JP2017105928A - Flame retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame retardant resin composition without using a halogen compound, without containing heavy metal compounds as impurities and capable of suppressing appearance defects during wetting while maintaining excellent flame retardancy equal to or more than that of conventional products.SOLUTION: There is provided a flame retardant resin composition containing (a) at least one kind of an acrylic resin emulsion, a styrene-butadiene resin emulsion and an urethane resin emulsion or a mixture thereof, (b) ammonium polyphosphate and (c) a water absorptive porous material having specific surface area of 300 m/g or more and 30% water dispersion viscosity of 3,000 mPa s or less of 1 to 30 pts.wt. based on 100 pts.wt. of a solid component of the resin emulsion (a).SELECTED DRAWING: None

Description

  The present invention relates to a flame retardant resin composition, and more specifically, when a fiber product imparted with flame retardancy using the flame retardant resin composition is used as an automobile sheet or the like, the appearance generated when wet It relates to the reduction of defects.

Conventionally, polyester fibers have been used in automobile interior materials such as seats and floor mats. Since automobile interior materials are required not to burn easily at the time of a fire, flame retardancy is imparted by treating fibers with a flame retardant resin composition to which a flame retardant is added.
Decabrom diphenyl oxide (DBDPO) and antimony trioxide (Sb2O3) have been used as typical flame retardants, but halogen compounds can generate harmful substances such as dioxins in the event of a fire, so they can be avoided. It has become. Also, antimony contains heavy metals such as lead as impurities, so that it can be avoided in the same way.

  Therefore, various phosphorus compounds have attracted attention as potential options and are actually widely used. Among them, ammonium polyphosphate is excellent in flame retardancy, has higher safety than other phosphorus compounds, and is difficult to bleed out. Therefore, it is used as a flame retardant for textile products for automobile interiors.

On the other hand, if the sheet is placed under hot and humid conditions, or if water or hot water is spilled on the sheet, ammonium polyphosphate will dissolve on the surface due to its water solubility, resulting in spots and slimes called “wrinkles” Sometimes.
In addition, when manufacturing a sheet for automobiles, ammonium polyphosphate is coated on a fiber lining together with a binder component such as an acrylic resin and bonded to a urethane sheet base material, but ammonium polyphosphate is eluted on the surface. There are cases where the appearance is poor when the sheet and the fabric are shifted and stuck together due to slimming, or when the sheet is wrinkled after drying.

Patent Document 1 discloses an ammonium polyphosphate-containing substance coated with a thermoplastic resin. However, only a decrease in flame retardancy is evaluated as an effect of elution, and appearance defects that cause problems even with slight elution are disclosed. Has not been fully studied. Moreover, the storage stability in an aqueous solvent tends to be reduced by being coated with a thermoplastic resin.
JP 2001-262466 A

  The problem of the present invention is that it does not use a halogen compound, does not contain a heavy metal compound as an impurity, and maintains an excellent flame retardance equivalent to or better than that of a conventional product, while suppressing the appearance defect when wet. It is to provide a flame retardant resin composition.

The present invention contains 1 to 30 parts by weight of the water-absorbing porous material (c) with respect to 100 parts by weight of the solid content of the resin emulsion (a), ammonium polyphosphate (b), and resin emulsion (a). It is the flame-retardant resin composition characterized.
Although the reason why the appearance defect when wet with water can be suppressed by the present invention is not clear, the textile treated with the flame retardant resin composition of the present invention can quickly disperse and absorb the attached water. Therefore, it is presumed that ammonium polyphosphate is hardly eluted as a result.

  The flame-retardant resin composition of the present invention can suppress the appearance defect when wet with water while maintaining flame retardance equal to or higher than that of the previous product without using heavy metal compounds and halogen compounds. Suitable for processing textile products that require flame resistance such as sheets.

  The flame retardant resin composition of the present invention contains a resin emulsion (a) as a binder component. Known resin emulsions can be used, but acrylic resin emulsions, styrene-butadiene resin emulsions or urethane resin emulsions are preferred from the viewpoints of flame retardancy, water resistance as a binder, prevention of blocking, flexibility, and the like. For the same reason, the glass transition temperature (Tg) is preferably 40 ° C. or lower.

The polyphosphate ammonium (b) is a polymer of ammonium phosphate represented by the following general formula (1) or (2) (wherein n is about 10 to 2000), and is not particularly limited.

Depending on the production method, ammonium polyphosphate has crystal structures of type I, type II, type III, type IV, and type V, any of which can be used.
The particle diameter of ammonium polyphosphate is preferably 1 to 100 μm in average particle diameter by laser diffraction (scattering method) of Microtrac MT3000II. When the average particle diameter is outside this range, the particles are coarse particles, which is not practically suitable. It is preferable to add 30 to 500 parts by weight of ammonium polyphosphate (b) with respect to 100 parts by weight of the solid content of the resin emulsion (a). By setting it as 30 weight part or more, a flame retardance improves notably, By making it 500 weight part or less, the influence on backing performance can be suppressed.

The flame-retardant resin composition of the present invention contains a water-absorbing porous material (c). When water-absorbing porous material is contained, when water adheres to the surface of the fiber product treated with the flame retardant resin composition, water can be quickly dispersed and absorbed, and polyphosphate ammonium and water It is presumed that the contact of this is reduced.
Specific examples of the water-absorbing porous material include activated carbon, silica, zeolite, and the like, and mixtures thereof. Among these absorptive porous materials, those having a specific surface area of 300 m ² / g or more are preferable because of excellent water dispersion and absorption, and more preferably 700 m ² / g or more.

On the other hand, the addition of the water-absorbing porous material increases the viscosity of the flame retardant resin composition, which may adversely affect processability and storage stability. Therefore, it is preferable to use one having a 30% aqueous dispersion viscosity of 3,000 mPa · s or less, and more preferably 900 mPa · s or less.
Moreover, it is preferable to add 0.1-30 weight part of a water absorbing porous agent with respect to 100 weight part of solid content of the said resin emulsion (a), and it is more preferable to add 1-15 weight part. When the amount is 0.1 parts by weight or more, the effect of suppressing appearance defects when wetted with water is significantly improved, and when the amount is 30 parts by weight or less, the composition can be prevented from excessively thickening.

By using the low molecular weight dispersant (d) having a molecular weight of 1,000 or less together with the water-absorbing porous material (c), it is possible to further enhance the effect of suppressing poor appearance when wet. When such a low molecular weight dispersant is contained, since it is generally feared that the water resistance is lowered, it is assumed that the appearance defect when wet becomes conspicuous. It was done. The reason for this is considered that the dispersibility of the water-absorbing porous material in the resin composition is improved, and that the drying property is improved because water easily spreads when wet.
Specific examples of the low molecular weight dispersant include low molecular weight surfactants, and sulfate-based surfactants such as sodium lauryl sulfate and ammonium lauryl sulfate are preferred. In addition, since the remarkable effect cannot be confirmed when molecular weight exceeds 1,000, it is unpreferable.

  In addition, when the addition amount of the low molecular weight dispersant becomes excessive, the effect of suppressing the appearance defect when wet with water is reduced. The preferred blending amount varies depending on the type of low molecular weight dispersant, but when ammonium lauryl sulfate is used, it is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the solid content of the resin emulsion (a).

In addition to the above-described blending components, various additives can be blended in the flame-retardant resin composition of the present invention as long as the excellent effects of the present invention are not hindered. Examples thereof include flame retardants such as aluminum hydroxide, boron compounds, melamine compounds, and zirconium compounds, and crosslinking agents such as isocyanate compounds.
Further, inorganic fillers, dispersants, thickeners, wetting agents, foaming agents, foam stabilizers, antifoaming agents, pigments, dyes, plasticizers, anti-aging agents, ultraviolet absorbers, preservatives and the like can be used.

  The solid content, pH, and viscosity of the flame-retardant resin composition of the present invention obtained as described above are not particularly limited, but in general, from the viewpoint of sedimentation stability of the composition, etc. The solid content is 30 to 70% by weight, preferably 30 to 60% by weight, the pH is 5 to 10, preferably 6 to 10, and the viscosity (BH viscometer, 20 ° C., 10 rpm) is 10,000 to 60,000 mPa · s. s, preferably 10,000 to 40,000 mPa · s.

  By using the flame retardant resin composition of the present invention as a backing layer for a fiber material such as a car sheet fabric, a car seat having excellent flame retardancy can be obtained. The car seat fabric is not particularly limited as long as it does not generate a harmful gas in a fire and uses a processing agent that does not generate formaldehyde as a processing agent such as a shrink-proofing agent. Examples thereof include synthetic fibers such as polyester, polypropylene, nylon, and acrylic, natural fibers such as wool, and blends thereof.

The coating amount of the backing layer of the flame retardant resin composition of the present invention, 10 to 200 g / ^{m 2} in solids, preferably 20 to 150 g / ^{m 2.} If the coating amount is less than 10 g / m ² , the flame retardancy may be insufficient, and if it exceeds 200 g / m ² , the texture is impaired and this is not economically preferable.

  EXAMPLES Hereinafter, although an Example, a reference example, and a comparative example are given and demonstrated in detail about this invention, a specific example is shown and it does not specifically limit to these.

Example 1
Acrylic copolymer resin emulsion containing styrene and acrylonitrile as monomers (manufactured by Aika Kogyo Co., Ltd., solid content 50%, Tg-40 ° C., trade name Ultrasol UL-2606) 100 parts by weight in solid content, melamine cyanurate 20 parts by weight, 85 parts by weight of ammonium polyphosphate, activated carbon (manufactured by Osaka Gas Chemical Co., Ltd., specific surface area 1,700 m ² / g, 30% aqueous dispersion viscosity less than 200 mPa · s, trade name Hakuho FPG-1 W-50 ) 1 part by weight, 4 parts by weight of ammonium lauryl sulfate in solid content, acrylic thickener (made by Aika Kogyo Co., Ltd., solid content 28%, Tg 25 ° C., trade name Ultrazol V-280) as a thickener, Furthermore, the flame-retardant resin composition of Example 1 was obtained by adding water and adjusting solid content to 48%.

Examples 2-6, Comparative Examples 1-5
In addition to the materials used in Example 1, silica (manufactured by Fuji Silysia Chemical Co., Ltd., specific surface area 700 g / m ² , 30% aqueous dispersion viscosity less than 200 mPa · s, trade name Cylicia 730) is used. Each flame retardant resin composition was similarly obtained by blending.

Flame retardant Each flame retardant resin composition was applied as 60 g / m ² as a solid content to a polyester fiber (weight per unit: 250 g / m ² ), and dried in an atmosphere of 140 ° C. for 10 minutes. The sample was cut into 350 mm × 200 mm and left in a 20 ° C., 65% RH atmosphere for 24 hours as a sample.
In accordance with FMVSS-302, which is a flame retardant standard for the automotive interior field, the prepared sample was subjected to a combustion test by the horizontal method. The test was conducted at 6 points, and the average burning rate (mm / min) and standard deviation (σ) were determined to be acceptable if the burning rate + 4σ = 100 or less.

Storage stability After measuring the initial viscosity of each flame retardant resin composition, it was sealed in a glass bottle and stored in an atmosphere at 40 ° C. for 1 month, then the viscosity was measured again, and compared with the viscosity before storage as follows. Evaluated.
A: Thickening less than 30% from initial viscosity B: Thickening from initial viscosity to 30% or more and less than 60% X: Thickening from initial viscosity to 60% or more

Stickiness test Each flame-retardant resin composition was applied to a thin fabric (weight per unit area: 200 g / m ² ) with a doctor knife so that the dry weight was 80 g / m ² . Thereafter, hot air drying was performed at 140 ° C. to reduce the water content to less than 5%, and then the specimen was cured overnight at 23 ° C. in a 50% atmosphere.
The test specimen was placed on the urethane foam so that the resin-coated surface (back surface) was down, and distilled water at room temperature was dropped from the top (front surface). After natural drying for 24 hours under an atmosphere of 23 ° C. and 50%, the presence or absence of a stain was visually confirmed from the surface side, and the following criteria were evaluated.
◎: No change in appearance ○: Color floating is observed when viewed from an oblique direction, but no stain due to water wetting is observed.
×: Spots accompanying water wetting are observed

When each flame retardant resin composition of the examples is used, the flame retardancy, storage stability, and appearance when wet are good, and those containing a low molecular weight dispersant have an appearance when wet. It was better.
On the other hand, when the flame retardant resin composition of the comparative example was used, any of the performances was insufficient.

Claims (4)

  1 to 30 parts by weight of the water-absorbing porous material (c) per 100 parts by weight of the solid content of the resin emulsion (a), ammonium polyphosphate (b), and resin emulsion (a) A flammable resin composition. The flame retardant resin composition according to claim 1, wherein the resin emulsion (a) is at least one of an acrylic resin emulsion, a styrene-butadiene resin emulsion, and a urethane resin emulsion, or a mixture thereof. The flame retardant according to claim 1 or 2, wherein the water-absorbing porous material (c) has a specific surface area of 300 m ² / g or more and a 30% aqueous dispersion viscosity of 3,000 mPa · s or less. Resin composition. The low molecular weight dispersant (d) having a molecular weight of 1,000 or less is contained in an amount of 0.5 to 15 parts by weight based on 100 parts by weight of the solid content of the resin emulsion (a). The flame-retardant resin composition as described in 2.