JPS63190080A - Treatment of fiber material - 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 [Field of Industrial Application] The present invention relates to a method for treating fibrous materials. More specifically, the present invention relates to a treatment method for imparting a durable flame retardant finish to cellulosic fibers or mixtures of cellulosic fibers and other fibers.

[Conventional technology]

Conventionally, the following methods have been known as methods for imparting durable flame retardancy to fiber materials.

For 100% cellulose fibers, the Proban method, which cures a condensate of tetrakis hydroxymethylphosphonium chloride (THPC) and urea, or the condensate of tetrakis hydroxymethylphosphonium chloride (THPS) and urea with ammonia, N-hydroxymethyl- 3 dimethylphosphonopropionamide (Pyrovatex
CP, manufactured by CIBA-CJIGY, etc.) and a triazine ring-containing compound in the presence of a catalyst, vinylphosphonate oligomer (Fyrol 76, 5t
There is a method of polymerizing N-methylolacrylamide and N-methylolacrylamide in the presence of a catalyst.

In addition, for preester fibers, there is a method of using an aqueous dispersion of hexabromocyclododecane and diffusing it into the fiber by an exhaustion method or a thermosol method, or a method of using an aqueous dispersion of hexabromocyclododecane to diffuse it into the fiber, and a method of diffusing it into the fiber by an exhaustion method or a thermosol method. A method in which a phosphorus-containing compound is absorbed into fibers by an exhaustion method or a thermosol method has been put into practical use.

[Problem that the invention seeks to solve]

However, if a mixture of polyester fiber and cellulose fiber contains a high proportion of cellulose fiber, flame retardant treatment using a flame retardant for cellulose fiber or vinyl phosphonate oligomer acrylic latex may be necessary. Some attempts have been made to use flame retardants, but it is difficult to achieve durable flame retardancy, and even if the optimal flame retardant is used for each of polyester fibers and cellulose fibers, each product alone cannot pass the test. The current situation was that even the standards for the micro burner method under the Fire Service Act could not be met. Moreover, it has not been possible to obtain a practical flame-retardant product with good flame retardancy, texture, and physical properties for materials with a blending ratio of polyester and cellulose of 70:30 to 30 nia-0. .

The reason why it is not easy to make flame retardant products made of a mixture of polyester fibers and cellulose fibers is thought to be due to the fact that the yarns made of a mixture of polyester fibers and cellulose fibers that have been treated with a flame retardant undergo some kind of interaction during combustion. The following three possibilities are listed. That is, (1) the original action of the flame retardant applied to one component is inhibited by a chemical reaction with the other component polymer or its decomposition product. (2) When two-component polymers or their reaction products receive reaction heat, the types of combustible thermal decomposition products and their production rate distribution differ from those in the case of a single polymer. ■As a result of physical mixing of heat-fusible components and non-fusible components, dropping of molten components from the system is suppressed. That is, the presence of cellulose or its charred product reduces the self-extinguishing properties of the polyester component.

For the above reasons, we have been studying techniques for applying durable flame-retardant treatments to mixed products of polyester fibers and cellulose fibers, as well as flame-retardant treatments that are resistant to washing and dry cleaning. As a result, we have completed the present invention.

[Means for solving problems]

According to the present invention, there is provided a method for treating a fibrous material, which comprises treating a fibrous material with the general formula (HOCH2)4PX [wherein X represents ct, Tso4 or OH]. vinegar〕
The reaction product of 1 mole of tetrakis hydroxymethylphosphonium salt and 0.2 to 3.0 moles of urea is expressed by the general formula.

Add 0.1 to 3.0 moles of N-hydroxymethyldialkylphosphonopropionamide represented by (RO)2CH2CH2C0NHCH20H [in the above formula, R represents an alkyl group having 1 to 3 carbon atoms or a halogen-substituted alkyl group] The method is characterized by forming a crosslinked film consisting of the processing agent obtained by the above method and a triazine ring-containing compound.

By treating with the method of the present invention, it is possible to impart flame retardancy to a mixture of synthetic fibers and cellulose fibers, which was previously impossible, and the flame retardancy is higher than that of conventional techniques. It is durable and has excellent breathability and texture. According to the present invention, a flame-retardant fiber product having such excellent performance can be stably produced in one step.

The fiber material as used in the present invention refers to cellulose fibers and mixtures of synthetic fibers and cellulose fibers, and more specifically, polyesters and polyamides.

It is composed of synthetic fibers such as acrylic and natural cellulose am, cellulose acetate, and semi-synthetic cellulose fibers such as rayon at a mixing ratio of 0:100 to 95:5%. refers to mixed spinning, mixed weaving, mixed knitting, mixed twisting, etc. Mana, its shape is thread-like, cotton-like, fabric,
It can be woven, knitted, non-woven, etc., and can be used for industrial materials, industrial and household textile products, clothing, clothes, and bedding.

Inchiriya or Efsteria supplies, sporting goods 5
Daily miscellaneous goods, etc.1 For example, canvas, sheets, tents, etc.
Ropes, curtains, carpets, wall coverings, chair coverings, bedding, futons, blankets, and sheets.

Cotton futons, work clothes, pajamas, slippers? braids, raised items, etc.
There is no problem with anything else.

Treatment agents useful in the present invention include, for example, 1 mole of the tetrakishydroxymethylphosphonium salt defined above and 0% urea.
．． to the reaction product with 2 to 0.3 mol.

It can be obtained by adding 0.1 to 3.0 mol t of N-hydroxymethyldialkylphosphonopropionamide defined above, or by reacting at 30 to 90°C after adding this.

When preparing a treatment agent, 2 to 3.0 mol of urine io per 1 mol of tetrakishydroxymethylphosphonium salt,
Preferably add 0.5 to 2.0 mol and heat at 30°C to 100°C.
The reaction is carried out at a temperature of preferably 40°C to 90°C for about 60 minutes.

Next, 0.1 to 3.0 mol, preferably 0.2 to 2 mol, of N-hydroxymethyldialkylphosphonopropionamide
．． Add 0 moles.

If necessary, this is further reacted at 30°C to 90°C to prepare a processing liquid. Here, the reaction is carried out at a ratio of 0.2 to 3.0 moles of urea per mole of tetrakis hydroxymethylphosphonium salt, but if the amount of urea is less than 0.2 moles, the texture of the treated material will be rough and hard. Significant decrease in strength. If the amount of urea is 3.0 moles or more, the washing resistance will be poor. N
-Hydroxymethyldialkylphosphonopropionamide is used in an amount of 0.1 mol to 3.0 mol, but 0.1 mol to 3.0 mol.
When the amount is less than 1 mol, the texture becomes rough and hard. If the amount is 3 moles or more.

It becomes sticky, has a poor texture, and has reduced washing resistance.

The concentration of the processing agent in the processing liquid is preferably 5 to 85% by weight, preferably 20 to 75% by weight.

Further, examples of triazine ring-containing compounds useful in the present invention include compounds represented by the following general formula.

In the above formula, R1-R6 are each independently -H, -OH.

-QCnH2n+1. -CH2QCnH2n+1. -C
H20H.

-CH2CH20H, -CH2CH20H20H, -C
ONH2° represents a positive integer, especially an integer from 1 to 10.

The specific product name is Sumite manufactured by Sumitomo Chemical Co., Ltd.
c Re5in M-LM-6, MC, MK, M-
Examples include 5S. The triazine ring-containing compound is contained in an aqueous solution or dispersion in an amount of 2% by weight or more, preferably 5 to 2% by weight.
It is preferable to use it at a concentration of 0 weight.

The reaction between the treatment agent of the present invention and the triazine ring-containing compound is as follows:
This is preferably carried out in the presence of a catalyst, such as aliphatic caldic acids such as formic acid and acetic acid, acrylic acid,
Examples include unsaturated carbenoic acids such as methacrylic acid, phosphorous acids, oxycaldic acids such as tartaric acid, aminocaldic acids such as glutamic acid, unsaturated dicardicic acids such as maleic acid, and their ammonium, sodium, and potassium salts. In addition, sulfuric acid, persulfuric acid, hydrochloric acid, phosphoric acid,
Examples include ammonium, sodium, magnesium, aluminum, and other salts of inorganic acids such as nitric acid, and double salts thereof. These catalysts are preferably used at bath concentrations ranging from 0.01 to 10 parts by weight.

The processing liquid containing the processing agent and triazine ring-containing compound in the present invention may be diluted by adding water, a solvent, etc. as necessary, and may be diluted with water, a solvent, etc. May be used in combination with other drugs. Any method such as dipping, spraying, coating, foaming, etc. may be used to apply the processing liquid to the fiber material. What is the amount of adhesion between the treatment agent and the triazine ring-containing compound?

3 to 40 weight ratio to fiber weight, preferably 5 to 30
He is in charge of weight. If the weight is less than 3, it lacks durable flame retardant performance.
If the weight ratio exceeds 40, the texture is hard and cannot be put to practical use.

The treatment according to the present invention is generally carried out by steaming treatment using microwaves or steaming treatment using a high-pressure steamer. That is, by steaming treatment using microwaves,
Since the fiber material impregnated with the treatment agent and the triazine ring-containing compound can be uniformly heated from deep inside, the crosslinking reaction between the treatment agent and the triazine ring-containing compound can be promoted and highly efficient fixation can be achieved. Also, this method.

Since the electromagnetic energy generated by microwaves can be effectively used to uniformly process the water and the moisture content can be used effectively, it is possible to achieve a flame retardant finish with very little whitening and a good texture, making it the most effective treatment. Chill depending on the reaction treatment method. On the other hand, even in the case of steam heat treatment using a high-pressure steamer, highly efficient fixation can be obtained by ensuring that the crosslinking reaction occurs from deep inside. However, even if a material to which a processing agent and a triazine ring-containing compound have been added is treated with only steam or dry heat curing, the fixation rate is low and the texture is rough and hard. Such excellent durable flame retardant performance cannot be obtained. Further, even if this treatment agent and a triazine-containing compound are applied to each in a two-step treatment, the fixation rate is low and excellent durable flameproofing properties cannot be obtained.

In the present invention, microwave heating in the presence of moisture is performed, for example, at a frequency of 2450 MHz, at a frequency of 0.2 to 20
kW, preferably at a power of 2 to l OkW, 10
It is preferable to carry out the reaction for a period of seconds to 60 minutes, preferably 10 minutes to 30 minutes, at a direct steam pressure of 0.1 to 3 kl/cm2.

On the other hand, in high-pressure steaming treatment, the vapor pressure is 9/cm to 0.1 to 3.
2, preferably 0.5 to 2.5 kg/an” and 10 to
It is good to carry out for 120 minutes, preferably for 30 to 90 minutes.

Next, a soaping process is performed to remove unfixed chemicals. This treatment is preferably carried out by soaping in hot water at 80 to 100°C or in an aqueous soda ash solution for 5 to 30 minutes. The soaping device may be any commonly used soaping device, and there is no particular limitation on its type.

The fibrous material thus obtained has far superior flame retardancy compared to those made by the prior art, and also has significantly superior washing resistance and dry cleaning resistance. Such treatment effects are obtained by the flame retardant treatment agent and triazine ring-containing compound used in the present invention being strongly adhered to the fibers while causing crosslinking through microwave steaming treatment or high pressure steaming treatment. , has a good texture,
It also has the characteristics of less loss of strength and easy manufacturing method.

〔Example〕

Below, a method for producing a processing agent useful in the present invention will be explained.

Production Example A 100 N of water and 200.9 (3,33 mol) of urea were added to 700 Ji' (2,76 mol) of an 80% aqueous solution of tetrakis hydroxymethylphosphonium sulfate, and the mixture was heated to 40°C to uniformly dissolve the urea. let Gradually increase the temperature and react at 75°C to 80°C for 60 minutes. Next, 250 g (1.18 mol) of N-hydroxymethyldimethylphosphonopropionamide was added and the mixture was heated at 60°C to
The reaction was carried out at 65°C for 30 minutes. For this, solid content is 80
A transparent aqueous solution (hereinafter referred to as flame retardant A) was obtained.

Production Example B 75I of water is added to an 80% aqueous solution of tetrakis hydroxymethylphosphonium sulfate 25419 (1 mol), urea 9011 (1.5 mol) is added, and the mixture is heated to 50°C to uniformly dissolve the urea. Gradually raise the temperature to 75℃
React for 60 minutes at ~80°C. Next, N-hydroxymethyldimethylphosphonopropionamide 211jl (
1 mol) was added to prepare a processing liquid. This was a transparent aqueous solution (hereinafter referred to as flame retardant B) with a solid content of 80%.

Production Example C Tetrakishydroxymethylphosphonium chloride 8
238g (1 mol) of 0% aqueous solution and 801% NaOH 50% water bath solution! Tetrakis hydroxymethylphosphonium hydroxide 1 was produced by gradually adding water at a temperature below 50°C, removing water under reduced pressure, and filtering the resulting NaCt crystals.
38II (0.8 mol.) to water 106I and urea 6o
Ii (1 mol) was added, urea was uniformly dissolved at 40°C, the temperature was gradually raised, and the reaction was carried out at 70-75°C for 60 minutes.

Next, 24# (0.1 mol) of N-hydroxymethyldiethylphosphonoprobionamide and 27g of N-hydroxymethyldiisoderopylphosphonoprobionamide (
0.1 mol) was added and reacted at 60-65°C for 30 minutes. In this case, a clear aqueous solution with a solid content of 70% (hereinafter referred to as
A flame retardant (referred to as flame retardant C) was obtained.

Production Example D 80% aqueous solution of tetrakishydroxymethylphosphonium sulfate (254II (1 mol)) to 75% water! Add urea 90Ii (1.5 mol) and heat to 50° C. to uniformly dissolve urea. Gradually raise the temperature to 80
React for 60 minutes at °C. Next, N-hydroxymethyl di-2-chloroethylphosphonopropionamide 309
I9 (1 mol) was added to prepare a processing liquid. This was a slightly cloudy aqueous solution (hereinafter referred to as flame retardant) with a solid content of 80%.

Comparative Preparation Example E (Using urea in an amount outside the range) Tetrakis hydroxymethylphosphonium sulfate 8
78.9' of water and 210# (3.5 mol) of urea are added to 254 J (1 mol) of a 0% aqueous solution and heated to 50°C to uniformly dissolve the urea. Gradually raise the temperature to 75℃~8
React for 60 minutes at 0°C. Next, N-hydroxymethyldimethylphosphonoglobionamide 106! i(0,
5 mol) was added thereto and reacted at 60 to 65°C for 30 minutes.

As a result, a transparent water bath liquid (hereinafter referred to as flame retardant E) with a solid content of 80% was obtained.

The physical property evaluation method and examples are described below.

Washing method Powder washing soap (JIS K3303 No. 11 Risui IJj
Using this cylinder 1y, supply water at 60°C, add detergent, add the test specimen, and then wash with liquid at 60°C for 15 minutes. Next, drain, add water, and rinse for 5 minutes with 40℃ water 3
The sample fabric was washed 5 times, 30 times, and 50 times, with each cycle being 1 cycle.

Dry cleaning method The dry cleaning method specified in Fire and Disaster Management Agency Notification No. 1 (861) was used. However, before performing dry cleaning, the sample shall be treated with hot water (40° C. for 30 minutes) and dried normally.

Flame retardant performance test method It was conducted in accordance with the performance test standards for flame retardant products.

Vertical method: Dimensions of specimen: 89+m x 254m each Conditioning of specimen: After drying in a constant temperature dryer at 50±20° C. for 24 hours, dry in a silica gel desiccator for at least 2 hours.

Vertical burner method Measure the length of the two flames upward from the highest point of the burner to 38
Adjust the flame so that it is light and check that the flame is stable. Move the burner and apply indirect flame to the test specimen for 3.0±0.2 seconds. After removing the burner flame from the test specimen, check the state of combustion on the test specimen support frame and the ignitability of the flame tube.

Judgment: For the 5 test pieces of fabric, the average carbonization length must be 178 cm or less, and the maximum carbonization length must be less than 254 m. The flame tube must not be ignitable.

45° mecenamine method: It was conducted in accordance with the performance test standards for flame retardant products.

B. Overlap the test specimen on the wire mesh of the test specimen support frame and fix it to the specimen support frame without loosening, and place mecenamine (Elli-
Place the Lilly product number 1588 (trade name Mecenamine) in a way that will not easily move it.

After igniting, use a pine tree to ignite the flame. Immediately after ignition, close the glass window of the combustion test box and leave it until combustion is complete.

C. The carbonization length shall be the maximum longitudinal length of the carbonized portion of the test specimen, and the maximum length for the three test specimens shall be 70sai or less, and the average value shall be 50cm or less.

45° micro burner method: Flame retardancy was judged according to the 45° micro burner method of the Fire and Disaster Management Agency Flame Retardant Test Regulations of the Ministry of Home Affairs.

In this case, the acceptance standard value is a carbonized area of 30cr112 or less.

Afterflame time is 3 seconds or less, and residual flame time is 5 seconds or less.

Example 1 50% polyester/50 cotton interwoven fabric (basis weight 1301
i/m'') by conventional methods, burning, desizing, scouring, bleaching,
Heat set and dyed and fixed under the following conditions.

Liquid formulation flame retardant A 40 Weight related catalyst Niammonium phosphate 1.5 Nonionic surfactant 0.1 #Emuldan 9
09 (Kao) This was applied with a 75% thickening and fixed using a microwave actuator Apollotex (manufactured by Jukin Industries) under the following conditions.

Micro skill output 7. OKW Reaction time 30 minutes Direct steam 0.7 hours/cm2 Winding speed
After that, it was soaped at 15 m/min and set to dry.

Comparative Example 1 50% polyester/50% cotton mixed woven fabric (basis weight 1301
7 m") was treated and dyed in the same manner as in Example 1, and then flameproofed under the following conditions.

Liquid formulation crosslinker N-methylol acrylamide 25 #
Catalyst Potassium persulfate 0.5 #This was applied with a pick ara f75%, dried at 120°C for 2 minutes, cured at 160°C for 3 minutes, and then soaped and dried.

Comparative Example 2 The same dyed fabric as in Example 1 was dyed with hexabromocyclododeca 7.
15% o, w*f, 30 at 130'C with 40% dispersion
After being subjected to exhaustion treatment for a minute, it was soaped and dried at 120° C. for 2 minutes. Next, flameproofing was performed under the following conditions.

Liquid prescription flame retardant 7 Eye Lure 6 40 Weight related crosslinking agent
N-methylol acrylamide 25 N-methyl
Medium Potassium persulfate o, 5 Apply this with a pickup 75, dry at 120"C for 2 minutes,
After curing at 0°C for 3 minutes, it was soaped and dried.

Comparative Example 3 The following prescription solution was applied to the same dyed fabric as in Example 1 using the pickup 75.

Liquid formulation crosslinking agent Bmltax Re5in M6 10
//Catalyst ammonium chloride 1
〃Wed 49 〃Total
100 then 120
It was dried at 120°C for 2 minutes, cured at 160°C for 3 minutes, soaped, and dried at 120°C for 2 minutes.

Comparative Example 4 The same dyed fabric as in Example 1 was treated with a 40% dispersion of hexabromocyclododecane at 15% O, W, F at 130°C for 30 minutes.
The hole diameter was subjected to exhaustion treatment for 1 minute, soaping was performed, and drying was performed at 120° C. for 2 minutes. Next, the following prescription solution was applied using a pickup 75.

Liquid prescription flame retardant Pyrovatex CP 40% by weight Crosslinking agent Sumitex Re+sinM5 10
1 Catalyst Ammonium chloride 11 Water
49 l total
100 1 then 120℃
It was dried at 160°C for 2 minutes, cured at 160°C for 3 minutes, soaped, and dried at 120°C for 2 minutes.

Comparative Example 5 An equimolar precondensate of tetrakis hydroxymethyl phosphonicum sulfate (80% water fljPl) and urea was applied to the same dyed fabric as in Example 1 with a pickup of 75 cm,
Comparative Example 6 The following formulation solution was applied to the same dyed fabric as in Example 1 at a pickup rate of 75%.

Liquid prescription flame retardant Pyropatex CP 40% by weight Crosslinking agent Sumitex ResinM6 10 1
Catalyst Ammonium Chloride 11 Then, it was fixed using Atex under the following conditions.

Microwave output 7. OKW reaction time
30 minutes Direct steam 0.7 kg/wound 2 winding speed 15 m 7 minutes Afterwards, soap and dry set.

Table 1 shows the results of evaluating the flame retardancy of the processed fabrics obtained in Example 1 and Comparative Examples 1 to 6.

Durable flameproofing has not been achieved except in the examples of the present invention.

Example 2 65% polyester/35% linen woven fabric (basis weight 100
J'/m2) was reeded, burnt, desized, scoured, bleached, heat set and dyed in the usual manner, and fixed under the following conditions.

Liquid formulation flame retardant A 50 Weight related crosslinking agent Sumitex Re5ln M6 15
//Catalyst diImonium phosphate 1.5〃
Surfactant emul? 909 0.1 #
Wednesday 33.4 //
This was applied with Pickup 75 and fixed using Apollotex under the following conditions.

Microwave output 7. O, kW reaction time
30 minutes Direct steam pressure 0.5 kg/an" Winding speed 15 m/min After that, soaping and drying were performed.

The flame retardant evaluation results of the processed fabric obtained in Example 2 are shown in Table 2. It can be seen that flame retardant properties with excellent durability were obtained.

Table 2 Example 3 80% polyester/20% cotton interwoven fabric (basis weight 1501
i//rn”) by conventional methods, burning, desizing, scouring,
Bleached, heat set and dyed fabrics were used as test fabrics.

Flame retardants A, B, C, D and E obtained in Production Examples A-E
The following treatment solution was prepared using

Liquid prescription flame retardant 50 Weight related crosslinking agent
Sumitex Re5in M6 15N
Catalyst Niammonium phosphate 1゜5N surfactant Emalgun 909 0.1 1 Water
33.4# total
100.07 Next, the test cloth was impregnated with the treatment liquid, and a reaction was carried out under the following conditions using a pickup 75qb and Apollotex.

Microwave output: 5.0 kW Reaction time: 30 minutes Steam pressure: 0.2 kg/cm2 Winding speed: 15 m 7 minutes Then, using a jet dyeing machine, dye the unfixed flame retardant for 30 minutes at 1.8°C and 0°C. After washing, drying and setting.

Clothing 3 shows the flame retardant evaluation results using the 45° mecenamine method.

The flame retardants A, B, C, and D of the present invention had flame retardant properties that withstand washing, but the comparative flame retardant E had insufficient durability.

Table 3 Example 4 A test cloth was used which was made of polyester 4mm (fabric weight: 100 17 m'') by conventional methods such as shingling, burning, desizing, scouring, bleaching, heat setting and dyeing.

In the following treatment solution, trimethylolmelamine Sumitex Re5i is used as a triazine compound.
n M3 Hexamethylol Melamine Sumitex
R@sin M6 trimethylol and hexamethylene Sum
Itex Re5in MC roll using three types of further condensation of melamine.

Liquid formulation flame retardant B 40 wt% triazino compound 10 Catalyst Niammonium phosphate 1.0 Surfactant Emulgun 909 0.1/1 water
48.9 N total
Impregnated with 100.0 7F treatment liquid,
The reaction was carried out under the following conditions using Apollotex and a 60% pick-up.

Microwave output: 10 kW Reaction time: 20 minutes Steam pressure: O82 kg/cm2 Winding speed: 20 m 7 minutes Then, unfixed flame retardant was removed by washing with water, dried, and set. Table 4 shows the results of evaluating the flame retardant properties of the processed fabrics. A flame-retardant fabric with excellent durability was obtained regardless of the type of triazine compound.

The following margin Example 5 50% polyester/50% cotton mixed woven fabric (Weight 2001
1/m") was subjected to hair burning, desizing, scouring, bleaching, heat setting, and dyeing according to conventional methods. Next,
The following treatment liquid was applied with a pickup of 70%.

Liquid prescription flame retardant C40 weight crosslinking agent Sumitex Re5in M6 10
1 Catalyst Ni/Monium Phosphate IN Surfactant Emulgun 909 0.1 tt Water
48.9 1 total
100.0 1 Next, it was fixed using Apollotex under the following conditions, and then soaped and dried -zft.

Microwave output: 6 kW Reaction time: 20 minutes Steam pressure: 1.0 kg/cW1" Winding speed: 17 m/min Comparative Example 7 Using the same dyed fabric as in Example 5, liquid formulation crosslinking agent Sumitex Reaith M6 1
0 weight catalyst Niammonium phosphate
IN surfactant Emalgun 909 0.1
tt water 88.9
tt meter 100.0
7 at a pick-up rate of 70%, and then processed using Apollotex at a microwave output of 6 kW, reaction time: 20 minutes, steam pressure: 0.7 Yu/cm2, winding speed: 15 m, 7 minutes, and then soaped and dried. . Next, a flame retardant 040 weight aqueous solution was applied at a pickup rate of 70%,
It was dried at 120° C. for 2 minutes, and after drying at 150° C. for 3 minutes, it was soaped and dried.

Comparative Example 8 Using the same dyed cloth as in Example 5, liquid formulation crosslinking agent Sumiter Re5in M6 10
Weight dependent catalyst Ammonium phosphorus
ll Surfactant Emuldan 909 0LI
#Wednesday 88.9
A total of 100.0 1 was applied with a pickup of 70%, and then treated with Apollotex at a microwave output of 6 kW, a reaction time of 20 minutes, a steam pressure of 0.7 cm, a winding speed of 15 m, and 1 minute, followed by soaping. , dried. Then.

Add a 40% flame retardant aqueous solution with a pick-up of 70%,
Steam treatment was carried out in saturated steam at 100° C. for 10 minutes. Next, it was soaked and dried.

Comparative Example 9 Using the same dyed fabric as in Example 5, liquid formulation crosslinking agent Sumitex Re5in M6 10
Heavy i% catalyst Niammonium phosphate 1
〃Surfactant Emalgun 909 0.
1 71 total 100.0
/1 with a pick-up of 70%, and then processed using a microwave output of 6 kW, reaction time: 20 minutes, steam pressure: 0.7, and 9/an2 winding speed: 15 m/7 minutes, followed by soaping. And dry friends. Next, after applying an aqueous solution by weight of flame retardant C40 at a pickup rate of 70%, it was processed using Apollotex at a microwave output of 6 kW, a reaction time of 20 minutes, a steam pressure of 0.7 kg, and a winding speed of 15 m/min. Afterwards, soaped and dried.

Regarding Example 5 and Comparative Examples 7 to 9, the amount of flame retardant adhering and the flame retardant performance by the vertical method were evaluated, and the results are shown in Table 5. In all samples other than Example 5, the flame retardant adhesion rate was low and the flame retardant properties after initial washing were insufficient.

Example 6 Mixed woven fabric of 50% polyester/50% cotton (basis weight 150%)
17m”) was subjected to six treatments of hair burning, desizing, scouring, bleaching, heat setting, and dyeing according to conventional methods.
The following treatment bath was applied at Pickara f75%.

Liquid prescription flame retardant A 30 Weight related crosslinking agent Sumitex Re5in M6 10
/1 Catalyst Niammonium phosphate 1
〃Surfactant Emalgun 909 0.1
〃Water 58゜9
〃Total 100.0 〃
Next, reaction fixation was carried out using Apollotex under the following conditions.

Microwave output 4.0 kW Reaction time 15
Steam pressure: 0.3 kll/cm2 Winding speed: 15 m7 minutes Next, soaping and drying were carried out.

Comparative Example 10 The same dyed fabric as in Example 6 was picked up with the following treatment solution 75
It was given in %.

Liquid prescription flame retardant A 30 Weight related crosslinking agent Sumitex R*aj+x M6 10
1 Catalyst Niammonium phosphate 1
〃Surfactant Emalgun 909 0.1
#Water 58.9N
Total 100. Then, steaming was carried out for 30 minutes in an atmosphere of 100° C. and 98% RH, followed by soaping and drying.

Comparative Example 11 The same dyed fabric as in Example 6 was picked up in the following treatment bath 75
It was given in %.

Liquid prescription flame retardant A 30 Weight related crosslinking agent 5uenit@x Re5in M6 10
N-catalyst ammonium phosphate 1 #
Surfactant Emalgun 909 0.1 #
Water 58.9 N Next, after drying at 120°C for 2 minutes, curing was performed at 160°C for 5 minutes, followed by soaping and drying.

Regarding Example 6 and Comparative Examples 10 and 11, the flame retardant adhesion rate and flame retardant performance were evaluated and the results are shown in Bag 6.

Compared to Example 6, Comparative Examples 10 and 11 had lower flame retardant adhesion rates and unsatisfactory flame retardant properties.

Margin Example 7 A 100-inch cotton fabric (with a basis weight of 140.F/m) was subjected to conventional methods such as shingling, burning, desizing, scouring, bleaching, and heat setting, and was treated under the following conditions.

Liquid formulation flame retardant A 30% by weight Crosslinking agent Sumitex Re5in M6 10
N catalyst Niammonium phosphate 11 Surfactant Emalgun 909 0.1 #Total
100.0# This was applied with a pickup of 75 cm, and fixed crosslinking was carried out using Apollotex under the following conditions: microwave output: 5.0 kW, reaction time: 20 minutes, steam pressure: 0.4 kg/art, and winding speed: 15 m/min. Then, soaping, drying and setting were performed.

Comparative Example 12 The same scouring and setting fabric as in Example 7 was treated with the following treatment solution at a pick-up of 75%.

Liquid prescription flame retardant Phyroll 76 40% by weight crosslinking agent
N-methylacrylamide 25 Catalyst Potassium persulfate 0.5 Water
49.5 #total
100. Then, after drying at 120°C for 2 minutes and curing at 160°C for 3 minutes,
Soaped and dried.

Comparative Example 13 The same scouring set fabric as in Example 7 was treated with the following treatment solution using a pick-up of 75 inches.

Liquid prescription flame retardant Pyrovatex CP 40% by weight
Crosslinking agent Sumitex Re5in M6 8
N surfactant Emalgun 909 0.
1 #Catalyst Magnesium chloride 1. O〃
Phosphoric acid (85%) 0.2#
It is then dried at 140°C for 2 minutes. It was then treated at 170° C. for 4 minutes, then soaped and dried.

Table 7 shows the results of evaluating the flame retardancy of the processed fabrics obtained in Example 7 and Comparative Examples 12 and 13.

Compared to Example 10, the flame retardant durability of Comparative Example is insufficient.

Margin Table 7 below Example 8 Rayon 1ooj fabric (fabric weight t3oy/m'') was subjected to conventional methods such as shearing, desizing, scouring, bleaching and heat setting, and flame retardant treatment was performed under the following conditions.

Liquid prescription flame retardant A 30% by weight Crosslinking agent Sumltex Re@in 1iC310# Catalyst Niammonium phosphate 11 Dark activator Emulgun 909 0.1 1 total
Apply 100.0 1 with pickup 75ch, use Apollotex, and microwave output 5. Fixing and crosslinking were carried out at a reaction time of 20 minutes, a steam pressure of 0.4 mm, and a winding speed of 15 m/min, followed by soaping, drying, and setting.

Table 8 shows the results of evaluating the flame retardancy of the processed fabric obtained in Example 8. It can be seen that excellent durable flame retardancy can be obtained.

Table 8 Example 9 Mixed woven fabric of 60% polyamide/40% cotton (basis weight 200g
/m") was subjected to sintering, desizing, scouring, bleaching, heat setting, and dyeing treatments according to conventional methods. Then, the following treatment bath was applied at a pickup rate of 70%.

Liquid formulation flame retardant B 40% by weight Crosslinking agent Summit@x Re5in M3 12
tt catalyst ammonium phosphate l
〃Surfactant Emalgun 909 0.1
#Total 100.0#
Next, reaction fixation was performed using Azolotex under the following conditions.

Microwave output: 3.5 kW Reaction time: 20 minutes Steam pressure: 0.4 k11/a++" Winding speed: 15 m/min Next, soaping and drying were performed.

Table 9 shows the results of evaluating the flame retardancy of the processed fabric obtained in Example 9.

Table 9 Example 10 Mixed woven fabric of 50% acrylic/50cm cotton (Weight: 2201I
/m was subjected to hair burning, desizing, scouring, bleaching, heat setting and dyeing treatments according to conventional methods. Next, the following treatment bath was applied using a 70-inch pickup.

Liquid formulation flame retardant 0 35 parts by weight Crosslinking agent Sumit@x Re5in MC10 #Catalyst Niammonium phosphate 11 Surfactant Emulgun 909 0.1 #Total
100.0#Next, reaction fixation was carried out using Azolotex under the following conditions.

Microwave output: 4.0 kW Reaction time: 20 minutes Steam pressure: 0.8 kg/lym Winding speed: 15 m/min Next, soaping and drying were performed.

Table 10 shows the results of evaluating the flame retardance of the 7'cjlO fabric obtained in Example 10.

Table 10 Example 11 Polyester 65fi/135fi mixed woven fabric (basis weight 10
0j'/m") according to conventional methods, by burning, desizing, scouring,
Bleached, heat set and dyed and fixed under the following conditions.

Liquid formulation flame retardant Production example A 50 parts by weight Crosslinking agent Sum1t@x Re5in M6 15
N Catalyst Ammonium Phosphate 11 Surfactant Emulgun 909 0.1z Water
33.9 N total
100.0 1 Then, using a high-pressure steamer machine, a reaction layer was carried out at a steam pressure of 1.7 to 9/- for 60 minutes, followed by soaping and drying. Table 11 shows the results of evaluating the flame retardant performance of the processed fabric obtained in Example 11.

Table 11

Claims (1)

[Claims] 1. Tetrakis hydroxymethylphosphonium salt 1 represented by the general formula (HOCH_2)_4PX (in the above formula, X represents Cl, (1/2) SO_4 or OH) for the fiber material. There are general formulas, ▲mathematical formulas, chemical formulas, tables, etc. for the reaction products of 0.2 to 3.0 moles of urea. (In the above formula, R is an alkyl group having 1 to 3 carbon atoms or a halogen-substituted alkyl group. It is characterized by forming a crosslinked film consisting of a processing agent obtained by adding 0.1 to 3.0 mol of N-hydroxymethyldialkylphosphonopropionamide represented by the following formula and a triazine ring-containing compound. , a method of processing textile materials.