WO2008098518A1

WO2008098518A1 - The flame retardant treatment method for light natural fiber material

Info

Publication number: WO2008098518A1
Application number: PCT/CN2008/070297
Authority: WO
Inventors: Weiguo Ou; Zhiguo Wei; Jianhua Xu
Original assignee: Weiguo Ou; Zhiguo Wei; Jianhua Xu
Priority date: 2007-02-15
Filing date: 2008-02-13
Publication date: 2008-08-21
Also published as: CN100545343C; CN101016694A

Abstract

A flame retardant treatment method for light natural fiber material has the following process steps: the ultramicro fiber material fabric - bleaching or dyeing - inflaming retarding by low temperature soaking and expanding - baking for cross linking - oxidation, neutralization, water washing - product inspection, wherein, the condition of low temperature soaking is 15-30°C; 10-30 seconds, and expanding is carried out at 35-60°C; for 20-40 minutes. Baking for cross linking is carried out at 145-185°C; for 2-8 minutes. Then the ultramicro flame retardant fiber material is treated with purificant, which is nanoscale titanium dioxide (TiO2) or/and zinc oxide (ZnO) and its ratio of weight is 1-12.0wt%, dispersant 0.2-1.5wt%; and the nano-composite dispersant is added in the water solution for the treatment.

Description

Flame retardant treatment method for light and thin natural fiber materials

The invention relates to a post-treatment method for light and thin natural fiber materials, in particular to a flame retardant and clean treatment method. Background technique

The ecological properties of fiber materials have been the focus of the world, and Europe, the United States and China have developed strict ecological standards. The fiber material with the ecological performance meets the requirements can ensure the health of the user and promote the harmonious development of the society.

In industrial production, transportation and residential life, the use of fiber materials has increased year by year. Fire damage and casualties caused by the flammability of fiber materials, especially ultra-thin, ultra-light, ultra-fine, ultra-soft fiber materials, and ultra-microfiber materials have been alarming and have been valued by governments. The United States has nearly 10,000 fire casualties and economic losses of more than 700 million U.S. dollars per year. Between 1989 and 1999, there were a total of 679,000 fires, 22,469 deaths, and direct economic losses of more than 10 billion yuan. 50% of these fires are caused by fiber materials. Railways, transportation, oceangoing vessels, aerospace vehicles, tourist hotels, special hospitals, senior apartments, prisons, schools, kindergartens, and even every home, often due to ultra-microfiber materials (bedding, pajamas, children's wear, decorative fabrics, etc.) Being ignited, indoors and cabin personnel are difficult to escape, resulting in a vicious and serious accident. Inventing and using ecologically flame-retardant natural fiber materials can prevent major fires, reduce fire accidents and their losses, protect people's lives and property, promote social stability, enhance national defense construction, and accelerate economic construction. The meaning.

In the 1970s, the domestic use of THPC-AP0, phosphorous resin, ammonium dihydrogen phosphate and other flame retardants to finish cotton fabrics was not satisfactory. In the early 1980s, due to the demand in the domestic market, Beijing and Liaoning successively introduced two Proban flame-retardant cotton fabric production lines from Albrightant-wilso, UK, and then started the synthesis of flame retardants in Beijing, Shanghai, Tianjin, Shaanxi and other places. With the application boom. Pykovetex CP (Switzerland) was already produced in the country in the 1990s. Fxorl 76 (United States), Proban (UK) and other flame retardants, the finishing process is also maturing, but it was not until 1998 that the national release of the "flame retardant protective clothing" standard, began small batch production and application.

At present, there are more than 10 enterprises producing flame-retardant cotton fabrics on the CP route in China. There are 5-6 enterprises producing flame-retardant cotton fabrics on the Proban route, but most of them are medium-thick fabrics (160g/m2 or more). Moreover, it has a rough feel and an odor, and is mainly used in China. The invention of lightweight natural fiber flame retardant material (90_150g/m2) has not been systematically reported. Light and thin The soft and delicate features make flame retardant processing very difficult.

The production of flame-retardant cotton fabrics in foreign countries is mainly based on the technology of Pykovetex CP New and Proban, and most of them are medium-thick fabrics. The inventions of light-weight natural fiber flame retardant materials are rarely reported, and the specific performance is unknown. The flame retardant processing technology of flame retardant viscose fiber is relatively mature abroad. In recent years, countries such as Europe, the United States, and Japan are keen on the invention and development of special high temperature resistant flame retardant fibers and materials. The invention and production of flame retardant natural fiber materials have a tendency to shift to foreign countries. In short, the flame retardant lightweight natural fiber materials are less invented at home and abroad and are more difficult.

Although there are some patent methods disclosed, including the method of the inventor of the present application, such as CN200510112307. 1 a heat-resistant flame-retardant fabric and a preparation method thereof, the heat-resistant flame-retardant fabric is blended from two flame-retardant fibers, The flame retardant fiber is aramid 1313 fiber, and the other flame retardant fiber is flame retardant viscose fiber. The flame retardant content of various fibers in the flame retardant fabric is: aramid fiber: 20%~80%, flame retardant adhesive Fiber: 20%~80%.

CN01813559. 5 Fireproof yarn and fabric made thereof, comprising: a) 5-90wt.% melamine fiber, b) 5-90wt.% natural fiber, c) 0. l-30wt.% by polyamide 66, polyamide 6 or a polyamide fiber made from a mixture thereof.

CN03811280. 9 High fireproof blend fabric prepared by co-braiding: 30%~70% by weight of strand (A), and 70%~30% by weight of cellulose fiber yarn (B), the strand (A) The halogen-containing fireproof fiber (a-1) is obtained by combining the halogen-containing fireproof fiber (a-1) and the other fiber (a_2), and contains 25 to 50 parts of hydrazine in 100 parts by weight of the acrylic-based copolymer. The compound, the acrylic-based copolymer is obtained by polymerizing a monomer mixture comprising 30% to 70% by weight of acrylonitrile, 30% to 70% by weight of a halogen-containing vinyl monomer, 0%~ 10% by weight of the vinyl monomer copolymerizable with them, the strand (A) has an elongation of less than 5% at a load of 300 mg/metric metric No. 17, at a temperature ranging from 100 T to 500 °C. rate.

CN200610085269. X Preparation of steam-permeable flame retardant, oil-proof, water-proof, acid-proof and near-infrared polyester tarpaulin, durable flame retardant finishing on polyester canvas, durable flame retardant finishing including padding, baking, baking temperature and time, 170 °C-200°C, 1-10 minutes, and including scratching and drying process on the fabric for flame retardant PU coating adhesive coating for waterproof and acid proof treatment, directly applied to fabric, dried and high temperature 170 -130 ° C baking 1-lOmin; Durable flame retardant finishing of the base fabric, dyeing: The front side is coated with flame-retardant PU coating glue or at the same time adding color paste for oil-proof, waterproof and acid-proof finishing.

200410065744. 8 The method for finishing the vapor-permeable acid-proof and oil-proof waterproof fabric, using the method of pre-coating and finishing to improve the acid-proof permeability of the fabric; the polymer materials used for the fabric coating mainly include polyacrylic water-based or solvent-based Resin or polyurethane water-based or solvent-based resin; acid-proof finishing using fluoropolymer materials.

CN200310112733. 6 Method for manufacturing antistatic flame retardant waterproof and oilproof natural fiber fabric, antistatic fabric, weaving, flame retardant, baking, soaping, deodorizing, waterproofing, oil proofing, tentering, finished product inspection; Electrostatic grey cloth test The antistatic method of weaving natural fiber fabrics is an organic conductive fiber or a metal conductive fiber.

Although the China Textile News reported on September 25, 2006, Xi'an Engineering University and other units successfully developed the "new high-strength, soft, flame-retardant and anti-static fabric", and said that the results filled the domestic gap. The result is a combination of three types of textile fibers, such as high-performance fibers, flame-retardant fibers and conductive fibers, to form new fabrics by blending and interlacing, focusing on the selection of fiber types, the determination of mixing ratios, and the blending and processing of blends. Key technical issues such as dyeing. It can be seen from the above reports that although the results are also soft and flame retardant (no ecological clean processing), the raw materials, technical routes, key technologies and product properties used are different from the present invention. The flame retardant processing of natural fiber materials and mixed materials of natural fibers and other fibers (including textiles) is often carried out by rolling and padding, and these methods are effective for flame retardant processing of medium-thick fabrics, but For ultra-thin, ultra-light, ultra-fine and ultra-soft fiber materials, good results are not obtained. Summary of the invention

The object of the present invention is to: propose a flame-retardant treatment method for a light and thin natural fiber material, and further propose a method for cleaning a fabric; thereby obtaining an ultra-thin, ultra-light, ultra-fine, ultra-soft natural fiber material to obtain a good flame retardant effect; Ultra-thin, ultra-light, ultra-fine and ultra-soft fiber materials have self-cleaning properties (sterilization and sterilization).

The technical solution of the invention is: a flame-retardant treatment method for light and thin natural fiber materials, which is treated by the following processes: Ultra-microfiber material fabric (light-weight cotton fabric) - bleaching treatment or dyeing - low temperature infiltration (flame retardant) One-to-one baking cross-linking one-to-one oxidation, neutralization, water washing one by one product inspection; wherein the low temperature infiltration conditions are: 15-30 °C, 10-30 seconds; puffing temperature 35-60 °C and 20-40 minutes Baking crosslinking temperature: 145-185 V, time: 2 to 8 minutes.

The fabric is low-temperature infiltrated and expanded, high-temperature baking and cross-linking; the flame retardant is Pyrovatex CP New or flame retardant JSJ-111: the cross-linked resin is mostly modified thiol melamine derivative with reactive groups, cross-linked resin Especially for JS J-302. 5-20%, the use concentration of flame retardant is 25% - 38%; ultra-fine fiber material low temperature (15-30 °0 with flame retardant, cross-linking resin, penetrant and other materials infiltration, time 20-30 Seconds; and parked at 20-80 ° C for 20-40 minutes; baking process using baking cross-linking temperature: 135-185 V, time: 2-8 minutes. Infiltration temperature 20-30 ° C, time 20-30 seconds And puff at 40-60 ° C and 20-40 minutes.

The kt%, dispersing agent 0. 2 - 1 . The weight ratio of the titanium dioxide (Ti02) or / ZnO to zinc oxide ZnO, the weight ratio is 1-12. (kt%, dispersing agent 0. 2 - 1 5wt%; and adding nanocomposite dispersant to treat in aqueous solution. Dispersing agent and adding water, mixing and mixing at high speed for 20-60 minutes under stirring; or adding

0. 1-0. 5^% NaOH was stirred for 10-30 minutes. Ecological cleanliness of nano-composite dispersions for ultra-fine flame-retardant fiber materials The processing adopts the conventional dipping-drying or baking process; the baking process adopts the baking crosslinking temperature: 135-185 V, time: 2-8 minutes, or is impregnated with the crosslinked resin and then baked, cross-linking resin The dosage is 2-10%. The amount of the nano-composite cleaner is 3-7 wt%, and the ratio of the titania to the zinc oxide ZnO is 20-80 wt. /^ 80-20wt%.

Flame retardant formula: flame retardant JSJ-11125— 38, crosslinked resin JSJ-302 5—10, auxiliary crosslinked resin JSJ-303 0.5—2.0, formaldehyde elimination agent JSJ-504 0.3—1.5; softener JSJ-1512 3; Catalyst JSJ-523 1-2; penetrant JSJ-312 1-2; cold water balance, the above is the percentage by weight, total 100%.

Cleaner nanocomposite dispersion formulation: nanomaterial titanium dioxide 0.2-2.0, adsorption material zinc oxide 0.9-12.0, dispersant surface activity, cosolvent JSJ-701 0.8-7.0; 30% NaOH aqueous solution 1.0-10.0; Softener JSJ-312 E; penetrant JSJ-151 F; E, F are 1-10; water is the balance, the above is the percentage by weight, total 100%.

The invention is characterized in that: this is a clean and flame-retardant treatment method for light and thin natural fiber materials; thereby obtaining a good flame retardant effect on ultra-thin, ultra-light, ultra-fine and ultra-soft natural fiber materials. At the same time, the ultra-thin, ultra-light, ultra-fine and ultra-soft fiber materials have self-cleaning properties (sterilization and sterilization). The invention adopts the low-temperature infiltration expansion and high-temperature baking cross-linking technology and the harmonious arrangement technology of flame retardancy, durability and hand feeling softness, and the processing of the fiber materials with the weight of 90-150 g/m2 has achieved the expected result. Using nano-composite ecological clean new technology, the nano-materials with photocatalytic properties, materials with adsorption and chemical reaction properties for odor and formaldehyde are made into a stable composite dispersion by special methods, and then the dispersion is used. Specific processing, durable attachment to the surface of the fiber material. This processing not only maintains the original properties of the fiber, but also gives the fiber material a safe and reliable ecological indicator. DRAWINGS

Figure 1 shows the effect of flame retardant concentration on fabric weight gain

Figure 2. Relationship between fabric weight gain and damage length

Figure 1 and Figure 2: 1-cotton plain cloth 128.4g/m ² (133X 100), 2-cotton twill 119. lg/m ² (128X68) Figure 3. Cross-linking resin for fabric washability and increase Heavy influence

1- The amount of cross-linked resin elution rate of the fabric (40 ^{^S} X40 ^S 128X68 washed 5 times)

2-crosslinking resin dosage and fabric weight gain (40 ^S X40 ^S 128X68)

ι, the effect of the amount of flame retardant on the flame retardancy and softness of fiber materials Due to the thinness, bulkiness, softness and large specific surface area of the ultrafine fiber material, the fiber material per unit mass contains a large amount of air, and the oxygen supply during combustion is sufficient, so that the ultrafine fiber material is relatively easy to ignite. In the flame retardant processing, the eco-efficient flame retardant is selected and the amount of the flame retardant is appropriately increased.

At present, the durable flame retardants which can be used for natural and mixed materials at home and abroad mainly include condensates of N-hydroxymethyl-3-dimethylphospholpropamide (Pyrovatex CP) and tetramethylolphosphonium chloride-urea. (Proban type), because Proban flame retardant is ammonia-cured when processing natural fiber materials, the degree of crosslinking is difficult to control, and the finishing products are harder, and the ultra-fine fiber materials cannot be used in flame-retardant processing. Pyrovatex CP flame retardants have a large number of domestic and foreign manufacturers and brands, and there is a certain gap in quality. Table 1 shows the performance comparison of six flame retardants.

Table 1 Comparison of properties of flame retardants at home and abroad

Note: The fabric is 119. Ig/m2 cotton twill.

From Table 1, it can be seen that the imported flame retardant Pyrovatex CP New and the domestic flame retardant JSJ-111 have higher flame retardant efficiency, softer and smoother fabric feel, and the two flame retardants are used in the study.

Figure 1. Effect of flame retardant concentration on fabric weight gain, Figure 2. Relationship between fabric weight gain and damage length

The amount of flame retardant used directly affects the flame retardancy, feel and production cost of the fiber material. Using natural materials such as flame retardant JSJ-111, infiltrated with a high temperature baking cross-linking process, processing two natural fiber materials according to orthogonal test The results of the test, Figure 1 gives the effect of the concentration of the flame retardant on the weight gain of the fabric; Figure 2 shows the relationship between the weight gain of the fabric and the length of the damage; Table 2 shows the effect of the flame retardant on the fabric properties. It can be seen from Figure 1 that as the concentration of the flame retardant is used, the fabric gains weight.

Table 2 Effect of Flame Retardant on Fabric Properties

Note: The cross-linking resin is JSJ 302, and the dosage is the same.

Rapid increase, but when the concentration reaches more than 35%, the weight gain rate of the fabric is slowed down; from Figure 2, it can be seen that as the weight gain of the fabric increases, the length of the damage decreases (the flame retardancy increases), but the weight gain reaches a certain value. After that, the speed at which the length of the damage is reduced is slowed down, and the weight gain due to the difference in fabric structure and the flame retardant requirement is also different (12.5%, 14.5%); the flame retardant can also be seen from the data in Table 2. The concentration of the agent also has a certain influence on the strength and color change of the fabric. Based on the above analysis, the concentration of the flame retardant used is 25% - 38% is an optimum value.

2, cross-linked resin and flame retardant durability

When the ultrafine fiber material is flame-retardant processed, the commonly used cross-linking resin is mostly a modified thiol melamine derivative with a reactive group, but its performance is also different due to the difference in chemical structure, molecular weight and reactive group content. Large differences, Table 3 lists the performance comparison of the five crosslinked resins. Table 3 Comparison of properties of five crosslinked resins

Note: The fabric is 119. lg/m ² of cotton twill; the flame retardant is domestic JSJ-111.

It can be seen from Table 3 that the cross-linking number of CHN and JSJ-302 cross-linked resin is high, and the finished fabric feels soft and smooth. The two cross-linking resins were used in this study.

Under certain conditions, the cross-linked resin can not only form a strong chemical bond with the active groups of the flame retardant and the fiber material, but also adhere to the surface of the fine structure of the fiber material by permeation, relying on the intermolecular secondary bond force. Strongly combined. When the ultra-microfiber material is flame-retarded, the amount of cross-linking resin directly affects the washing fastness, weight gain, and feel of the finished fabric. Figure 3 shows the effect of the amount of cross-linking resin on the washability and weight gain of the fabric. Table 4 lists the relationship between the cross-linking resin and the fabric feel, strength, color change and other indicators.

It can be seen from Fig. 3 that: with the constant amount of flame retardant, as the amount of cross-linking agent increases, the weight gain of the fabric increases and the elution rate decreases significantly; as can be seen from Table 4, along with cross-linking Increase in the amount of the agent, the texture of the fabric becomes hard, and the color turns yellow.

Table 4 Properties of crosslinked resin and fabric

- 1 - Note: The fabric is cotton twill (119. lg/m ² ); the flame retardant is JSJ-111, the same amount of use; the cross-linked resin is JSJ-302. Coordination of indicators, the use concentration of cross-linked resin is 5.0% - 10% is most suitable.

3, low temperature infiltration, high temperature baking cross-linking

The ultra-microfiber material is infiltrated with a flame retardant, a cross-linking resin, a penetrating agent, etc. at a low temperature (15-30 ° C), and is parked at a lower temperature (20-80 ° C) for a certain period of time, at which time the fiber material is puffed. The loose and low-molecular additives are easily penetrated into the fine structure of the fiber material, and when dried and cross-linked, the surface resin is not formed, thereby greatly improving the hand feeling and strength of the flame-retardant fiber material. Table 5 shows the effect of the expansion temperature and time on the properties of the fabric.

Table 5 Effect of expansion temperature and time on fabric properties

Note: 1 Flame retardant formula is the production formula;

2 Infiltration temperature 20 ° C, time 20-30 seconds;

3 The fiber material is: cotton twill (40 ^s X40 ^s 119. lg/m ² ).

It can be seen from Table 5: (1) When the puffing temperature is 20 ° C and the puffing time is 20-40 minutes, although the fabric feels soft and smooth, the fabric weight gain is low (12.2%, 13%), and the elution rate is high ( 48.8%, 48.1%), the damage length is also higher (126 let, 123mm); (2) When the puffing temperature is 80 °C, the puffing time is 20-40 minutes, although the flame retardancy of the fabric is very good (the damage length is 90.5 respectively) Let and 90 let), the elution rate is low (28.2%, 28.0%), but the fabric weight gain is too high (15.6%, 16.0%), and the fabric feels not soft and smooth. (3) When the puffing temperature is 50 °C and the puffing time is 20-40 minutes, not only the flame retardancy meets the requirements of the project index (the damage length is 110 and 112 respectively), and the elution rate is low (25.9%, 28.0%). The fabric has a moderate weight gain (14.5%, 13.9%) and a high fabric strength. Therefore, 50 °C and 20-40 minutes are the most ideal expansion temperature and expansion time.

High temperature baking cross-linking is a key process in the flame retardant processing of fiber materials, which largely determines the hand of the finished product. Sense, washability, loss of strength and color change. High temperature baking cross-linking is a very complicated physical and chemical process; it has cross-linking between flame retardant and fiber material, cross-linking between fiber material, flame retardant and cross-linking resin, as well as flame retardant and cross-linking. The co-resin penetrates and adheres to the inside of the fiber material, and forms a very strong physical adsorption by the intermolecular bond force. The key parameters of high temperature baking cross-linking are baking temperature and baking time: high temperature and long time. Although the chemical reaction is thorough, the degree of crosslinking is high, and the fabric has good washing durability, it will make the hand feel hard and the strength loss is large. At the same time, the side reaction is increased, and the formed compound reacts with free formaldehyde to form a fatty amine substance with fishy smell; if the baking temperature is too low and the time is too short, the crosslinking is insufficient, thereby affecting the washing resistance of the fiber material. Fastness and flame retardancy, a large number of tests have proved: the baking temperature is 145-185 °C, and the baking time is -8 minutes, which is a reasonable high-temperature baking crosslinking condition.

4. Research on ecological clean technology of nanocomposites

4-1. Ecological clean theory analysis of ultra-fine flame retardant fiber materials

Ultrafine fiber materials produce trace amounts of free formaldehyde and fatty amines with fishy odor during flame retardant processing, and fatty amines with fishy odors, during storage and transportation of products, such as encountering suitable temperatures and Humidity will also be produced in small amounts. Among the ecological indicators of fiber materials, heavy metal content, limited flame retardant and ra value are easier to solve, while odor and free formaldehyde have become key indicators, and these two indicators are largely interrelated. There are three main technical approaches currently available to remove odors and formaldehyde:

(1). Photocatalytic clean technology of nanomaterials

Ultra-fine flame-retardant fiber materials can generate free electrons and holes under the irradiation of sunlight or light after introducing nano-scale zinc oxide (ZnO) or titanium dioxide (Ti0 ₂ ), and oxygen and water molecules in the air. The reaction produces a highly oxidizing ability of hydroxyl radicals and active oxygen, and thus has a strong photo-oxidation-reduction function. Harmful organic matter (formaldehyde, fatty amines, etc.), odors, bacteria, etc., which are adsorbed by active oxygen, are immediately reduced to harmless carbon dioxide, water and oxygen. However, the shortcoming of this technology is: The flame retardant fiber material is not visible or the light is weak during packaging or transportation, which will affect the photocatalytic effect of the nano material.

(2). Adsorption-desorption technology

The odor or formaldehyde on the ultrafine flame retardant material is adsorbed by a material having micropores, voids or a large specific surface area, and stored in its internal structure. The problem with this method is that the adsorption has a saturation process, and at the same time, during the water washing, desorption occurs and some of the gas is released again.

(3) Chemical deodorization technology

A substance that can react chemically with fatty amines and formaldehyde is applied to the ultra-fine flame-retardant fiber material, which can easily remove odor and formaldehyde, but the adhesion and use of the material to the fiber material is incomprehensible. The problem. In this study, three kinds of materials with photocatalytic function, adsorption function and chemical reaction function were used to clean the ultrafine fiber flame retardant materials, and good results were obtained.

4. 2 effects of five kinds of cleansing agents on fiber materials

The ultra-viral flame retardant fiber materials were treated with three ecological cleanliness theories and five cleansers were selected. The results are shown in Table 6.

Table 6. Performance of Cleaner and Fiber Materials

Note: 1 The fiber material is: flame retardant cotton flat cloth ( 40 ^s X 40 ^s 128. 4g/m ² );

2 damp heat conditions: temperature 45 ° C, humidity 80%, time 24 - 48 hours;

3 The amount of detergent used is the same.

It can be seen from Table 6: The three nanomaterials (JSJ-602, JSJ-603, JSJ-606) have good deodorizing effect, soft fabric feel, but the surface has a slight dusty feeling, and the color is yellowish, which will affect The use of the product; the adsorption type cleaning agent (JSJ-605) has a good deodorizing effect and no change in the color of the fabric, but the hand feel is slightly hard; the chemical reaction type cleaning agent (JSJ-601) has a small change in taste, feel and color. , but the affinity with fiber is poor. In short, three types of cleansers, each with its own advantages and disadvantages, and their composite application are the best choice.

4-3. Preparation and application of stability dispersion of nanocomposites

Since the ultrafine particles of nanomaterials have a tendency to agglomerate with large surface energy and activity, it is difficult to prepare a stable dispersion of nanomaterials, which has become a bottleneck for its application on fiber materials. This project systematically studied the variety and dosage of dispersant, the variety and dosage of cosolvent, the amount and proportion of nanocomposite cleaner, the process parameters of dispersion preparation, etc., and prepared for long-term stability (not more than three months) Layered, non-precipitating) nanocomposites The dispersion is successfully used for the ecological clean processing of ultra-fine flame retardant fiber materials. Through 73 sets of experiments and analysis of 2284 data, the optimal formulation and preparation process of nanocomposite dispersions were obtained.

Nanocomposite dispersion formulation:

Cleaner JSJ-606 (nanomaterial) 0. 2— 2. 0

Cleaner JSJ-605 (adsorbing material) 0. 9— 12. 0

Cleaner JSJ-601 (Reactive material) 0. 5— 5. 2

Dispersing agent JSJ- 504 0. 2—1. 5

Cosolvent JSJ-701 0. 8—7. 0

Aqueous NaOH solution (30%) 1. 0— 10. 0

Softener JSJ-312 E

Penetrant JSJ-151 F

Water (deionized) G

Total 100 copies

Nanocomposite dispersion configuration process:

Cold water JSJ-701, JSJ-605 (with stirring) JSJ- 504, JSJ-601, JSJ-606 (high speed shear mixing, 40 minutes) JSJ-151, JSJ-312, NaOH (stirring, 30 minutes), add at the same time Or the effect of adding only one or two of SJ-606 and JSJ-605 is not much different.

The nano-composite dispersion uses a conventional impregnation-drying-bake process for the ecological clean processing of ultra-fine flame-retardant fiber materials. The results are shown in Table 7.

Table 7 Properties of Nanocomposite Cleaner and Ultrafine Flame Retardant

Measured value

Performance

Afterburning time s 0 ^ 2

Flame retardant smoldering time s 0 ^ 2

Damage length mm 107. 5 ^ 150

Melt dripping

Burning holes without Free formaldehyde mg/kg 50 ^ 75

Odor no

PH value 6. 0 4. 5-7. 5

Soft and smooth 3cm (total length of bending resistance) Note: 1 Fiber material: Flame-retardant cotton flat cloth (40 ^s X 40 ^s 128. 4g/m ² ).

2 Nano-composite clean liquid does not stratify, not demulsification, and no precipitation during use.

3 After 6 washes (180 minutes), the flame retardancy and ecological indicators remain unchanged.

It can be seen from Table 7 that the ultra-fine flame retardant fiber material processed by the nano-composite cleaning liquid is not affected by the flame retardancy, and the main ecological indexes and other physical properties meet the requirements of the project index. This proves the scientific and reliable nature of the ecological cleansing technology of nanocomposites.

5. Mass industrial production was carried out in the production equipment of Xinchangjiang Printing and Dyeing Co., Ltd. in September 2006. It produced three varieties of ecologically flame-retardant fiber materials, more than 14,000 meters (about 2800kg), and the finished product rate was over 90%. The color of the product was bleached. , rice ash and dark green. In the whole batch industrial production process, due to the fuller preparation of laboratory research and various processes, the trial production is relatively smooth, the process is stable, the equipment is operating normally, and the product performance not only meets the requirements of the project technical indicators, but also meets the national and international standards. It is stipulated that more than 12,000 meters of products are sold to the United Kingdom and Australia, and more than 1,000 meters are purchased by foreign trade customers. The customers of the UK and Australia are satisfied with the quality of the products and have the intention to continue cooperation. 6, batch industrial production process and formula

(1) Process:

Ultra-microfiber material (light-weight cotton fabric) Bleaching or dyeing - low temperature infiltration (flame retardant) - one baking cross-linking - oxidation, neutralization, water washing - nano-ecological clean - finished product inspection

(2) Key process parameters:

Low temperature infiltration, infiltration, 15-30 °C, 10-30 seconds

Puffing: 50 °C 20-40 minutes

Baking crosslinking temperature: 145-185 V

Time: 2-8 minutes

(3) Flame retardant formula:

Flame retardant JSJ-111 —38

Crosslinked resin JSJ-302 Auxiliary crosslinked resin JSJ-303 0.5-2.0

Formaldehyde eliminator JSJ-504 0.3-1.5

Softener JSJ-151 A

Catalyst JSJ-523 B

Penetrant JSJ-312 C

Cold water (deionized) D

Total 100 (%)

(4) Nanocomposite clean liquid formula

Cleaner JSJ-606 (nanomaterial) 0.2- 2.0

Cleaner JSJ-605 (Adsorbed material) 0.9—12.0 Cleaner JSJ-601 (Reactive material) 0.5— 5.2

Dispersing agent JSJ- 504 0.2-1.5

Cosolvent JSJ-701 0.8-7.0

Aqueous NaOH solution (30%) 1.0-10.0

Softener JSJ-312 2 penetrant JSJ-151 2, add water to 100 (%) The main performance indicators of eco-flame retardant fiber materials are listed in Tables 9 and 10.

Table 9 Flame retardant and ecological properties of ecological ultra-fine flame retardant fiber materials

Burning holes without

Burning

Sex

can

Free formaldehyde 55 75 75 mg/kg

Raw odor no no no

PH value 6.0 4.5-7.5 4.5-7.5 Too extractable No cadmium 0.1 Cadmium 0.1 Heavy metal mg/kg Lead, no lead 0.2 Lead 0.2 Standard Flame retardant limited Three kinds of limited flame retardant Flame retardant

Note: The fiber material is: Eco-flame-retardant cotton flat cloth (40 ^S X40 ^S , 133X100).

Table 10 Physical properties of ultra-fine flame retardant fiber materials

Note: The fiber material is: Eco-flame-retardant cotton flat cloth (40 ^S X40 ^S , 133X100). As can be seen from Table 9 and Table 10:

(1) The flame retardancy and washability of ecological ultra-fine flame retardant fiber materials meet the requirements of project indicators, and are superior to GB8965, GB50222 and BSEN533 and other domestic and foreign flame retardant protective clothing and flame retardant bedding standards.

(2) The ecological standard of ecological ultra-fine flame retardant materials not only meets the requirements of project indicators, but also exceeds the technical requirements of domestic and foreign ecological textiles such as GB/T18885 and Oeko-Tex standardlOO.

(3) The indexes of fracture strength, washing dimensional change rate, color fastness and bending stiffness (fabric hand feeling) of ecological ultra-fine flame retardant fiber materials are superior to project indicators and national industry standards.

Through the choice of technical route, research on flame retardancy, durability, softness and harmony, and research on nano-composite ecological clean technology, process test, batch industrial production, comprehensive evaluation of product quality, feedback from test customers, ecological ultra-fine The research on flame retardant fiber materials and manufacturing methods has met the requirements of the original project technical indicators.

Specifications The values reached The values specified in the project Flame retardancy (before and after washing)

Afterburning time, s 0 2

Smoldering time, s 0 2

Damage length, mm 115 (after washing 135) 150

Melt dripping

Burning holes no

Free formaldehyde, mg/kg 55 75

Technical indicators

Odor no

Extractable heavy metals, mg/kg cadmium, no cadmium 0.1

Lead, no lead 0.1

Ra value 6.0 4.5-7.5

Limited flame retardant

Breaking strength, N T-578 ^250

W-450

Wash fastness, grade 3.5 3 - 4

Color fastness to rubbing, dry 3.5 wet 3.0 dry 3 - 4 wet 3 - 4

Bending stiffness, mN. cm 4.0 5.5 11. Preparation and application of stability dispersion of nanocomposites

The use of nano-material dispersion-nano-composite cleaner directly affects the ecological properties of the fiber material, the softness of the hand, and the production cost. Table 11 shows the effect of the nano-composite cleaner on the properties of the fiber material.

Table 11 Effect of nanocomposite detergent dosage on fiber properties

(1) The fiber material is: cotton flat cloth (40sX40s, 128.4g/m ² )

(2) Similar effects can be obtained for different fiber material compositions and structures.

It can be seen from Table 7.2: (1) As the amount of nano-composite cleaner increases, the fabric gains increase and the production cost is higher. (2) As the amount of nanocomposite cleaner increases, the fabric feel deteriorates. (3) After the amount of nano-composite detergent reaches a certain value, the ecological index of the fiber material does not change much. Considering the comprehensive factors of production cost and fiber material performance index, the amount of nano-composite cleaner is 3 - 7%.

Claims

Claim

1. A flame retardant treatment method for light and thin natural fiber materials, which is characterized by the following processes: ultra-micro fiber material, fabric bleaching treatment or dyeing, low temperature infiltration, puffing, flame retardant treatment, baking, cross-linking, oxidation, neutralization, washing

—— Finished product inspection; The low temperature infiltration conditions are: 15-30 °C, 10-30 seconds; puffing temperature 35-60 °C and 20-40 minutes; baking crosslinking temperature: 145-185 V, time: 2 - 8 minutes.

2 . The method of claim 1 , wherein the ultra-fine flame-retardant fiber material is treated with a cleaning agent, and the cleaning agent is nano-sized titanium dioxide or/and zinc oxide Zn0. The weight ratio is from 1 to 12. 0 wt%, the dispersant is 0.2 to 1.5% by weight _; and the nanocomposite dispersant is added to be treated in an aqueous solution.

The method for flame-retardant treatment of a light and thin natural fiber material according to claim 1 or 2, characterized in that the fabric is low-temperature infiltrated and expanded at a high temperature, and cross-linked at a high temperature; the flame retardant is Pyrovatex CP New or a flame retardant JS J-111 : Crosslinking resin is mostly modified thiol melamine derivative with reactive groups, the dosage is 5-20%, the concentration of flame retardant is 25% - 38%; the temperature of ultrafine fiber material is 15-30 ° Under C, infiltrate with flame retardant, cross-linking resin, penetrant and other materials for 20-30 seconds; and park at 20-80 °C for 20-40 minutes; baking process using baking cross-linking temperature: 135-185 V , Time: 2-8 minutes.

A flame-retardant treatment method for a light-weight natural fiber material according to claim 3, wherein the cross-linking resin is, in particular, S-302.

The flame-retardant treatment method of the light and thin natural fiber material according to claim 3, characterized in that the low temperature infiltration temperature is 20-30 ° C for 20-30 seconds; and the expansion is carried out at 40-60 ° C for 20-40 minutes.

0-0. 1-0. The method of the method of the present invention, the method of the present invention, the method of the present invention Stir the 5% NaOH for 10-30 minutes.

The flame retardant treatment method for a light and thin natural fiber material according to claim 2, wherein the nano composite dispersion liquid adopts a conventional impregnation-drying or baking process for ecologically clean processing of the ultra-fine flame-retardant fiber material. The baking process adopts baking crosslinking temperature: 135-185 V, time: 2-8 minutes, or is baked by cross-linking resin, and the amount of cross-linking resin is 2-10%.

The flame retardant treatment method for a light and thin natural fiber material according to claim 2 or 6, wherein the nano composite cleaning agent is used in an amount of 3 to 7 wt%, and the ratio of titanium dioxide to zinc oxide ZnO is 20 to 80 wt. 80_20wt%.

The method for the flame-retardant treatment of the light and thin natural fiber material according to claim 2 or 6, characterized in that the detergent nanocomposite dispersion formulation: the nano material titanium dioxide 0. 2 - 2. 0, the adsorption material zinc oxide 0 9-12. 0, The dispersing agent is surface-active, cosolvent JSJ-701 0. 8-7. 0; 30% aqueous NaOH solution 1. 0-10. 0; softener JSJ-312 E; penetrant JSJ-151 F; E, F All are 1-10; water is the balance, and the above is the percentage by weight to 100%.

The flame-retardant treatment method of the light and thin natural fiber material according to claim 2 or 6, characterized in that the flame retardant formula: flame retardant JSJ-111 25-38, cross-linked resin JSJ-302 5-10, auxiliary intersection Coupling resin JSJ-303 0. 5—2. 0, Formaldehyde elimination agent JSJ-504 0. 3—1. 5; Softener JSJ-151 2-3; Catalyst JSJ-523 1-2; Penetrant JSJ-312 1 -2; cold water balance, the above is the percentage by weight to 100%.