JPH055278A - Flame proofing processing of cellulosic fiber - Google Patents

Abstract

PURPOSE:To provide cellulosic fiber with flame proofing performances with excellent washing durability without producing liberated formaldehyde and yellowing with time by sticking a treating solution containing a specific phosphazene compound and an alkyl silicate to the fiber in the presence of an alkali and treating with steam heat. CONSTITUTION:Cellulosic fiber (preferable example: cotton) is immersed in an alkaline emulsified solution containing an alkoxyphosphazene compound (e.g. polybutoxyphosphazene) shown by formula I (R is ethyl, propyl or butyl; m is >=3) and an alkyl silicate shown by formula II (R is alkyl; n is 0 or >=1), preferably ethyl silicate and then treated with steam heat to provide the cellulosic fiber with flame proofing performances having excellent washing resistance and stability without causing liberated formaldehyde and other offensive small and yellowing with time.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flameproofing method for cellulosic fibers.

[0002]

2. Description of the Related Art Conventionally, tetrakis hydroxy has been used as a method for subjecting cellulosic fibers to flameproof processing that is wash resistant.
Provan processing using methylphosphonium sulfate-urea condensate or tetrakis-hydroxy-methylphosphonium chloride-urea condensate (Albright
And Wilson) and N-methylol dimethyl
Pyrovatex CP using phosphonopropionamide
The law (Ciba Geigy) is well known.

However, all of these methods have a methylol group as a reactive group, and the reaction with a cellulosic fiber is due to a methylene ether bond. Therefore, generation of free formaldehyde is unavoidable, and sufficient post-treatment alkali washing is performed. However, hydrolysis due to aging is inevitable, and the free formaldehyde increases with time due to the hydrolysis.

US Pat. No. 2,661,264 describes H ₂ N-P0 _2- (N
(H)-and phosphorus oxychloride are disclosed for aging by reacting ammonia, and in U.S. Pat.No. 2,782,133, a working fluid containing an amidophosphazene compound is attached to a cellulosic fiber, followed by drying and curing. A flameproofing method characterized by ringing and soaping is disclosed. Although these methods have solved the problem regarding the generation of free formaldehyde, they have created a new problem that the odor and yellowing due to the amide group of the drug cannot be removed.

Further, various methods using an amidophosphazene compound are disclosed in JP-A-61-183383 and JP-A-61-266668.
JP-A-61-266669, JP-A-61-266670, JP-B-1-14343, JP-A-62-191572, JP-A-62-276077.
As disclosed in JP-A-1-49827, the amidophosphazene compound is unstable in an aqueous solution and decomposes, so that it cannot be stored as an aqueous solution. Therefore, it is difficult to use industrially. However, as described above, there was a problem of offensive odor and yellowing.

Further, Japanese Patent Publication No. 46-40489 discloses a method of kneading a polyalkylphosphazene compound during spinning of regenerated cellulose. However, it is difficult to apply this method to flameproofing of a knitted fabric made of cellulosic fibers, and there is a drawback that a processed product excellent in washing resistance cannot be obtained by simply attaching it.

[0007]

SUMMARY OF THE INVENTION The present invention does not give rise to free formaldehyde and other off-flavors, and
An object of the present invention is to provide a method for flameproofing a cellulosic fiber, which is capable of imparting stable and durable flameproofness to the cellulosic fiber without causing yellowing due to aging during processing. In particular, it is an object of the present invention to provide a novel flameproofing method capable of finishing a cellulosic fiber into a flameproofed article having excellent practicability which can be used as a side material of a futon or sheets.

[0008]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a general formula for knitting and woven fabrics of cellulosic fibers is obtained.

[0009]

[Formula 1]

(Wherein R represents an ethyl group, a propyl group or a butyl group, and n represents an integer of 3 or more);

[0011]

[Formula 2]

(Wherein R is an alkyl group, n is 0 or 1
By applying a treatment liquid containing a compound having the above integer) and an alkali and subjecting it to a steam heat treatment, it is possible to obtain flameproof performance excellent in washing durability without generating free formaldehyde. I found it. The polyalkoxyphosphazene compound used in the present invention is a polybutoxyphenylphosphazene cyclic compound, a polypropioxyphosphazene cyclic compound or a polyethoxyphosphazene cyclic compound having a 6-membered ring, an 8-membered ring or a 10-membered ring. Can be mentioned. Practically, a plurality of member rings of each cyclic compound are mixed and used.

The number of carbon atoms of the alkyl group of the alkyl silicate used in the present invention is not particularly limited, but preferred examples of those generally used include ethyl silicate, propyl silicate and butyl silicate. From the viewpoint of reaction, use of ethyl silicate is most preferable. Methyl silicate has a problem of toxicity and is difficult to handle, and an alkyl silicate in which the alkyl group has 5 or more carbon atoms has a slow reaction and is not preferable.

Next, examples of the alkali used in the present invention include soda salts such as sodium carbonate, sodium bicarbonate and caustic soda, and potassium salts such as potassium carbonate. Use of soda salts is economically preferable.

In the present invention, it is preferable to use a polyalkoxyphosphazene compound, which is poorly soluble in water, by emulsifying it in water by adding a surfactant. The amount of the surfactant used for this purpose is the amount in the treatment liquid. For example, a stable emulsion may be obtained at 1 to 10% by weight.

As the surfactant used, anionic surfactants of sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, polyoxyethylene nonyl sulfate soda salt, polyoxyethylene phenyl sulfate soda salt, Polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, polyoxyethylene sorbitan monolaurate,
There are nonionic surfactants such as polyethylene glycol monostearate. These can be used alone,
You may use together 2 or more types.

The aqueous treatment liquid of the present invention generally contains a softening agent, an amino-modified silicone resin, an epoxy-modified silicone resin, a dimethyl silicone resin, a reactive dye fixing agent or a penetrating agent used for knitting and woven fabrics of cellulosic fibers. It may be added.

The cellulosic fibers of the present invention include
Includes cotton, polynosic, rayon, cupra, etc.
Particularly preferred is cotton.

The above-mentioned aqueous treatment liquid is adhered to such a cellulosic fiber, squeezed with a rubber mangle, and without drying,
Steam heat treatment. The steaming temperature is preferably 100 ° C. to 105 ° C., and the treatment time is preferably 30 seconds to 10 minutes.

[0020]

EXAMPLES Next, the present invention will be described in more detail with reference to examples. The evaluation methods of products in the examples are as follows.

Measurement of free formaldehyde According to JIS L 1096-1979 6.39.1.2 (1) B-1 method.

Washing Test The washing test was carried out by the following two methods. (1) A method in accordance with the Washing and Washing Test Method of the Fire Service Agency Notification No. 11 “Washing resistance performance standards related to flameproof performance (hereinafter referred to as“ Notification No. 11 ”) dated June 1, 1973. (2) Method of continuously washing with a liquid at 60 ° C for 75 minutes. In either method, the detergent is powder laundry soap (JIS K3303
1 type) specified in 1) and 1 g per 1 liter of water was used.

Flameproof performance test According to the 45 ° mesenamin method of the bedside bedding set by the Flameproof Product Certification Committee.

Tear strength test According to JIS L-1096-1990 6.15.5 D method (Bendurum method) (negative data indicates increased strength). Tear strength reduction rate (%) = [(Tear strength after processing-Tear strength before processing) / Tear strength before processing] x 100

Evaluation of texture A sensory evaluation was made by comparing the texture of the fabric before processing. ×: Remarkably hard, paper-like feeling △: Slightly hard ○: Same level ◎: Flexible

Odor evaluation x: There is an unpleasant odor. Δ: There is an unpleasant odor. ○: Almost no odor ◎: No odor

Chemical Adhesion Ratio Chemical Adhesion Ratio (%) = [(weight after chemical adhesion-excess dry weight) / excess dry weight] × 10
0

Example 1 A twill fabric made of 40-count cotton yarn, having 144 warp and 110 weft, was desizing, scouring, bleaching, mercerizing, and baking soda using a reactive dye. The printed, color-developed, water-washed and dried cloth was used as a cloth to be flameproofed by the following method. That is, the cloth to be processed is dipped in the composition of Formula A and squeezed to 48.5% with a rubber mangle.
After steaming at 02 ℃ for 10 minutes, wash with water, soaping,
Dried. Formulation A Polypropoxyphosphazene (average molecular weight 1400 ± 200) 40 parts Ethyl silicate 10 parts Polyoxyethylene nonylphenol ether 10 parts (Ethylene oxide 8 mol adduct) Sodium carbonate (10% aqueous solution) 10 parts Water 30 parts Obtained in this way As shown in Table 1, the processed cloth had durability and excellent flameproofness, and the tear strength was also improved. Example 2 A cotton cloth having the following cloth standard was used as a cloth to be processed, and the formulation B was used.
The composition was immersed in the composition of Example 1 and squeezed to 51.5% with a rubber mangle, and the same treatment as in Example 1 was performed. Fabric standard Designation: 230 threads Broad yarn count: 40 × 40 Density: 125 × 105 Formulation B Polypropoxyphosphazene (average molecular weight 1400 ± 200) 40 parts Ethyl silicate 10 parts Polyoxyethylene nonylphenol ether 10 parts (Ethylene oxide 8 mol adduct) Sodium carbonate (10% aqueous solution) 10 parts Aliphatic quaternary ammonium emulsion (solid content 30%) 2.5 parts Amino-modified silicone resin emulsion (solid content 30%) 3.0 parts Dye fixing agent (polyamine-based) 2.0 parts Polyethylene emulsion (solid content 30%) 2.0 parts Water 20.5 parts

Example 3 Polynosic fabric was desizing, scouring, bleaching, printing with a baking soda baking method using a reactive dye, coloring, washing with water, and drying. The processed cloth was flameproofed by the following method. processed. That is, the work cloth was dipped in the composition of Formula C, squeezed to 51.5% with rubber mangle, and treated in the same manner as in Example 1. Formulation C Polyethoxyphosphazene 40 parts Ethyl silicate 40 (made by Colcoat) 20 parts Polyoxyethylene nonylphenol ether 10 parts (Ethylene oxide 8 mol adduct) Sodium carbonate (10% aqueous solution) 30 parts The processed cloth thus obtained is As shown in Table 1, it was durable and had excellent flame resistance, and the tear strength was also improved.

Comparative Example 1 The treatment liquid was applied in the same manner as in Example 1 except that the composition of Formulation D was used as the treatment liquid, and the composition was dried at 120 ° C. After heat treatment at 6 ° C. for 6 minutes, it was washed with water and dried. Formulation D Pirovatex CP Conc (Ciba Geigy) 30.0 parts Sumitex Resin M-6 (Sumitomo Chemical Co., Ltd.) 10.0 parts Aliphatic quaternary ammonium emulsion (solid content 30%) 2.5 parts Amino Modified silicone resin emulsion (solid content 30%) 3.0 parts Dye fixing agent (polyamine type) 2.0 parts Polyethylene emulsion (solid content 30%) 2.0 parts Penetrant 1.0 parts Sumitex Accelerator ACX ( Sumitomo Chemical Co., Ltd.) 5.0 parts Water 44.5 parts The results of the performance test of the processed cloth are shown in Table 1. The processed cloth has excellent flameproof performance, but has a hard texture and a formalin odor. It was

Comparative Example 2 The composition of Formulation E was used instead of the composition of Formulation B as the processing liquid, the treatment liquid was applied in the same manner as in Example 2, dried at 120 ° C., and then 150 times. After heat treatment at 6 ° C. for 6 minutes, it was washed with water and dried. Formulation E Amidophosphazene AA-1000 (manufactured by Nippon Soda Co., Ltd.) 30.0 parts Aliphatic quaternary ammonium emulsion (solid content 30%) 2.5 parts Amino-modified silicone resin emulsion (solid content 30%) 3.0 Parts Dye fixing agent (polyamine type) 2.0 parts polyethylene emulsion (solid content 30%) 2.0 parts water 60.5 parts The performance test results of the processed cloth are shown in Table 1. Although it had a certain flameproof property and a soft texture, it had an unpleasant odor and was not practical. Further, the stability of the treatment liquid is such that when left at 40 ° C. for 3 hours, nearly 30% is decomposed, which is not preferable in practical use.

[0032]

[Table 1]

Examples 4-12 230 Broad cotton fabric treated in the same manner as in Example 1 was used as a work cloth. Using the treatment liquids shown in Table 2, the same treatment as in Example 1 was carried out. Flame processed. The processed cloths thus obtained all had excellent flameproofness as shown in Table 2 except for Example 4.
The relationship between the amount of polypropoxyphosphazene deposited and the carbonization length obtained in Examples 4 to 12 is shown in a graph as shown in FIG. From this, it can be seen that the method of the present invention exhibits good flameproof performance when the amount of phosphazene attached is about 15% owf or more.

[0034]

[Table 2]

[0035]

EFFECT OF THE INVENTION The non-formaldehyde flameproof knitted fabric of the present invention is repeatedly used, and the flameproof performance is not significantly deteriorated by washing.
It has no odor and is soft to the touch, making it extremely useful for applications such as futon side sheets and sheets.

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between the amount of polypropoxyphosphazene attached and the flameproof performance (carbonization length).

[Chemical 1]

[Chemical 2]

Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location // D06M 101: 06 7199-3B D06M 15/643

Claims (1)

Claim: What is claimed is: 1. A compound having the general formula [Formula 1] (wherein R represents an ethyl group, a propyl group or a butyl group, and n represents an integer of 3 or more) in the cellulosic fiber. And a compound having the general formula [Formula 2] (wherein R represents an alkyl group and n represents 0 or an integer of 1 or more) and an alkali, and a treatment liquid is adhered to the mixture, followed by steam heat treatment. A flameproofing method for cellulosic fibers. 2. The flameproofing method according to claim 1, wherein the treatment liquid is emulsified with an emulsifier.