JPH07107142B2 - Flame retardant water dispersion - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention relates to a halogen-containing polymer latex and a fine particle diameter.
Sb ₆ O _{13 A} flame-retardant water dispersion comprising an aqueous sol.

(Prior art) Various latexes (emulsions) are used in the fields of paints, textile processing, paper processing, adhesives, etc. Especially when flame retardancy is required, vinyl chloride type, vinylidene chloride type, etc. The halogen-containing polymer latex of, also, a halogen-free polymer latex, a halogen compound, Al
Flame-retardant treatment is performed by using together with a flame retardant such as a compound or a P compound.

It has also been known for a long time that the flame retardancy is further improved by using an Sb compound in combination with a halogen-containing flame retardant substance, and various antimony oxide compounds used for such purposes are known. ing.

However, since the conventional antimony oxide compound has a particle diameter of a pigment level, a flame-retardant treated product using such coarse particles of antimony oxide has a texture, hue,
The transparency, weather resistance, etc. deteriorates, and since it is necessary to use a large amount of expensive antimony oxide compounds in order to impart the target flame retardancy, the physical properties of flame-retarded products are further impaired. There was a drawback.

In order to solve these drawbacks, a method for obtaining a fine particle antimony oxide compound has been studied in recent years, and, for example, a method for producing an antimony pentoxide (Sb ₂ O ₅ ) colloid sol has been disclosed in JP-A-52-
123997 JP, is disclosed in JP-B-57-11848 Publication, the particle diameter of the Sb ₂ O ₅ is still large, and because they contain impurities coming from the production process, such Sb ₂ O _{5 To} solve problems such as deterioration of the texture, hue, transparency, etc. of the product that imparts flame retardancy even when colloidal sol is used, and deterioration of weather resistance due to impurities in Sb ₂ O ₅ colloidal sol. I haven't arrived. Furthermore, when such Sb ₂ O ₅ colloidal sol is blended with latex such as vinyl chloride or vinylidene chloride, there is also a problem of lacking chemical stability such as aggregation and coalescence of Sb ₂ O ₅ particles. A flame-retardant water dispersion which retains the performance of the latex main body for flame-retardant treatment such as paper processing and does not have the above-mentioned problems based on an antimony compound is not known at present.

(Problems to be Solved by the Invention) An object of the present invention is to industrially provide a flame-retardant water dispersion that can be used for paints, fiber processing, paper processing, adhesives, etc. Another object is to provide a flame-retardant water dispersion which does not deteriorate the weather resistance, texture, hue, transparency and other properties of the flame-retardant treated product.

An object of the present invention described above (means for solving the problems) are halogen-containing polymer latex and the particle size is achieved by the flame-retardant aqueous dispersion consisting of Sb ₆ O ₁₃ aqueous sol of 1～100Emumyu.

Hereinafter, the present invention will be described in detail.

The halogen-containing polymer latex as the main component of the flame retardant water dispersion of the present invention, vinyl chloride, vinylidene chloride,
Halogen-based polymer latex containing at least one halogen-containing monomer such as vinyl bromide as a main component; halogen such as chlorinated polyethylene, chlorinated polypropylene, chlorosulfonated polyethylene, chlorinated polyether, polystyrene bromide, etc. And a halogen-free polymer latex such as polyvinyl alcohol-based, polyvinyl acetate-based, polyacrylic acid ester-based, epoxy resin-based, synthetic rubber-based, etc. Mixtures can also be used.

Depending on the purpose of use, flame retardants such as phosphorus compounds, tin compounds, aluminum compounds, iron compounds and halogen compounds may be used in combination in the halogen-containing polymer latex.

Further, Sb used in combination with the halogen-containing polymer latex
_{As the 6} O ₁₃ aqueous sol, the particle size of Sb ₆ O ₁₃ needs to be 1 to 100 mμ, and when Sb ₆ O ₁₃ having a particle size of 100 mμ or more is used, not only the flame retardant performance is deteriorated, It is not preferable because it deteriorates various properties such as the texture of flame-retardant treatment, hue, transparency, and weather resistance. The Sb ₆ O ₁₃ aqueous sol used in the present invention has a particle size of Sb ₆ O ₁₃ of 1 to 100 mμ, preferably 1 to 30 mμ.
And when blended with the halogen-containing polymer latex, polymer particles in the latex or Sb
_Use any Sb ₆ O ₁₃ aqueous sol as long as the ₆ O ₁₃ particles themselves do not coarsen due to agglomeration and do not contain unnecessary impurities that cause the physical properties of the flame-retardant product to be impaired. However, it can be produced by the following method, for example, based on the invention of Japanese Patent Application No. 60-266866 related to the invention of the present inventors.

First, antimony trioxide (Sb ₂ O ₃ ) and hydrogen peroxide (H ₂ O 3
₂ ) and a specific alkali metal compound from 1: 1.25 to 1.8: 0.0
The reaction is carried out at a ratio of 15 to 0.3 mol.

The particle size of Sb ₂ O ₃ is 100μ or less, but dispersibility in water, H ₂
From the viewpoint of reactivity with O ₂ , it is preferably 0.1 to 10 μm. To disperse this Sb ₂ O ₃ in an aqueous medium to prepare a dispersion, the concentration of Sb ₂ O ₃ in the dispersion is 5 to 40% by weight,
It is preferably 7 to 25% by weight.

The compounding amount of H ₂ O ₂ is 1.25 to 1.8 mol per 1 mol of Sb ₂ O ₃ , and if it is less than 1.25 mol, colloidal fine particles cannot be obtained. It is not preferable because the chemical stability to the electrolyte is lowered, and unreacted H ₂ O ₂ remains in the obtained aqueous sol.

The alkali metal compound blended in the Sb ₂ O ₃ dispersion is selected from sodium hydroxide, sodium hydroxide, lithium carbonate and sodium carbonate. When other alkali metal compounds such as potassium hydroxide and calcium hydroxide are used, fine particle Sb ₆ O ₁₃ is not formed. The specific alkali metal compound content is Sb ₂ O ₃ 1
The amount is 0.015 to 0.3 mol, preferably 0.02 to 0.2 mol, based on mol. If the blending amount of the alkali metal compound is less than 0.015 mol, the reaction will be slow, so it is necessary to maintain the reaction temperature near or above the boiling point of water, and in the high-concentration reaction system, Sb ₆ O ₁₃ The particle size becomes large. On the other hand, if the amount of the alkali metal compound added exceeds 0.3 mol, Sb ₆ O _{13 in the} form of fine particles cannot be selectively produced, and the particle size becomes extremely coarse in a high-concentration reaction system.

The order of mixing the above raw materials Sb ₂ O ₃ , H ₂ O ₂ and the alkali metal compound is not particularly limited, and for example, the three may be mixed at the same time to form an aqueous dispersion, and Sb ₂ O ₃ and the alkali metal compound may also be mixed. H ₂ O ₂ may be mixed with the aqueous dispersion of

The temperature for reacting the aqueous dispersion is 30 ° C. or higher, preferably 50 to 100 ° C., but since the reaction can be started even at a low temperature of 50 ° C. or lower, the energy required for heating the reaction system decreases. Not only that, the amount of heat generated by the reaction is mostly absorbed as the amount of heat for raising the temperature of the reaction system to the boiling point, so there is little need for external cooling, and there is no need to adjust the temperature to prevent bumping. .

The solid content concentration in the aqueous sol obtained by the above reaction is 6 to 45% by weight depending on the concentration of Sb ₂ O ₃ in the aqueous dispersion,
The content is preferably 8 to 28% by weight, but by further concentrating the aqueous sol as necessary, an aqueous sol having a solid content concentration of 45% by weight or more can be obtained without adding a stabilizer.

Such Sb ₆ O ₁₃ aqueous sol is a Sb ₆ O ₁₃ particle size 1~100mμ, Sb ₆ O ₁₃ concentration higher concentrations, yet the thermal stability are excellent aqueous sol in chemical stability, Furthermore, based on the invention of Japanese Patent Application No. 60-266742 relating to the application of the present inventors, the chemical stability is remarkably high without causing agglomeration / coalescence of particles even in mixing with a latex in which an inorganic salt or the like is present. An excellent Sb ₆ O ₁₃ aqueous sol can be obtained.

That is, after treated by adding an organic silicon compound represented by the following general formula with respect to Sb ₆ O ₁₃ Sb in the aqueous sol in a proportion of 0.5 to 2.5 wt%, the pH is adjusted to within the range of 2.5 to 12 .

The Sb ₆ O ₁₃ aqueous sol thus obtained is blended with the halogen-containing polymer latex to obtain the flame-retardant water dispersion of the present invention.

The ratio of the latex and the Sb ₆ O ₁₃ aqueous sol to be used is determined by the use of the flame-retardant water dispersion, the method of use, the required flame-retardant performance, etc. and is not uniquely determined. The molar ratio of Sb to the halogen in the combined latex is generally 0.01 to 1 mol, preferably 0.1.
It is desirable to use it together so as to be 02 to 0.3 mol.

The flame-retardant water dispersion of the present invention is usually a mixture of a halogen-containing polymer latex and an Sb ₆ O ₁₃ aqueous sol, which is used separately as a result (for example, latex The aqueous sol may be used later or vice versa).

(Operation) Although flame retardant aqueous dispersion of the present invention is made of Sb ₆ O ₁₃ aqueous sol containing Sb ₆ O ₁₃ of the halogen-containing polymer latex and the fine particle size, Sb ₆ O ₁₃ aqueous sol The excellent properties are exhibited, and the flame-retarded product using the water dispersion is remarkably excellent in flame retardancy. The reason for this is that the Sb compounded in the present invention is
₆ O ₁₃ The particle size of the aqueous sol is 1 to 100 mμ, preferably 1 to 30 m
μ and ultrafine particles, and evenly dispersed in the halogen-containing polymer latex without any aggregation, as a result, the specific surface area of Sb ₆ O ₁₃ is significantly higher than that of the conventional product. It is increasing.

Further, since Sb ₆ O ₁₃ having a fine particle size is used, there is no concealing action due to the antimony compound, and thus it is considered that a product having excellent transparency and a clear color tone can be obtained.

Furthermore, since the Sb ₆ O ₁₃ aqueous sol does not contain impurities, the weather resistance of the product does not deteriorate due to the impurities.

(Examples) Next, examples of the present invention will be shown, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. The percentages and parts in the examples are based on weight.

The light transmittance, the combustion test, and the weather resistance test were according to the following methods.

Light transmittance: The light transmittance of white light for an antimony oxide aqueous sol having a concentration of 0.4% in terms of Sb was measured by HITAC HI-101 Spectrop
It was measured using a hotometer (manufactured by Hitachi Ltd.), and the larger the value, the smaller the particle size.

Combustion test: Fire Defense Law 45 degree micro burner method or FMVSS (Feder
al Motor Vehicle Safety Standard) 302 method.

Weather resistance test: The surface condition after exposure was observed with a Sunshine Super Long Life Weather Meter manufactured by Suga Test Instruments Co., Ltd.

Example 1 B Preparation of Sb ₆ O ₁₃ aqueous sol A three-necked flask (capacity 1) equipped with a stirrer was immersed in a constant temperature water bath at 90 ° C., and water, Sb ₂ O ₃ (concentration 13% by weight,
Average particle size 0.8μ) and NaOH aqueous solution (NaOH / Sb ₂ O ₃ = 0.1
(1 / molar ratio) and when the temperature of the contents reached 50 ° C, H ₂ O ₂ (H ₂ O ₂ / Sb ₂ O ₃ = 1.3 / 1 molar ratio) was added and reacted for 1 hour. Thus, an Sb ₆ O ₁₃ aqueous sol having a particle size of 1 to 20 mμ, a light transmittance of 92%, and a chemical stability of 88% (light transmittance when mixed with 5% NaCl) was prepared.

To the obtained Sb ₆ O ₁₃ aqueous sol, 5% of monomethyltrimethoxysilane (vs Sb ₆ O ₁₃ ) was added, reacted at 85 ° C. for 1 hour with stirring, and then 20% NaOH aqueous solution was added to adjust pH to 7. .

(B) Preparation of flame-retardant water dispersion Take 100 parts of vinyl chloride latex (trade name; Sumikaflex-840, solid content 53%) manufactured by Sumitomo Chemical Co., Ltd. in a three-necked flask (volume 1) and stir at room temperature. A flame-retardant water dispersion was prepared by adding the Sb ₆ O ₁₃ aqueous sol prepared in b) to 8% as Sb ₆ O ₁₃ .

Similarly, instead of the Sb ₆ O ₁₃ aqueous sol, a commercially available Sb ₂ O ₅ aqueous sol was added so that the amount of Sb was equal to prepare a flame-retardant water dispersion (comparative example). Table 1 shows the evaluation results of the miscibility and the storage stability of the flame-retardant water dispersion thus prepared.

C. Flame-retardant treatment of fiber material Commercially available polyester fiber woven fabric (weight of 200 g / m ² ) is sprayed with 200 g / m ^{2 of} flame-retardant water dispersion prepared in step 8 to give 8
After drying at 0 ° C. for 10 minutes, it was subjected to dry heat treatment at 150 ° C. for 5 minutes to make it flame-retardant.

The results of the weather resistance test and the combustion test of the flame-retardant treated cloth,
The results are shown in Table 2 together with the comparative examples.

As described above, the product of the present invention is excellent in miscibility with the latex and leaving stability, and by using the flame-retardant water dispersion of the present invention, the weather resistance of the flame-retardant-treated product is excellent in the flame-retardant effect. You can see that there is.

Adjusting the following flame-retardant water dispersion with Sb ₆ O ₁₃ aqueous sol prepared in b of Example 1.

Lee flame adjustment Toagosei of retardant aqueous dispersion Co. salt production fluoride latex (Aron D-5040, 50% solids) a Sb ₆ O ₁₃ aqueous sol to 100 parts Sb ₆ O
₁₃ % 5% and triethylphosphite 40% were mixed with stirring at room temperature to prepare a flame-retardant water dispersion.

Similarly, instead of the Sb ₆ O ₁₃ aqueous sol, a commercially available Sb ₂ O ₅ aqueous sol was added so that the amount of Sb was equal to prepare a flame-retardant water dispersion (comparative example).

(B) Flame-retardant treatment of fiber material A commercially available cotton fabric (Basis weight: 200 g / m ² ) was dipped in the flame-retardant water dispersion prepared in step (i) and squeezed with a rubber angle roller to a pickup rate of 70%. Drying was performed at 5 ° C for 5 minutes, and dry heat treatment was performed at 130 ° C for 3 minutes to perform flame retardant treatment.

The weather resistance test and combustion test results of the flame-retardant treated cotton cloth,
The results are shown in Table 3 together with the comparative examples.

From the above table, it is clear that the product of the present invention is excellent in weather resistance and flame retardancy by using the flame retardant treated product.

(Effect of the invention) The flame-retardant water dispersion of the present invention has a fine particle diameter of Sb ₆ O _{13 which} is uniformly dispersed in the halogen-containing polymer latex without agglomeration. When flame-retarding paints, fibers, paper, etc. using the body, it is possible to significantly improve the flame retardancy compared to conventional products using antimony oxide, which in turn results in flame retardant water dispersion. It is possible to reduce the amount of body used or the amount of Sb ₆ O ₁₃ compounded in the flame-retardant water dispersion, prevent the deterioration of the physical properties of the treated product due to the addition of the flame-retardant water dispersion, and excel in economic efficiency. It is a remarkable effect of the present invention that the flame-retardant water dispersion can be provided.

Further, since the flame-retardant water dispersion of the present invention uses the Sb ₆ O ₁₃ aqueous sol having a fine particle size and containing no impurities, it is possible to obtain a treated product having excellent transparency and weather resistance. It is possible.

Claims (2)

[Claims] 1. A halogen-containing polymer latex and a particle size of 1.
Flame-retardant water dispersion consisting of ~ 100 mμ Sb ₆ O ₁₃ aqueous sol. 2. The flame-retardant water dispersion according to claim 1, wherein the particle size of the Sb ₆ O ₁₃ aqueous sol is 1 to 30 mμ.