JPWO2007097146A1 - Flame retardant fiber products - Google Patents

Abstract

Suppresses the hygroscopicity of polyphosphoric flame retardant, does not generate formaldehyde residual gas, is easy to handle, has a good texture, and exhibits stable flame retardant effect without worrying about moist heat aging or discoloration Provide flame retardant textile products. A fiber product in which a flame retardant is adhered together with a binder, comprising a composite particle of a flame-retardant polyphosphoric acid compound and a film-forming organopolysiloxane, and the flame retardant The pH of the flame retardant adhering surface of the adhered fiber product is 5 to 7.

Description

  The present invention relates to a flame retardant fiber product having flame retardant properties having good texture (no slime) and good performance without fear of discoloration and embrittlement, and without risk of generation of halogen or formaldehyde.

Conventionally, halogen-based flame retardants containing halogen as a main component have been widely used to make resin compositions and textiles flame-retardant.
However, it is said that a resin composition or a fiber product that has been flame-retarded with a halogen-based flame retardant causes pollution problems during combustion.
For this reason, recently, a polyphosphoric flame retardant containing no halogen has attracted attention.
However, polyphosphoric flame retardants are prone to moisture, and during storage, the particles of polyphosphoric flame retardant aggregate and enlarge, making it difficult to evenly disperse in resin compositions and flame retardant treatment solutions during use. Metal appliances that tend to vary in the flame-retardant treatment effect, and that the treated resin composition or textile product is damp and feels bad, so that the flame-retardant resin composition or textile product can be used in use. It is easy to induce rust and deterioration discoloration of textile products.

  Therefore, in order to suppress the hygroscopicity of the polyphosphoric acid flame retardant, the following method has been developed. (1) A method of adding melamine to a polyphosphate flame retardant in the presence of melamine or melamine urea as a raw material at the time of manufacturing the flame retardant (see, for example, Patent Document 1), (2) Difficulties caused by melamine-added polyphosphate flame retardant A method for imparting water resistance by adding melamine phosphate to a treatment liquid blended with a flame retardant in flame retardant treatment (see, for example, Patent Document 2), (3) Raw material or production during production of a polyphosphate flame retardant A method of blending a melamine / formaldehyde resin into the subsequent dispersion and encapsulating a polyphosphoric acid flame retardant into microcapsules to form stable particles that are difficult to hydrolyze (see, for example, Patent Document 3), (4) Melamine-added polyphosphorus A method in which a silane coupling agent is allowed to coexist in an acid flame retardant, and bleeding of a polyphosphoric flame retardant from a workpiece provided with the flame retardant is suppressed (for example, Patent Document 4) 5,6 see).

However, in these methods, the melamine-added polyphosphoric acid flame retardant generates formaldehyde residual gas and is difficult to handle, and causes environmental pollution problems when used.
JP-A-49-061099 JP-A-51-023312 JP-A 61-103962 Japanese Patent Laid-Open No. 02-263851 Japanese Patent Laid-Open No. 03-020342 Japanese Patent Laid-Open No. 03-056547

  Therefore, a flame retardant obtained by silane-treating ammonium polyphosphate is commercially available, but with this, it is difficult to treat the fiber with a good texture, and the treated product has disadvantages such as slime and moisture heat aging. was there.

  Therefore, the present invention suppresses the hygroscopicity of the polyphosphate flame retardant, does not generate formaldehyde residual gas, is easy to handle, has a good texture, and is stable without worrying about moist heat aging or discoloration. It is an object to provide a flame-retardant fiber product that exhibits a flame-retardant effect.

  The present inventor uses a fiber product in which a flame retardant is adhered together with a binder, which is composed of composite particles of a flame-retardant polyphosphate compound and a film-forming organopolysiloxane. The said subject was solved by adjusting pH value of this flame retardant adhesion surface to 5 to 7.

  Organopolysiloxane, which is capable of forming a film, is hydrophobic and does not absorb moisture, and its resin film is flexible and difficult to crack. In particular, silicone resins consisting of tetrafunctional monomer units and trifunctional monomer units are tough and heat resistant. The polyphosphoric acid flame retardant particles wrapped in the resin film are not sticky and agglomerated during storage, and are uniformly dispersed in the resin composition and flame retardant treatment solution, and stirred. The dispersed state is stably maintained without cracking the resin film during the process.

  In the present invention, as the polyphosphate compound, any of those generally known as a flame retardant can be used. For example, ammonium polyphosphate, polyphosphate amide, polyphosphate carbamate, sodium tripolyphosphate, potassium polyphosphate, ammonium polyphosphate -Potassium, guanidine polyphosphate, etc. are all useful, but ammonium polyphosphate is particularly preferred.

  The polyphosphoric acid compound preferably has a weight average polymerization degree of 20 to 2,000. Those having a weight average degree of polymerization of less than 20 are water-soluble, and those having a weight average degree of polymerization of more than 2000 lack practicality because of a long polymerization time and high cost. Moreover, it is preferable that it is a particle | grain with an average particle diameter of about 3-50 micrometers.

  Next, the organopolysiloxane used in the present invention is applied so as to coat particles of a polyphosphoric compound, and is composed of a monofunctional monomer unit combined with a tetrafunctional monomer unit or a trifunctional monomer unit. Those are particularly preferred.

Organopolysiloxane has, for example, the general formula (RnSiO _{(4-n) / 2} ) _m (where R is an alkyl group such as a methyl group or an ethyl group, a fluorinated alkyl group, a phenyl group or a vinyl group) Group, n = 1-3, m ≧ 2).
Usually, a monofunctional monomer unit represented by the formula (CH ₃ ) ₃ SiO _1/2 and a tetrafunctional monomer unit represented by SiO ₂ and / or a trifunctional monomer unit represented by the formula (CH ₃ ) SiO _3/2. A relatively hard organopolysiloxane consisting of a combination of functional monomer units is also recommended in terms of toughness and heat resistance.
A monofunctional monomer unit organopolysiloxane represented by the formula (CH ₃ ) ₃ SiO _1/2 , a bifunctional monomer unit organopolysiloxane represented by the formula (CH ₃ ) ₂ SiO, or these A silicone resin that is oily or gum-like and lacks film-forming ability, such as a combination of a monofunctional monomer unit and a bifunctional monomer unit, is not preferred.

  The organopolysiloxane capable of forming a film is preferably used by dissolving it in a solvent, but it may also be used as a dispersion. When preparing the dispersion, the organopolysiloxane resin particles should be finer than the polyphosphoric acid compound particles and the particle size should be 3 to 25 μm to cover the surface of the polyphosphoric acid compound particles. .

  The amount of the organopolysiloxane having film-forming ability may be about 2 to 20 weights with respect to 100 parts by weight of the polyphosphoric acid compound.

  In order to effectively coat the particles of the polyphosphate compound with the organopolysiloxane, the polyphosphate compound and the organopolysiloxane coexist or the organopolysiloxane resin solution or resin dispersion and the polyphosphate compound are mixed. It is preferable to mix and agitate the powder or dispersion and heat-treat. As a solvent for the organopolysiloxane resin solution or the resin dispersion, a hydrophilic organic solvent such as acetone, ethyl acetate, or methyl alcohol may be used.

  In addition, in order to coat the polyphosphoric acid compound particles with organopolysiloxane capable of forming a film, a mixed liquid of a dispersion of organopolysiloxane resin particles having an average particle diameter of 3 to 25 μm and a polyphosphoric acid compound powder dispersion Or a mixture of an organopolysiloxane and a polyphosphate compound obtained by drying a mixed solution in which a fine powder of a polyphosphate compound is mixed with a resin solution obtained by dissolving organopolysiloxane resin fine powder in toluene or another organic solvent. Alternatively, the powder may be pulverized by a pulverizer such as a ball mill or a jet mill to form a fine powder.

  Organopolysiloxane with film-forming ability may be prepared as a mixed composition with UV absorbers, antioxidants, color pigments, etc., and the resin film that coats the surface of particles of polyphosphoric acid compounds is hardened. For this purpose, a polymethyl acrylate resin may be mixed with the organopolysiloxane.

The flame retardant obtained by coating the particles of the flame retardant polyphosphoric acid compound thus obtained with organopolysiloxane is used as a flame retardant resin composition blended in a binder resin.
As the binder resin, an acrylic resin, a urethane resin, an ethylene / vinyl acetate resin, or the like is used, but an acrylic resin or a urethane resin is preferably used.
As a matter of course, for the purpose of the present invention, a binder resin containing no halogen component or formaldehyde component is used.

  In addition, what is important in this invention is that the pH of the flame retardant adhesion surface of the textile processed with this flame retardant is adjusted to 5-7. If this pH is low, there are problems such as aging of fiber products and resin discoloration under high temperature and high humidity conditions, and it is not possible to obtain a quality product having flame retardancy, and the pH is If it exceeds 7, the flame retardant may be decomposed, which is not preferable.

In order to adjust the pH of the flame retardant adhering surface to an appropriate range, as shown in the examples, after manufacturing the flame retardant, it is washed with water and dried, and the drying temperature and time are appropriately adjusted to produce a textile product. It is necessary to select an appropriate drying temperature after the flame retardant treatment. The washing of the flame retardant with water removes the solvent and polyphosphoric acid compound adhering to the surface of the flame retardant, and the subsequent drying temperature is preferably about 60-120 ° C. The drying time is not particularly limited, but may usually be about 5-20 hours.
Next, the drying temperature of the fiber product treated with the flame retardant is preferably about 120-160 ° C. When the amount of the organopolysiloxane adhering to the surface of the polyphosphoric acid compound is large, the treatment conditions for obtaining a predetermined pH value are widened.

  In the present invention, the mixing amount of the flame retardant and the binder may be about 10:90 to 80:20 as a solid content ratio, and particularly about 25:75 to 60:40 is easy to handle.

In addition, the amount of the flame retardant attached to the fiber product varies depending on the type of the fiber product, but when the fiber product is a fabric, it may be about 10 to 80 g / m ² , particularly about 20 to 60 g / m ² . Is preferred.

Textile products to be flame-retardant treated with the flame-retardant resin composition of the present invention include fiber yarn, rope, string, woven fabric, knitted fabric, nonwoven fabric, woven pile fabric, knitted pile fabric, tufted pile fabric, raised fabric, As long as the main material is a fiber such as an electrostatic flocking fabric, a fiber web, and a nonwoven fiber laminated cushion material, the entangled structure and use of the fiber are not particularly limited.
Textile products that are used by touching the skin only on one side, such as chairs, ceilings / walls, carpets (fiber flooring, rugs), especially woven pile fabrics, knitted pile fabrics, tufted pile fabrics, and raised fabrics In a thick fabric such as an electrostatic flocking fabric, a flame retardant is preferably applied to the back surface that does not directly touch the skin, even in ensuring the surface texture.

Organopolysiloxane capable of forming a film does not generate halogen gas or formaldehyde gas, has water repellency, is hydrophobic and does not absorb moisture, and its resin film is flexible and difficult to crack. For this reason, the particles of the polyphosphate flame retardant of the present invention in which the polyphosphate compound is covered with an organopolysiloxane do not absorb moisture during storage and are not agglomerated and are not aggregated. Sometimes it is uniformly dispersed in the resin composition or the flame retardant treatment liquid, and the dispersed state is stably maintained without cracking the resin film during the stirring process.
As a result, when applied to textile products, there is no variation in adhesion spots and flame retardant performance, and there is no stickiness or inducing sick house syndrome. I can do it.
Furthermore, in the present invention, by adjusting the pH value of the flame retardant-treated surface to 5-7, it is possible to prevent the influence of acid due to the hydrolyzability of the polyphosphoric acid compound, and to significantly improve the heat resistance and durability of the product. It is possible to provide a stable product having no problem with aging.

Hereinafter, the present invention will be described according to examples.
[Polyphosphate flame retardant]
<Example 1>
Polyphosphorus having an average particle size of 8 μm and a weight average polymerization degree of 1000 in an ethanol / acetic acid solution of an organopolysiloxane (monofunctional monomer unit combined with a trifunctional monomer unit) made by Shin-Etsu Chemical Co., Ltd. Ammonium acid particles were blended with ethanol so that the amount of the ammonium polyphosphate particles was 96 parts by weight with respect to 4 parts by weight of the resin. After stirring, the organic solvent was removed under reduced pressure, and the ammonium polyphosphate particles coated with organopolysiloxane A was obtained. Similarly, an ammonium polyphosphate particle B coated with organopolysiloxane was obtained by blending so as to be 90 parts by weight of ammonium polyphosphate particles with respect to 10 parts by weight of the resin.
These particles A and B were washed with water to remove the solvent and ammonium polyphosphate adhering to the particle surface, and then the temperature was changed (80 ° C., 110 ° C., 140 ° C., 170 ° C.) and dried for about 12 hours. did.
50 parts by weight of the flame retardant thus obtained is dispersed in 50 parts by weight of water to obtain a paste product, 100 parts by weight of acrylic resin is added, the viscosity is adjusted to 50000 mPa · S with HEC, did.
Each coating composition was applied to the back surface of a pile warp knitted fabric with a polyester basis weight of 450 gf / m ² so as to be about 200 g / m ² in a wet state, and the temperature was changed (130 ° C., 150 (C, 170 ° C.) for 2 minutes. Approximately 50 g / m ^{2 of the} organopolysiloxane-coated ammonium polyphosphate was deposited.
The pH of the flame retardant treated surfaces of the 24 types of products obtained was measured by the following method. The results are shown in Table 1.
<PH measurement method>
A pH test paper (standard pH test paper) wetted with distilled water was lightly pressed on the coating surface of each product, and the pH value was measured.

As shown in Table 1, it is possible to adjust the pH value of the treated surface of the fabric by adjusting the drying temperature of the flame retardant after washing with water and the drying temperature after the fabric treatment.

<Example 2>
The flame retardants A and B of Example 1, which were washed with water and dried at 110 ° C., were applied to a polyester fabric in the same manner as in Example 1 and applied to a polyester fabric, and the temperature was changed (130 ° C., 150 (C, 170 ° C.) for 2 minutes, and the performance test of the obtained product was performed. The results are shown in Table 2. Table 2 also shows the results of laminating the fabric thus treated on urethane foam and measuring the laminate strength (adhesive strength).
1. pH measurement: In the same manner as in Example 1, the pH of the product flame retardant treated surface was measured.
2 Discoloration test: A fabric treated with a flame retardant was cut into a 10 cm square, placed in a gear oven at 110 ° C. for 200 hours and heat-treated, and then the degree of discoloration of the coating surface was confirmed.
○ ・ ・ ・ No discoloration △ ・ ・ ・ Slightly yellowing × ・ ・ ・ Severe yellowing Flame retardant performance: The burning rate of the horizontally supported test piece was measured in accordance with the US automobile safety standard (FMVSS-302), and when the flame did not reach the marked line, it was determined as “flame retardant”.
4). Laminate strength: The laminate peel strength was tested after being left for 500 hours under conditions of 95% humidity and 50 ° C.
○: Maintains good strength Δ: Slightly reduced strength ×: Significantly reduced strength

When the pH of the flame retardant-treated surface was set to 5 according to the present invention, a stable product without discoloration was obtained, and the laminate product was also practical without decreasing the adhesive strength.

<Example 3>
The flame retardant B of Example 1 which was washed with water and dried at 110 ° C. was coated in the same manner as in Example 1, applied to a polyester fabric, dried at 130 ° C. for 2 minutes, and commercially available. The following tests were conducted on those using the flame retardant. The results are shown in Table 3.
[Evaluation of formaldehyde generation]
The fabric treated with flame retardant is cut into 10cm squares, sealed in odor bags (Omi Odo Air Service Co., Ltd.), injected with 2000cc of air, and heated at 80 ° C for 1 hour. The concentration of formaldehyde to be measured was measured with a Gastec detector (formaldehyde detector tube No. 9L manufactured by Gastec Corporation).
○ ... Formaldehyde is not detected.
X: Formaldehyde is detected (the detected concentration is indicated by a numerical value in ppm).
[Evaluation of slime feeling]
5 cc of 60 ° C hot water is applied to the center of the back side (flame retardant application surface) of the test piece cut into 20 cm square of the flame retardant treated fabric, and after 5 minutes, the top is touched with a finger. Existence was tested.
○ ... No slime is felt.
Δ: A slight slime is felt.
X ... Clear and slimy.

As shown in Table 3, the product of the present invention was a flame retardant fabric having a very good texture without generating formaldehyde, but the product treated with a commercially available flame retardant having a silane-treated ammonium polyphosphate surface. Even when the pH of the fabric surface was set to 5, the product had a strong slime feeling and a product with commercial value could not be obtained. In addition, the use of the flame retardant treated with melamine has no slimy feeling, but the generation of formaldehyde cannot be avoided and cannot be used.

[0004]
[0014]
The amount of the organopolysiloxane having film-forming ability may be about 2 to 20 parts by weight with respect to 100 parts by weight of the polyphosphoric acid compound.
[0015]
In order to effectively coat the particles of the polyphosphate compound with the organopolysiloxane, the polyphosphate compound and the organopolysiloxane coexist or the organopolysiloxane resin solution or resin dispersion and the polyphosphate compound are mixed. It is preferable to mix and agitate the powder or dispersion and heat-treat. As a solvent for the organopolysiloxane resin solution or the resin dispersion, a hydrophilic organic solvent such as acetone, ethyl acetate, or methyl alcohol may be used.
[0016]
In addition, in order to coat the polyphosphoric acid compound particles with organopolysiloxane capable of forming a film, a mixed liquid of a dispersion of organopolysiloxane resin particles having an average particle diameter of 3 to 25 μm and a polyphosphoric acid compound powder dispersion Or a mixture of an organopolysiloxane and a polyphosphate compound obtained by drying a mixed solution in which a fine powder of a polyphosphate compound is mixed with a resin solution obtained by dissolving organopolysiloxane resin fine powder in toluene or another organic solvent. Alternatively, the powder may be pulverized by a pulverizer such as a ball mill or a jet mill to form a fine powder.
[0017]
Organopolysiloxane with film-forming ability may be prepared as a mixed composition with UV absorbers, antioxidants, color pigments, etc., and the resin film that coats the surface of particles of polyphosphoric acid compounds is hardened. For this purpose, a polymethyl acrylate resin may be mixed with the organopolysiloxane.
[0018]
The flame retardant obtained by coating the particles of the flame retardant polyphosphoric acid compound thus obtained with organopolysiloxane is used as a flame retardant resin composition blended in a binder resin.
As the binder resin, an acrylic resin, a urethane resin, an ethylene / vinyl acetate resin, or the like is used, but an acrylic resin or a urethane resin is preferably used.
As a matter of course, for the purpose of the present invention, a binder resin containing no halogen component or formaldehyde component is used.
[0019]
In addition, what is important in this invention is that the pH of the flame retardant adhesion surface of the textile processed with this flame retardant is adjusted to 5-7. If this pH is low, the fiber is

Claims (9)

  A fiber product in which a flame retardant is attached together with a binder, wherein the flame retardant is composed of composite particles of a polyphosphoric acid compound having flame retardancy and an organopolysiloxane capable of forming a film, and the flame retardant is attached The flame retardant fiber product, wherein the flame retardant-adhering surface of the fiber product has a pH of 5 to 7.   The flame-retardant fiber product according to claim 1, wherein the organopolysiloxane is a combination of a monofunctional monomer unit and a tetrafunctional monomer unit and / or a trifunctional monomer unit.   The flame-retardant fiber product according to claim 1 or 2, wherein a weight blending ratio of the polyphosphoric acid compound and the organopolysiloxane in the flame retardant is 98-80: 2-20.   The flame-retardant fiber product according to any one of claims 1 to 3, wherein the organopolysiloxane coats the particle surface of the polyphosphoric acid compound.   The flame-retardant fiber product according to any one of claims 1 to 4, wherein the polyphosphate compound is ammonium polyphosphate.   The flame-retardant fiber product according to any one of claims 1 to 5, wherein the polyphosphoric acid compound has an average degree of polymerization of 20 to 2,000.   The flame-retardant fiber product according to any one of claims 1 to 6, wherein the binder is an acrylic resin.   The flame-retardant fiber product according to any one of claims 1 to 7, wherein the flame retardant and the binder are mixed and used in a solid content ratio of 10:90 to 80:20. Flame-retardant fiber product according to any one of claims 1 to 8 weight attached to the fiber product of the flame retardant is a 10 to 80 g / m ^2.