JPH06200234A - Formaldehyde acceptor ad its application to textile - Google Patents

Abstract

PURPOSE:To provide an acceptor suitable for suppressing the formation of formaldehyde from a textile product treated with a formaldehyde resin. CONSTITUTION:A reactional product of an alkylenediamine or a polyalkylenepolyamine with a urea, cyanic acid or a cyanate is used as a formaldehyde acceptor. When this acceptor is applied for the treatment of a textile product with a formaldehyde resin, the formation of formaldehyde can be suppressed and the deterioration of the properties of the resin-treated textile product is little.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to formaldehyde scavengers and their application to fibers. More specifically, it is preferable to reduce the generation of formaldehyde from textile products processed with formaldehyde resin.
It is the one that tries to suppress it.

[0002]

2. Description of the Related Art Textile products are widely processed with formaldehyde resins to improve various physical properties such as wrinkle resistance, dimensional stability and texture. However, one of the problems is the generation of formaldehyde from textile products processed with such resins. Therefore, in order to reduce and suppress the generation of formaldehyde, many methods have been proposed and implemented so far.

For example, Japanese Patent Laid-Open No. 61-34281 and Japanese Patent Laid-Open No.
Proposals for improving formaldehyde resins have been made in 4-153369, etc., and proposals for improving processing methods have been made in JP-B-36-14347 and JP-B-49-14440. There is. However, the use of formaldehyde scavenger is the most general purpose because there are problems such as the limit of improvement effect and the effect on the balance of various physical properties, and the economical efficiency of the processing method, due to such improvements in resins and processing methods. It is an important technology that is being carried out.

Urea, thiourea, ethylene urea, dicyandiamide, glyoxal monourein, etc. have been known as formaldehyde scavengers. Such formaldehyde scavengers are described, for example, in US Pat.
As described in the specification of No. 3,670, etc., it is widely applied to textiles by a method of treating with a formaldehyde resin in the same bath, or after processing with a formaldehyde resin, attaching by spraying or the like.

[0005]

Although these known formaldehyde scavengers work effectively to reduce the generation of formaldehyde from the textile products processed with formaldehyde resin, they have a processing effect, for example, a wrinkle-preventing effect and There are drawbacks such as a reduction in shrinkage prevention effect, chlorine damage, and deterioration of the fastness of the reactive dye to sunlight. For example, urea and glyoxalmonourein greatly deteriorate chlorine damage, and ethylene urea significantly reduces the fastness to sunlight of the reactive dye. In addition, dicyandiamide has a small adverse effect on chlorine fastness and the fastness of a reactive dye to sunlight, but has a large reduction in processing effect.

In view of the present situation, the inventors of the present invention have made earnest studies and, as a result, have reached the present invention. Therefore, an object of the present invention is to provide a formaldehyde scavenger with less deterioration in processing effect and less adverse effects on chlorine damage and adverse effects on the fastness of a reactive dye to sunlight.

[0007]

DISCLOSURE OF THE INVENTION The present invention is intended to solve the above problems, and a reaction product of an alkylenediamine or polyalkylenepolyamine with a urea, cyanic acid or a cyanate salt is treated with formaldehyde. It is characterized by being used as a scavenger. When this formaldehyde scavenger is applied to a textile product processed or processed with a formaldehyde resin, a particularly excellent effect is obtained.

The present invention will be described in more detail below.

In the production of the formaldehyde scavenger of the present invention, the amine which is one of the starting materials is alkylenediamine or polyalkylenepolyamine. Alkylenediamine has two primary amino groups in the molecule,
It can be an aliphatic diamine in which both are bound by alkylene, and ethylenediamine, propylenediamine and the like are exemplified. The polyalkylene polyamine has 1
Aliphatic polyamine having two primary amino groups and at least one secondary amino group in the molecule, and alkylene being interposed between the primary amino group and the secondary amino group, or further between the secondary amino groups. Can be diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine, 3-azahexane-
1,6-diamine, 4,7-diazadecane-1,10-
Diamine and the like are exemplified. Among these amines, ethylenediamine, diethylenetriamine, triethylenetetramine, etc., and particularly diethylenetriamine and triethylenetetramine are industrially advantageous.
These alkylenediamines or polyalkylenepolyamines are used alone or as a mixture of two or more kinds.

The other raw material is urea, cyanic acid or cyanate. Examples of ureas include thiourea, guanylurea, methylurea and dimethylurea in addition to urea, and among these, urea is industrially advantageously used. Examples of cyanic acid or salts thereof include cyanic acid, sodium cyanate, potassium cyanate, and the like.

When the alkylenediamine or polyalkylenepolyamine is reacted with urea, it is usually 100 to
At a temperature of about 200 ° C., preferably about 100 to 160 ° C., while removing generated ammonia out of the system,
The reaction is performed for about 0 hours. This reaction may be carried out without solvent or may be carried out in a solvent. Examples of the solvent that can be used include water, ethylene glycol, dimethyl sulfoxide and the like. Further, this reaction proceeds without a catalyst, but can also be carried out in the presence of a catalyst. Examples of the catalyst that can be used include acid catalysts such as hydrochloric acid and sulfuric acid. In the reaction, the amount of urea used is preferably in the range of 0.5 to 1 mol with respect to 1 mol of the amino group in the alkylenediamine or polyalkylenepolyamine.

When alkylenediamine or polyalkylenepolyamine is reacted with cyanic acid or a salt thereof, it is usually about -20 to 100 ° C, preferably 0 to 70 ° C.
The reaction is carried out at a temperature of about 0.5 to 5 hours. This reaction is usually carried out in a polar solvent such as water or alcohols, and when cyanates are used, they are carried out in the presence of 1 mol or more of a protic acid per 1 mol of cyanates.
The protonic acid used here includes hydrochloric acid, sulfuric acid, nitric acid,
Examples include formic acid and acetic acid. This reaction may be carried out by charging all the raw materials at the same time, but a method in which cyanic acid or a salt thereof is gradually added or a protic acid is gradually added is also preferable. In reaction,
The amount of cyanic acid or a salt thereof used is preferably in the range of 0.5 to 1 mol with respect to 1 mol of the amino group in the alkylenediamine or polyalkylenepolyamine.

The formaldehyde scavenger of the present invention thus obtained is preferably used in order to reduce or suppress the generation of formaldehyde from the textile products processed with the formaldehyde resin. The method of use is not particularly limited, but preferred specific embodiments will be described below.

Textile products include cotton, rayon, hemp,
A woven fabric using cellulosic fibers such as acetate, synthetic fibers such as vinylon, nylon, polyester, polypropylene, acrylic and polyurethane, animal fibers such as wool and silk, either alone or in combination of two or more. , Knitted fabrics, non-woven fabrics, and papers and paperboards made of various pulps. Above all, it is preferably applied to woven fabrics, knitted fabrics, non-woven fabrics and the like of natural or synthetic fibers.

As the formaldehyde resin, melamine-formaldehyde resin, urea-formaldehyde resin, thiourea-formaldehyde resin, ethylene urea-formaldehyde resin, propylene urea-
Formaldehyde resin, dihydroxyethylene urea-
Examples thereof include formaldehyde resin, methyltriazone-formaldehyde resin, methylcarbamate-formaldehyde resin, acrylamide-formaldehyde resin.

In order to improve various physical properties such as wrinkle resistance, dimensional stability, and texture of the textile product as described above, when processing with the formaldehyde resin as described above,
By processing by adding the formaldehyde scavenger of the present invention to a processing liquid containing a formaldehyde-based resin, or after processing with a processing liquid containing a formaldehyde-based resin, the formaldehyde scavenger of the present invention is applied by impregnation, spraying or the like. Therefore, the effect required by the present invention can be obtained. Of course, it is also possible to apply the formaldehyde scavenger after processing with a processing liquid containing the formaldehyde scavenger together with the formaldehyde resin.

The processing with the formaldehyde resin can be carried out by a conventional method which has been conventionally carried out, and there is no particular limitation in applying the present invention.

[0018]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In addition,% in the examples is% by weight unless otherwise specified.

Example 1 (a) Production of formaldehyde scavenger In a four-necked flask equipped with a thermometer, a reflux condenser and a stirring bar, 60 g (1 mol) of ethylenediamine and 90 g of urea were added.
(1.5 mol) and 150 g of water were charged, and the mixture was refluxed for 10 minutes.
Deammonification reaction was carried out at 0 to 120 ° C. for 5 hours, and water was added to the obtained reaction product to obtain a water suspension having a concentration of 33%. This is designated as formaldehyde scavenger A.

(B) Application to textile products Using the formaldehyde scavenger A obtained in (a) above,
A processing liquid was prepared according to the formulation shown in Table 1. This processing liquid was impregnated with scouring, bleaching, and mercerized No. 40 single yarn cotton broad and squeezed with a mangle so that the wet pick-up rate was 65%. Then 1 with a pin tenter heat treatment machine
It is dried at 00 ℃ for 2 minutes and then at the same machine at 150 ℃.
Curing was performed for 3 minutes. The following physical properties of the obtained processed cotton cloth were measured and the results are shown in Table 1.

Amount of free formaldehyde: JIS L 1096
It was measured by the B2 method described in 6.39.1.2. Washing shrinkage ratio: Measured according to JIS L 0217 103 method. Chlorine injury: The degree of coloring after scoring was judged based on JIS L 1041 section 5.4.

Comparative Example 1 Example 1 was repeated except that no formaldehyde scavenger was used.
A processed cotton cloth was obtained in the same manner as in (b), and the same physical properties were measured. The test results are shown in Table 1.

Comparative Example 2 A processed cotton cloth was obtained in the same manner as in (b) of Example 1 except that urea was used as a formaldehyde scavenger, and the same physical properties were measured. The test results are shown in Table 1.

[0024]

[Table 1] ^{* 1} Sumitex Resin M-3: Sumitomo Chemical Co., Ltd., melamine-formaldehyde resin, 80% active ingredient product ^{* 2} Sumitex Accelerator ACX: Sumitomo Chemical Co., Ltd.
Made, organic amine hydrochloride catalyst, 35% active ingredient

Example 2 (a) Preparation of formaldehyde scavenger A device similar to that used in Example 1 (a) was charged with 103 g (1 mol) of diethylenetriamine, 180 g (3 mol) of urea and 40 g of water, Deammonification reaction was performed at 100 to 120 ° C. for 3 hours, and water was added to the obtained reaction product to obtain a 40% aqueous suspension. This is designated as formaldehyde scavenger B.

(B) Application to Textile Products Using the formaldehyde scavenger B obtained here, Table 2
A processing liquid was prepared with the formulation shown in. After scouring, bleaching and mercerization, 40th single dyed by the usual continuous dyeing method (pad-dry-steaming) using a 10g / L concentration dyeing bath of Sumifix Supra Blue BRF (Sumitomo Chemical Co., Ltd.) The cotton wool broad was impregnated with the above-mentioned working liquid, and squeezed with a mangle so that the wet pickup ratio was 65%. Then, it was dried at 110 ° C. for 2 minutes by a pin tenter heat treatment machine, and further cured at 160 ° C. for 2 minutes. The following physical properties were measured for the obtained resin-processed cloth, and the results are shown in Table 2.

Free formaldehyde amount: measured in the same manner as in Example 1. Wrinkle resistance: Measured by the B method described in 6.22.1 of JIS L 1096. Color fastness to carbon arc light: JIS L 0842
Tested according to.

Example 3 (a) Preparation of formaldehyde scavenger A device similar to that used in Example 1 (a) was charged with 146 g (1 mol) of triethylenetetramine, 300 g (5 mol) of acetic acid and 300 g of water. After charging, a solution prepared by dissolving 324 g (4 mol) of potassium cyanate in 1000 g of water was added.
Slowly added at 20-40 ° C, further reacted at 40-60 ° C for 2 hours, cooled with ice and filtered to obtain a white powder. This is designated as formaldehyde scavenger C.

(B) Application to textile products A resin-treated cloth was obtained in the same manner as in (b) of Example 2 except that the formaldehyde scavenger C obtained here was used, and the same physical properties were measured. . The test results are shown in Table 2.

Example 4 The procedure of Example 2 was repeated except that no formaldehyde scavenger was used.
After obtaining a resin-treated cloth in the same manner as in (b),
Formaldehyde scavenger B of 40% concentration prepared in (a)
Was further diluted with water to a concentration of 5%, and sprayed so that the amount of adhesion (the amount of the 5% aqueous solution applied to the weight of the cloth) was 10%. Example 2 also regarding this processed cloth
Physical properties were measured in the same manner as in (b) above, and the test results shown in Table 2 were obtained.

Comparative Example 3 Example 3 was repeated except that no formaldehyde scavenger was used.
A resin-treated cloth was obtained in the same manner as in (b), and the same physical properties were measured. The test results are shown in Table 2.

Comparative Example 4 A resin-treated cloth was obtained in the same manner as in (b) of Example 2 except that ethylene urea was used as the formaldehyde scavenger.
The same physical properties were measured. The test results are shown in Table 2.

Comparative Example 5 A resin-treated cloth was obtained in the same manner as in (b) of Example 2 except that dicyandiamide was used as the formaldehyde scavenger, and the same physical properties were measured. The test results are shown in Table 2.

[0034]

[Table 2] ^{* 3} Sumitex Resin NS-18: manufactured by Sumitomo Chemical Co., Ltd.
Dihydroxyethylene urea-formaldehyde resin,
45% active ingredient ^{* 4} Sumitex Accelerator X-110: Sumitomo Chemical Co., Ltd., composite metal salt catalyst, 20% active ingredient

[0035]

INDUSTRIAL APPLICABILITY As described above, the formaldehyde scavenger of the present invention can preferably reduce and suppress the generation of formaldehyde when used in the processing of textile products using formaldehyde resin, and also can prevent wrinkle and shrinkage. It exhibits various excellent effects such as less deterioration in processing effects such as properties and less adverse effects on chlorine damage and reactive dyes on the fastness to sunlight.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location D06M 15/39 D06M 15/39

Claims (4)

[Claims] 1. A formaldehyde scavenger comprising a reaction product of alkylenediamine or polyalkylenepolyamine and ureas, cyanic acid or cyanate. 2. A method for treating a textile product, which comprises applying the formaldehyde scavenger according to claim 1 to the textile product when processing the textile product with a formaldehyde resin. 3. The method according to claim 2, wherein the processing liquid containing the formaldehyde resin is mixed with a formaldehyde scavenger and applied to a textile product. 4. The method according to claim 2, wherein the formaldehyde scavenger is applied to the textile product treated with the formaldehyde resin.