JPS6021973A - Water resistant and flame-proof processing of cotton yarn and fiber product - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION TECHNICAL FIELD The present invention relates to a flameproofing method for cotton yarn and cotton fiber products. More specifically, the present invention relates to a method for flameproofing cotton yarn and cotton fiber products to provide good texture and water resistance.

Prior Art Conventionally, inorganic compounds such as ammonium phosphate, ammonium sulfamate, ammonium bromide, borax, boric acid, chlorinated paraffin, decabromodiphenyl oxide, tetrabromo organic halogen compounds such as bisphere)-A,
Phosphorus compounds such as tris dichloroglobyl phosphate, tris chloroethyl phosphate, tricresyl phosphate, tetrakis hydroxymethylphosphonium chloride (THPC), tetrakis hydroxymethylphosphonium sulfate' (THPS), dialkylphosphonopropionamide-N-methyl Reactive organic phosphorus compounds such as -ru compounds are known. However, when these flame retardants are applied to the surface of cotton fibers or cotton textile products, the surface becomes white, sticky, or rough, resulting in poor texture. make it extremely worse.

Furthermore, THPC, THPS, etc. have the disadvantage of reducing the strength of cotton. Furthermore, these materials produce particularly unpleasant odors during processing, and at the same time, they corrode processing equipment due to the generation of formaldehyde, hydrogen chloride, and sulfuric acid. Special equipment is therefore required to protect against odors and corrosion.

OBJECTS OF THE INVENTION An object of the present invention is to provide a processing method that can eliminate these drawbacks and at the same time impart water resistance and flame retardant properties to cotton yarns and cotton fiber products.

Structure of the Invention The present invention provides a method for waterproofing and flameproofing cotton threads and cotton fiber products, and this method comprises applying 1% to the weight of the cotton threads or cotton fiber products to the cotton threads or cotton fiber products. ~4
0% by weight of the general formula [In the formula, R and R' may be the same or different, each representing all aliphatic hydrocarbon residues having 2 to 3 carbon atoms 4 (however, as R' may be chlorinated), m is 1 or 2
and n represents an integer of 1 to 30] and t171 fat having a film-forming ability of 1 to 30% by weight.

Detailed Description of the Structure of the Invention In the phosphorus compound represented by the general formula used in the method of the present invention, n is 1 to 30, preferably 1 to 15. When a compound in which n is 30 or more is used, the processed product becomes rough and stiff and has a poor texture, which is not preferable. Further, a compound in which n is 0 has poor water resistance and cannot be used. The amount of phosphorus compound deposited is 1 to 40 cents by weight, preferably 3 to 30 percent by weight, based on the weight of the cotton yarn and cotton fiber product. Even if 40% or more is deposited, no particular improvement in flame retardant performance will be observed, and the disadvantage is that the texture will deteriorate. Further, the amount of the resin having film-forming ability attached is 1 to 30% by weight, preferably 3 to 30% by weight.
6 out of 20 cents.

If the amount of adhesion is less than 1%, the water resistance will be weak, and if it is more than 30%, it will have a negative effect on the texture and flame retardant performance, which is not preferable.

Typical phosphorus compounds used in the present invention are shown below.

n = 1 to 30 n = 1 to 30 n = = 1 to 30 n = 1 to 30 n = 1 to 30 Representative examples of resins having film-forming ability used in the method of the present invention are shown below.

TrimethylolmelamineMelamine-formaldehyde initial condensate Urine-formaldehyde Initial metal etherification Melamine-formaldehyde initial sulfate Phenol-formaldehyde Initial M condensate Urea-melamine-formaldehyde initial condensate Acrylic acid ester resin Vinyl acetate resin Vinyl chloride resin Chloride Vinylidene resin SDR resin Ethylene-acetate-vinylidene chloride copolymer resin Acrylic acid-vinylidene chloride copolymer resin Cotton yarn and cotton fiber products that can be flame-retardant treated using the method of the present invention include cotton fibers, cotton fiber products, and These are fibers and textile products that are blended, interwoven, knitted, or mixed with other fibers and textile products whose main component is These may be dyed, resin-treated, mold-proofed, insect-proofed, etc. Further, it is also possible to apply flame retardant treatment to the dyed or other processed item, and further perform water-repellent, oil-repellent treatment, etc. in the next step. If necessary, flame retardant treatment, water repellent treatment, oil repellency treatment, etc. can be performed in the same bath, and treatments other than flame retardant treatment can also be used in the same process.

The cotton yarns and cotton fiber products that can be processed by the method of the present invention include filamentous materials (blending, intertwisting), fabrics, woven fabrics, knitted fabrics, non-woven fabrics, industrial materials, industrial and household textile products, clothing, etc.
Specifically, bedding/bedding, inchiniya, efsteriya-related items, sports equipment, daily miscellaneous goods, etc., such as canvas, sheets, tents, ropes, curtains, carpets, etc.
Wall upholstery, chair upholstery, futons, blankets, bedding, futon cotton, clothing such as work clothes, pajamas, accessories such as lyxo, braided cords, etc. - 1 Raised products, etc., and other items of any shape. There is no problem. In addition, flame-retardant treatment can be applied to thread-like, fiber-like, cloth-like materials, etc., and any article can be made using these materials.

Conventional methods can be used to perform flameproofing using the method of the present invention. That is, a phosphorus compound represented by the general formula and a resin having film-forming ability are dissolved, emulsified, or dispersed in water, a solvent, etc., other additives are added as necessary to form a processing liquid, and cotton yarn and cotton fibers are added to the processing liquid. Soak the product;
There are other methods such as squeezing 9, drying, and applying a processing liquid by spraying, brushing 9, applying with a roller, etc., and then drying. The machining fluid may be applied using any other method.

In the processing method of the present invention, the processing liquid may be water, an organic solvent, or a mixture of these, but from the viewpoint of fire risk, water-based liquids are preferred. It is preferable to have one.

These processing fluids may be used as solvents, activators, emulsifiers, dispersants, penetrants, color activating agents such as dyes, water repellents, oil repellents, antifouling agents, antibacterial agents, and insect repellent agents, as required. It may contain additives, softeners, finishing agents, resin processing agents, weathering agents, ultraviolet absorbers, antioxidants, catalysts, thickeners, and other 9) 1 (fuel agents, etc.).

The evaluation of flame retardancy in this specification was carried out in the form of yarn and cloth using the method described below.

Method for evaluating flame retardancy in thread form A sample is obtained by bundling threads with a weight of 311 and a length of 30 ounces, and tying them at two points 10 m from the ends with similar threads. The sample was immersed in warm water at 50°C for 30 minutes, squeezed, dried, and left overnight in a silica gel desiccator at 20°C. A 7-length section of an 8 crn Alco' 1 -Ruranzo flame was exposed to indirect flame for 5 seconds, and after the flame was removed, the afterflame time, residual time, and carbonization length were measured.

Method for evaluating flame retardancy in cloth A cloth with a size of 25 crn x 35 crn was immersed in warm water at 50°C for 30 minutes, wrung out and dried. Conduct a combustion test in accordance with the Fire and Disaster Management Agency test).

EXAMPLES The present invention will be further explained by the following examples. In the examples, "parts" indicate parts by weight.

Production Example of Flame Retardant Production Example 1 Sitatris was synthesized from phosphorus trichloride and ethylene oxide according to the method described in Japanese Patent Publication No. 37-12651.
Chloroethyl phosphite (P (0CH2CH2CL)
)3) Chloroethyl phosphorodichloridite (C1
CH2CH20PCL2) 1 mole of the mixture is reacted with 2 moles of propionaldehyde at 15°C to 20°C. Next 1. Gradually heat at 90°C to 95°C for 60 minutes to remove by-product dichloroethane while heating to 100°C to 11°C.
Heat to 0°C. Further, low volatile components were removed under reduced pressure of 1 wnHg to obtain the desired product. The characteristics of the product were as follows.

Viscous/oily liquid Molecular weight: Approximately 639 P content: 14.5% Ct content: 27.7% Production example 2 Ethylene chlorophosphite synthesized from ethylene glycol and phosphorus trichloride according to the method of Japanese Patent Publication No. 42-19337. Synthesized by reaction with acetone.

Starch syrup-like, viscous substance Molecular weight: Approximately 3037 P content: 16.3 Ct content: 21.0% Production example 3 H5 Phosphorus trichloride and Tris-chlorozorobyl phosphite obtained by reaction of pyrene oxide at 130℃~
Add it little by little into a flask kept at 140°C for isomerization,
After the entire condensation reaction was completed, low volatile components were removed under reduced pressure of 0.5 mm Hg to obtain the desired product.

Viscous oil, liquid Molecular weight: Approximately 510 P content: 12.1% Ct content: 27.8cm Reference production example 0CH2CH2Ct I was produced by the reaction of ethylene chlorophosphite and acetone according to the method of Japanese Patent Publication No. 19337/1973.

Softening point: 39-44°C, transparent solid Molecular weight: about 6727 n=35 P content: 165% Ct content: 20.0% Aqueous solution) Gradually add 500g while stirring, and finally add 50g of water.
An aqueous dispersion with a flame retardant component of 45% is obtained. Next, this 45
% aqueous dispersion 45 parts, trimethylolmelamine bisolid content 8
0% aqueous solution, Sumitex Resin Al1-
3) 10 parts, Acrylic acid ester resin liquid (solid content 50%, Sannin Shoji Co., Ltd., y Ncozo zSHX-10
1) 14 parts, 1 part of triethanolamine as a catalyst,
Mix 15 parts of water to prepare a total of 85 parts of processing fluid. A fine count 10 double-thread cotton introduction thread is dipped in the above processing solution,
Centrifugal dewatering removes excess processing fluid and reduces the shrinkage rate to 126
%. This thread was pre-dried at 80°C and further dried at 150°C.
Curing was performed at ℃ for 5 minutes.

When the flame retardant performance of the obtained processed yarn was evaluated, the afterflame time was 0.
A flame-retardant processed yarn with extremely excellent water resistance was obtained with a carbonization length of 9 m and a drying time of 0 seconds. The strength of this processed yarn is 1
．． 44'l and elongation of 8.2%, which is comparable to the same unprocessed yarn with strength of 1.494L and elongation of 8.3%. Furthermore, this flame-retardant processed yarn had a good feel.

Furthermore, using the thus obtained flame-retardant processed yarn, a knitted fabric with a basis weight of 29,417 m2 was created using a flat knitting machine, and its flammability was evaluated.
Seconds, time left. seconds, carbonized area 25 pieces, 2 pieces, again 3
In the case of second heating, the afterflame time was 3 seconds, the residual flame time was 0 seconds, and the carbonized area was 12 cm2, passing the Hiroshima Fire Department test. The texture was also good.

Example 2 500 gr of polyvinyl alcohol (12% solids aqueous solution) was gradually added to 450 gr of the compound obtained in Production Example 1 with stirring, and finally 50 gr of water was added to make the flame retardant component 45 g. an aqueous dispersion of ioo'.

grt - get. Next, 5 parts of this 45% pure aqueous dispersion, 1 part of trimethylolmelamine (80% solids aqueous solution)
0 parts, acrylic acid ester resin liquid (solid content 50%) 14
1 part of triethanolamine as a catalyst and 15 parts of water to prepare a total of 85 parts of processing fluid. Eye weight 250&
/m2 of cotton cloth is dipped in the above processing solution and squeezed with a mangle to obtain a drawing rate fl:io.

Let's do it. After pre-drying at 80°C, further drying at 150°C
Curing was performed at ℃ for 5 minutes. When the flame retardant performance of the obtained processed fabric was evaluated, after heating for 1 minute, the afterflame time was 6 seconds, the residual flame time was 0 seconds, and the carbonized area was 28 countries, and the carbonized area was 2 seconds. Time: 0 seconds, carbonized area: 21
It was a flame-retardant fabric with a rating of 2, passed the Fire and Disaster Management Agency test, and had good texture and water resistance.

Example 3 280 gr of the compound obtained in Production Example 1, F! J Methylolmelamine (solid content 809J aqueous solution) l 00
Mix 620 g of grs methanol and dissolve uniformly to obtain a processing liquid. A tent site with a basis weight of 460 y/m2 was sprayed with the processing liquid at a rate of 46017 m2.

When pre-drying at 80°C and curing for 4 minutes at 15'O°C was performed, the S flammability was evaluated, and when heated for 2 minutes, the afterflame time was 0 seconds and the residue time was 0.
In the case of heating for 6 seconds with a carbonized area of 26 cm2, the afterflame time is 1 second, the residual dust time is 0 seconds, and the carbonized area is 19 crn2, passed the Fire and Disaster Management Agency test, and has a good texture and water resistance. It was a flame treated tent site.

Example 4 A nonionic activator sog'4 was dissolved in 500 gr of the compound obtained in Production Example 2, and 420 &f, c-
Add it gradually while stirring well until the concentration is 50% +7
) to obtain a c-mulsion. To 45 parts of this emulsion, 10 parts of urea-formaldehyde condensate (aqueous solution with a solid content of 85%, Sumitomo Chemical, Sumitex Silub 250 Conc),
Add 16 parts of enalene-vinyl acetate-vinyl chloride copolymer resin liquid (solid content 50%, Sumikaflex 830, Sumitomo Chemical), 2 parts of softener, and 17 parts of water to obtain a total of 90 parts of processing liquid. The entire length of fine count 10 twin cotton yarn is immersed in this processing liquid, and the excess processing liquid is removed by centrifugal dehydration to obtain a reduction ratio of 110%. After pre-drying this total light at 80°C, a plain woven fabric (basis weight 500'11/m2) was created, and 0.2% of water and oil repellent was applied to the plain woven fabric, and after pre-drying. , curing was performed for 5 minutes in a dryer at 150°C. When heated for 1 minute, the obtained processed cloth had an afterflame time of 0 seconds, a residue time of 0 seconds, and a carbonized area of 25 crn2.
In addition, in the case of heating for 3 seconds, the afterflame time is 2 seconds, the residual flame time is 0 seconds, and the carbonized area is 20 (1) 2, so it has flame retardant performance that passes the 6C1 Fire and Disaster Management Agency test. Water repellent, oil repellent finishing 14
It was & things. This fabric also had a good feel.

Example 5 After dissolving 75 gr of a nonionic surfactant in 500 gr of the compound obtained in Production Example 3, 425 g of water was added little by little and stirred well to make 1000 gr of a 50% emulsion.
I got it. Add 45 parts of this 50% emulsion to a urea-melamine-formaldehyde initial condensate (27% aqueous solution, Sumitomo Chemical,
Sumitex Resin ULY) 25 parts, vinyl acetate resin liquid (solid content 50 t, Juju Chemical, Sumikaflex 752)
15 parts, 1 part of antibacterial and insect repellent processing agent, 0.2 part of ultraviolet absorber,
25.8 parts of water was added to prepare a processing liquid consisting of a total of 95 parts. A fine count 10 twin cotton thread was dipped in this processing liquid, and the excess processing liquid was removed by centrifugal dewatering to reduce the shrinkage rate to 18.
5%, then pre-dried at 105°C, and further dried for 1
Curing was carried out at 50°C to obtain flameproof, antibacterial, and insectproof yarn. The flame retardant properties of this processed yarn include an afterflame time of 2 seconds, a residual burn time of 0 seconds, a carbonization length of 8.5 cm, and a good texture.
there were.

Comparative Example 1 350 gr of the compound obtained in the reference production example was dissolved in 550 gr of methanol, and 100 gr of trimethylolmelamine (aqueous solution with a solid content of 80 g) was added to give a total of 10 gr.
00 gr of processing fluid was prepared. Cotton yarn of fine count 10 twin cotton yarn was immersed in this processing solution, excess processing solution was removed by centrifugal dewatering, squeezing rate f: 80%, and after pre-drying, the same method as in Example 4 was carried out. I tried to make a textile, but the thread was too stiff and I couldn't weave it.

Comparative Example 2 500 gr of bis(dichloroglobil) dichloropropyl phosphonate (in the general formula, m = o, R, R' = zolopyl residue, m = 2) and 80 gr of nonionic activator
- 420 gr of water was added to the solution with stirring to make a 50% emulsion. This 50
% emulsion to 50 parts of trimethylolmelamine (solid content: 80 parts)
% aqueous solution), 14 parts of acrylic acid ester resin liquid (solid content 50%), triethanolamine 1 as a catalyst
1 part and 10 parts of water were added to prepare a total of 85 parts of processing fluid.

Cotton yarn made of fine count 10 twin cotton was immersed in the processing liquid, and the excess processing liquid was removed by centrifugal dewatering to obtain a squeezing rate of 100%. After pre-drying this cotton yarn at 80°C, it was used to prepare a knitted fabric in the same manner as in Example 1, and the entire knitted fabric was cured at 150°C for 5 minutes to obtain a knitted fabric with a basis weight of 28097 m2. It was confirmed that the flame retardant property was completely burnt out when heated for 1 minute and 3 seconds, and that it did not have water resistance.

Procedural Amendment (Spontaneous) August 3, 1981 Director of the Patent Office Kazuo Wakasugi 1, Indication of the Case 1988 Patent Application No. 130199 26 Title of Invention Water-resistant and flame-retardant processing method for cotton yarn and cotton fiber products 3. Relationship with the case of the person making the amendment Name of patent applicant Name Marubishi Yuka Kogyo Co., Ltd. Name of Toyo Senki Co., Ltd. 4. Agent 5. Column 6 of “Detailed Description of the Invention” of the specification to be amended; Amendment Page 19 of the detailed description of contents, line 6, "185 cm" is corrected to "85 cm".

that's all

Claims (1)

[Claims] 1. A cotton yarn or cotton fiber product containing 1 to 40% by weight of the general formula [wherein R and R' are the same even if they are the same] each aliphatic hydrocarbon residue having 2 to 3 carbon atoms (However, the aliphatic hydrocarbon residue as R' may be chlorinated), m is 1 or 2 represents an integer of n
represents an integer from 1 to 30], a method for waterproofing and flameproofing cotton yarn and cotton fiber products, characterized by adhering a phosphorus compound shown and a resin having a film-forming ability of 1 to 30% by weight. .