JPS6025548B2 - Finishing method for textile products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a finishing method for imparting durable anti-count properties and anti-odor properties to textile products containing cellulose fibers.

Conventionally, urea resin, melamine resin, methylolethylene urea resin, methylolglyoxal monourein resin, etc. have been used as finishing agents to improve the grade protection, wash and wear properties, etc. of textile products containing cellulose fibers. Formaldehyde-based resins of the N-methylol type are mainly used, and in recent years, particularly low-formaldehyde versions of these resins and non-formaldehyde-based resins such as glyoxal-based cyclic urea derivatives have been used.

However, these methods have many drawbacks.

In other words, the method of using formaldehyde-based resin as a finishing agent is a useful method as it imparts durable albino-resistance to textile products; It has the disadvantage that formaldehyde remains and it is difficult to completely eliminate it, and the texture becomes paper-like. This formaldehyde odor varies somewhat depending on the type of formaldehyde resin used, but all formaldehyde resins contain free formaldehyde, and formaldehyde is also generated during heat treatment in the processing process, and there is a cleaning process after processing. Even after this process, formaldehyde still remains in processed products, causing clothing pollution. In particular, since formaldehyde became the subject of the Cabinet Order stipulating the substances in Article 2, Paragraph 2 of the Act on the Regulation of Household Products Containing Hazardous Substances in October 1939, formaldehyde remaining in processed products has been reduced. Regulations have been implemented, and for this reason, research is progressing on the development of so-called "low formaldehyde resins" that contain less formaldehyde than before, and on the use of formaldehyde scavengers in combination, and currently there are products on the market that can pass the formaldehyde regulations. It became. However, on the other hand, low-formaldehyde resins are not only inferior to conventional formaldehyde-based resins in terms of effectiveness for processing purposes, particularly in terms of durable brood-proofing properties, but also may be accompanied by chlorine damage.

Furthermore, when using formaldehyde scavengers, etc.,
In most cases, the scavenging effect cannot be obtained unless a large amount of scavenger is used, which has the disadvantage of impairing the texture. Regarding the above-mentioned non-formaldehyde resins, after the formaldehyde regulation, various types of so-called "non-formaldehyde resins" were developed especially for clothing for infants under 24 months old, but in the end, they are not used in the current market. Of those available, glyoxal-based cyclic urea conductor resins are the most popular.

However, the performance of this primary non-formaldehyde resin is considerably lower than that of its predecessor, N-methylol formaldehyde resins, and their low-formaldehyde versions. A major disadvantage is that it is difficult to obtain a shark-like characteristic and is accompanied by an unpleasant odor that is different from that of formaldehyde. The inventors of the present invention should simultaneously improve the above-mentioned drawbacks. As a result of three intensive studies, we have arrived at the present invention.

That is, the present invention involves adding a polyaldehyde carboxylic acid vinyl polymer to the treatment liquid when treating delicate products containing cellulose fibers with a treatment liquid consisting of a resin that is reactive with cellulose and an acidic catalyst. This invention relates to a finishing method for textile products containing cellulose fibers, characterized by: The polyaldehyde carboxylic acid vinyl polymer used in the present invention is obtained by oxidative polymerization of acrolein or polymerization of acrolein and acrylic acid, and has a structure mainly composed of the following units. may contain small amounts of units.

(In the formula, x+y=1, x and y represent the units in the polymer and the ratio of positions, and p represents the degree of polymerization.

) This polyaldehyde carboxylic acid vinyl polymer can be prepared by a known method (USP 3,793,222, Japanese Patent Publication No. 51-24
552, Special Publication No. 51-24553, Special Publication No. 50-6
No. 323).

The polyaldehyde carboxylic acid vinyl polymer has a degree of polymerization of 200 or less, x/y = 5/95 to 50'50,
Preferably, the degree of polymerization is 70 or less, x/y = 15/85 ~
40'60, and the commercially available product is Degussa (D
Examples include polyaldehyde carboxylic acid vinyl polymer (trade name: POCHS series) manufactured by E Liusa Co., Ltd.

Polyaldehyde carboxylic acid vinyl polymers have conventionally been used as detergent builders, water softeners, scale inhibitors, additives for metal degreasing baths, etc., but textile products containing cellulose paper such as the present invention The present inventors are the first to discover that this material has been used in textile processing to provide a durable brood-proofing property and the effect of reducing residual formaldehyde odor and/or other unpleasant odors. .

The amount of polyaldehyde carboxylic acid vinyl polymer added is
0.0% per solid content of resin reactive with the cellulose used.
1 to 2% by weight, preferably 1 to 20% by weight.

If the amount added is less than 0.1% by weight, the effect of the present invention cannot be obtained, while if the amount added is more than 20% by weight, it is not only economically unfavorable, but also has a paper-like texture, resulting in particularly noticeable effects. It is not allowed. A resin that is reactive with cellulose used in the present invention (hereinafter abbreviated as cellulose-reactive resin).

) include ureas such as dimethylol urea, dimethylol ethylene urea, dimethylol dihydroxy ethylene urea, dimethylol propylene urea, dimethyloluron, tetramethylol acetylene diurea, dimethylol triazone, or alkyl compounds thereof; Formaldehyde-based resins consisting of N-methylol compounds such as resins, melamine resins, dimethylol alkyl carbamates, and acid amide polymethylol compounds, as well as formaldehyde resins of the formula (in the formula R
, = one day, one C is one CH2C5OH, R2 = one day, one CH3, one CH2CH20 days, , R3 = one day, one CH3
and non-formaldehyde resins made of glyoxal monourein derivatives having the chemical structure:

These cellulose-reactive resins can be used alone or in combination of two or more. In the present invention, the acidic catalyst used in the treatment solution together with the cellulose-reactive resin includes 1
0,000 or more, and exhibits acidity when subjected to heat treatment, such as inorganic acids such as hydrochloric acid, phosphoric acid, and nitric acid, organic acids such as oxalic acid, acetic acid, formic acid, and citric acid, or their ammonium salts, amine salts, and magnesium chloride. , zinc nitrate, zinc sulfate, zinc shelf fluoride, and other metal salts. The amount of acidic catalyst used varies depending on the type and amount of cellulose-reactive resin used, but is usually 10 to 3% by weight based on the weight of the resin. The fiber products containing the cellulose fibers used in the present invention include materials in which at least a portion of the fibers constituting the fibers are recycled chicks such as natural fibers such as cotton and hemp, piscose rayon, cupola, and polynosic fibers. These cellulose fibers are partially blended or woven with synthetic fibers such as polyamide, polyester, polyacrylonitrile, and polyvinyl chloride, cotton such as silk and wool, and natural fibers other than hemp. Examples include various knitted fabrics, nonwoven fabrics, and secondary products obtained from. To further explain the specific method of the present invention, embodiments of the present invention using the above-mentioned materials are carried out by completely conventional methods.

That is, it is only necessary to add a predetermined amount of polyaldehyde vinyl carboxylic acid polymer per solid content to one or more so-called base resins selected from the cellulose-reactive resins and uniformly stir the mixture. In this case, it is normal to add polyaldehyde carboxylic acid vinyl polymer to the base resin when preparing the processing solution during processing, but it is preferable to add polyaldehyde carboxylic acid vinyl polymer to the base resin in advance. It's okay. However, in this case, depending on the type of base resin, storage stability may be adversely affected due to changes in pH, etc., so this point must be taken into account when selecting the base resin. Next, using the obtained polyaldehyde carboxylic acid vinyl polymer-added cellulose-reactive resin as a base resin, the resin is processed by a completely conventional method.

That is, a treatment liquid is prepared by adding a predetermined amount of the acidic catalyst used in the present invention to the base resin and adding water. In this case, it is possible to add other commonly used auxiliary agents to the processing solution, and it is also possible to form a stable solution for so-called appositional processing by adding a specified fluorescent dye. Next, the treatment liquid prepared by the method of the present invention is applied to textile products by any means used in ordinary textile finishing, such as a pad method or a spray method, and after pre-drying, the treatment solution is cured. The object of the invention is achieved. Although the amount of treatment liquid attached in this case varies depending on the type of treatment liquid, the amount
% by weight or more, preferably 100% by weight or more, and the treated textile product then has a
Heat treatment is performed for 1 to 10 minutes at a temperature of 0 qo.

When a polyaldehyde carboxylic acid vinyl polymer is applied to the N-methylol-formaldehyde-based cellulose-reactive resin as a treatment liquid, the processed fiber products thus obtained can be further improved in antlerotic property and shark-repellent after washing. It has such durability that there is almost no deterioration in its properties, and in some cases it even improves, and it has a remarkable formaldehyde scavenging property that the residual formaldehyde detected in processed fiber products is extremely low. Furthermore, it imparts repellent elasticity and even a slimy feel in some cases without damaging the texture, and also has the ability to improve chlorine damage resistance. Next, when a polyaldehyde carboxylic acid vinyl polymer is applied to a non-formaldehyde-based cellulose-reactive resin as a treatment liquid, the shark resistance is improved to the extent that it reaches the level when the treatment liquid is applied, In addition, there is almost no decrease in shark resistance after washing, and in some cases it maintains such durability that it even improves. Further, in this case, the effect that the unpleasant amine-based odor currently generated from the processed cloth is almost completely eliminated is imparted. Hereinafter, the present invention will be explained in more detail with reference to Examples.

In the examples, parts are based on weight ratios, and % is weight %. W indicates warp, F indicates stripe direction, and each measurement method is as follows. Chill resistance: In preparation for JIS L-1041C method, (
Displayed as W+F)o Drawing strength: JISL-1004 Pendulum method shrinkage rate: JISL-1004, L-1005
, Washing method: JISL-1042F-1 method Chlorine damage resistance: JISL-1041 scorch test method Whiteness (Hunter): 457 mm Measured with Nippon Denshoku ND-101D color meter Amount of residual formaldehyde: Acetylacetone method (
(Ministry of Health and Welfare Ordinance No. 34 Law) Unpleasant odor: Immediately after processing, the processed fabric (25 mm x 200 mm long) was sealed in a polyethylene bag, left at 20 qC for 24 hours, opened, and judged by hand feel. Bursting strength determined by: JIS L-1018 Example 1 Scouring bleached mercerized cotton 4 fine flea broad and desizing scouring bleached mercerized under tension 180qo, heat set for 30 seconds 65% polyester, 35% cotton blend 45
70%
Narrow down to the amount of adhesion, pre-dry for 3 minutes at 90oo, then dry at 150℃
Heat treatment was performed for 3 minutes.

In the upper table of Table 1, Milben Resin HP-2 is an aqueous solution containing 50% of the active ingredient consisting of dimethylol dihydroxyethylene urea resin manufactured by Showa Kobunshi ■, and POC. HS-2020 is a 30% aqueous solution of polyaldehyde carboxylic acid vinyl polymer manufactured by Degussa Corporation with an average degree of polymerization of 20 and x/y=24/76.

The first table treatment bath was prepared by sequentially adding these ingredients during resin processing. The results of measuring the processing effect are shown in Table 2-1.
and as shown in Table 2-2. Table 2 Table 2-2 As is clear from Tables 2-1 and 2-2, the method of the present invention is more effective than cellulose-reactive resins such as conventionally used dimethylol dihydroxyethylene urea resins. This shows further improvement in weather resistance, durability, and excellent formaldehyde scavenging properties.

In particular, the amount of polyaldehyde carboxylic acid vinyl polymer added is only 3% (2.
The effect is remarkable with a small amount of 6% (method of the present invention) and 6% (method of the present invention), and even after washing, the grade resistance does not decrease at all, and even a slimy feeling is imparted without impairing the hand. Further, the amount of residual formaldehyde is further reduced by the water washing step. Example 2 The same cotton broadcloth and polyester/cotton broadcloth materials used in Retention 1 were soaked according to the treatments shown in Table 3 and finished under the same heat treatment conditions as in Example 1 above.

Third friend, POCHS-0010, HS-2020, HS
-5060 and HS-65120 are both 30% aqueous solutions of POCHS type polyaldehyde carboxylic acid vinyl polymer manufactured by Degussa, and have the following properties (particularly molecular weight).

* The number of COO monomer units and C
The ratio (%) of the number of COO group monomer units to the sum of the number of HO group monomer units is shown. Table 4 shows the measurement results of processing effects according to predetermined dimensions.

Table 4 As is clear from Table 4, it is preferable that the polyaldehyde carboxylic acid vinyl polymer used in the method of the present invention has a low molecular weight, and in particular, one with an average molecular weight of 4,000 or less (average degree of polymerization of 70 or less) is preferable. Recognize.

*Example 3 The same wire broadcloth and polyester/cotton thick broadcloth materials used in Example 1 were immersed in the treatment bath shown in Table 5, and low formaldehyde processing was performed under the same heat treatment conditions as Example 1. .

In the upper table of Table 5, Milben Resin SL-65 is a dimethylol dihydroxyethylene urea-based low formaldehyde cellulose-reactive resin (45% active ingredient) manufactured by Showa Kobunshi ■, and was prepared in the same manner as in Example 1. The processing bath was adjusted during processing.

The processing effect was as shown in Table 6. As can be seen from the results in Table 6 (Note) Excellent ◎ ○ △ × Poor, this type of base resin with low formaldehyde generally does not suffer from a decline in performance, and by applying the present invention, For example, 1. of Example 1 which is not reduced in formaldehyde. Compared to the conventional method, the magnetic shielding properties are further improved and the durability is also improved.
There is even an improvement in chlorine damage resistance.

In addition, the formaldehyde trapping effect is remarkable, and the texture is not impaired and the material exhibits durability. Example 4 4G wire broad, polyester/wire blend (65/35)
For broadcloth and cotton knit fluorescent dye yarn-dyed knitted fabric materials, normal padding and
The scale-proofing process was carried out using non-formaldehyde resin using the and-dry method.

[1' Treatment Clause 7 In the table above, Milben Resin SL-51 is a 45% resin aqueous solution of a glyoxal-based cyclic urea derivative manufactured by Showa Kobunshi ■. During processing, the treatment bath was adjusted to the same machine as Example 1. did.

{21 Processing conditions (for textiles) Pad Predry Curelink (70-80 multiple drawings) (110℃ x 2
minutes) (160℃ x 1.5 minutes) (for knitted fabrics) Hard Predry -M-Cure (80-90% reduction) (110℃ x 2 minutes) (160℃ x
1 minute) The processing results under the above processing conditions are as shown in Table 8-1 and Table 8-2.

8th Companion-l Table 8-2 As is clear from this example, by applying the method of the present invention to a non-formaldehyde base resin, durable albino repellency can be obtained. The characteristic unpleasant odor was also reduced and was either very low or almost completely absent, and the texture was also improved.

Example 5 4 Anti-electrical wire broad was used as a material, and it was immersed in the same bath treatment solution for the photoresist dye shown in Table 9, reduced to about 75%, and 90q
After pre-drying for 3 minutes at 150°C, it was cured for 3 minutes at 15°C.

Next, it was diluted with a 60° C. treatment solution containing Monogen (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) for 15 seconds, soaped, and dried to perform a non-formaldehyde type anti-chicken treatment. In the upper table of Table 9, Cahol PBN is a fluorescent dye for cotton manufactured by Nippon Kayaku ■.

The measured physical properties of the processed fabric are as shown in Table 1.
In addition, the unprocessed cloth was blanched after fluorescent beam dyeing. Table 10 As is clear from the results of this example, durable anti-counterfeit properties,
Reduction of unpleasant odor and improvement of texture are possible through non-formaldehyde resin processing using fluorescent dye bath.

Claims (1)

[Claims] 1. A fiber characterized by adding a polyaldehyde carboxylic acid vinyl polymer to the treatment liquid when treating a textile product containing cellulose fibers with a treatment liquid consisting of a resin reactive with cellulose and an acidic catalyst. A finishing method for textile products containing elementary fibers.