain a 40% aqueous solution of dimethylhydroxyethylene urea. The following polyurethane containing terminal isocyanate groups was added to 100 parts of this aqueous solution, and the mixture was stirred at room temperature for 5 hours to obtain the object of the present invention. A Ethylene oxide-propylene oxide obtained using ethylene glycol as an initiator (9:
1) Self-emulsifying polyurethane (NCO% = 4.0) made by reacting a copolymer (OH value 90) and isophorodiisocyanate at a ratio of NCO/OH = 1.8...
... Addition amount 10 parts B Polyether polyol obtained by adding ethylene oxide using glycerin as an initiator and xylylene diisocyanate NCO/OH = 2.0
Water-soluble polyurethane (NCO% = 4.0) obtained by reacting at a ratio of 10 parts C A water-soluble polyurethane obtained by masking 50% of the isocyanate groups of the compound B above with methyl ethyl ketone oxime (NCO% = 4.0) Example: 10 parts added 2 Polyurethane obtained by reacting polyester polyol (OH value 135) obtained from adipic acid and polyethylene glycol with tolylene diisocyanate at a ratio of NCO/OH = 1.6 (NCO
= 4.5) 10 parts of a water-soluble polyurethane in which 50% of the isocyanate groups were masked with sulfite was added to 100 parts of a 40% aqueous solution of dimethyldihydroxyethylene urea obtained in Example 1, and stirred for 5 hours to obtain the object of the present invention. I got something. Performance Test and Comparative Test The objects of the present invention obtained in Examples 1 and 2 were applied to cotton fabrics brightened with fluorescent dyes to investigate the treatment effects, and the results obtained in Examples 1 and 2 were The fiber treatment agent before addition of polyurethane and the fiber treatment agent disclosed in Example 1 of JP-A-48-75898 were simultaneously tested and compared with the case according to the present invention. Processing conditions: Formulation A (present invention) Target product obtained in Examples 1 to 2 20 parts 45% zinc borofluoride aqueous solution 2 parts Formulation B (comparative example) JP-A-48-75898 described in Example 1 Polyurethane resin A (pure content) 2 parts dimethyldihydroxyethylene urea (40%)
20 parts 45% zinc borofluoride aqueous solution 2 parts Formulation C (comparative example) Dimethyl dihydroxyethylene urea (40%)
20 parts 45% zinc borofluoride aqueous solution 2 parts Formulation D (comparative example) Polyurethane A used in Example 1 2 parts 45% zinc borofluoride aqueous solution 2 parts Formulation E (comparative example) Polyurethane A used in Example 1 5 parts 45% zinc borofluoride aqueous solution 2 parts Squeezing ratio 70% Drying Heat treatment at 100℃ for 3 minutes 150℃ for 3 minutes

【table】

[Table] As is clear from the table, the treatment agent of the present invention provided excellent wrinkle resistance, whiteness, and fish odor prevention effects. Furthermore, when processing with Formulation B and C, the wrinkle resistance obtained varies significantly with a slight change (decrease) in the heat treatment temperature, but with Formulation A, the wrinkle resistance can be improved even with a change of about ±5°C. The quality effect remains almost unchanged;
It offers great advantages in industrialization.

Claims (1)

[Scope of Claims] 1. When glyoxal and an amide are reacted to produce a glyoxal-amide adduct, during or after the production, the polyurethane containing terminal isocyanate groups is treated with the amine coexisting with the glyoxal-amide adduct and the excess amount. A method for producing a glyoxal-amide adduct, which comprises adding polyurethane having a terminal isocyanate group in an amount equivalent to or more than the amount of the amide. 2. The manufacturing method according to claim 1, wherein the amide is dimethylurea. 3. The manufacturing method according to claim 1, wherein the polyurethane containing terminal isocyanate groups is self-emulsifying or water-soluble.