JPS6058453A - Flame-retardant for halogen-containing vinyl resin - Google Patents

Abstract

PURPOSE:The titled resin providing improved flame retardance without damaging transparency and thermal stability of resin, obtained by combining antimony pentoxide as a main component with an alkali metal, an alkaline earth metal, an organic acid, etc. CONSTITUTION:A flame-retardant containing 3-15wt% M2O (M is Na or K) as an alkali metal, (B) 5-20wt% M'O (M' is Mg, Ca, Sr, Ba, Zn, or Pb) as an alkaline earth metal and/or zinc or lead, (C) 1-8wt% organic acid, (D) 0.5- 3wt% P2O5 as phosphoric acid and/or alkali phosphate, and (E) the rest of antimony pentoxide. A molar ratio of (M2O+M'O)/Sb2O5 is preferably 0.8-2.5, and a molar ratio of organic acid/M'O is 0.05-0.5. This flame-retardant is effective for making non-rigid resin blended with plasticizer and rigid resin blended with reinforcing material for impact strength into flame-retardant resin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a flame retardant for halogen-containing vinyl resins containing antimony pentoxide as a main component. This invention relates to a flame retardant for halogen-containing vinyl resins containing antimony oxide (Sb205) as a main component.

Halogen-containing vinyl resin itself has excellent flame retardancy, but for example, so-called soft vinyl chloride resin plasticized with a plasticizer such as dioctyl chloride, or halogen-containing vinyl resin blended with flammable resin, can easily Burn. Widely used as automobile interior materials, electrical/electronic parts, construction materials, etc., F-1 canvas, electric wires, films,
H-smoking is especially essential for soft vinyl chloride products such as sheets, or hard vinyl chloride products containing impact reinforcement materials.

Various types of fuels are used to burn these resins. Inorganic substances such as antimony trioxide (sb2o3), sodium antimonate, aluminum hydroxide, zirconium oxide, zinc borate, and borax, and organic compounds such as tricresyl phosphate, tric00 ethyl phosphate, and chlorinated paraffin are used. There is. In rare cases, organic bromine flame retardants are also used. These have advantages and disadvantages in terms of flame retardant effect, transparency, p) stability, weather resistance, cold resistance, bleed/bloom resistance, etc.

Antimony trioxide usually has a particle size of about 0.5 to 10μ, has a large refractive index, and has low light transmittance, so it has extremely strong hiding properties, so it completely eliminates the transparency that is the most important feature of halogen-containing vinyl resin. I will lose it. Furthermore, when coloring is carried out by adding a pigment, there are disadvantages such as a large amount of pigment being required for the concealing property, and the types of colors that can be obtained being limited. In order to improve this drawback, it has been proposed to make the 1' particle diameter extremely small (Japanese Patent Publication No. 4G-7170) or to increase the particle size by forming a single crystal. All of these methods are used to improve light transmittance, and the former method significantly improves transparency, but when pigments are added, hiding properties increase and
The latter method deteriorates the thermal stability of the resin and increases manufacturing costs, and sufficient transparency cannot be obtained with the latter method. Antimony pentoxide is an antimony-based flame retardant that can be applied to halogen-containing vinyl resin without losing the transparency of the resin (J, Coate
d Fabric Vol 11. P, 137198
2), this is antimony pentoxide sol (particle size 20-1
00mμ) was powdered by spray drying or the like, and is antimony pentoxide tetrahydrate. This antimony pentoxide tetrahydrate has a small refractive index, and since the -order particles are extremely small particles, the transmittance of light is high, resulting in very good transparency. However, this antimony pentoxide has a defect that significantly deteriorates the thermal stability of the resin (see Comparative Example). In order to compensate for this deficiency, the use of Ba-Cd-Zn-based stabilizers or tin mercaptide-based stabilizers has been proposed (J, Coated Fabric Vol 11.
P, 1371982), but the former cannot be used practically because of the toxicity of cadmium and the occurrence of bleed bloom, and the latter has poor weather resistance. Sodium antimonate has a small external combustion effect when the particle size is large, but this
It has been reported that a product partially neutralized with acid after being pulverized to ~8μ shows good transparency, flame retardancy, and thermal stability (Japanese Patent Publication No. 36863/1983). However, if the primary particle size falls within this range, sufficient transparency cannot be obtained, and since this neutralization is partial neutralization, most of the content is sodium antimonate, so sufficient flame retardance cannot be obtained.

Inorganic substances such as aluminum hydroxide, zirconium oxide, zinc borate, and borax have inferior flame retardant effects compared to antimony trioxide and antimony pentoxide, and lose transparency in the same way as antimony dioxide.

Phosphorous plasticizers such as tricresyl phosphate, which have a plasticizing effect without losing transparency, and chlorinated paraffins have a flame retardant effect inferior to that of antimony dioxide, so they must be added in large amounts. As a result, it tends to bleed and has poor cold resistance. In other words, with conventional products and technologies,
It has not been possible to economically convert it into Iffa without impairing transparency, which is the most important feature of halogen-containing vinyl resins, and while satisfying physical properties such as thermal stability.

The present inventors have completed the present invention as a result of extensive research into flame retardants that do not have the above-mentioned drawbacks.

That is, the inventors of the present invention aimed to take advantage of the characteristic that antimony pentoxide does not impair the transparency of the resin when applied to a halogen-containing vinyl resin, while overcoming the disadvantage that it worsens the thermal stability of the resin. Various studies were conducted.

Unlike antimony trioxide, antimony pentoxide is a fairly strong solid acid, so it contains Na, Mg, and Ca.

It has the property of strongly binding with basic and amphoteric substances containing Sr, Ba, Zn, Cd, Pb, etc. Therefore, when antimony pentoxide is applied directly to plasticized halogen-containing vinyl resin as a flame retardant, these substances Because it reacts with metal soap stabilizers commonly used in the industry, such as zinc stearate, barium stearate, magnesium stearate, etc., its function as a stabilizer is significantly reduced. It is assumed that this deteriorates the thermal stability of the plasticized halogen-containing vinyl resin and causes discoloration and bleed/bloom phenomena.

Based on the above facts and reasoning, the present inventors first added Na, Ca, and Mg to antimony pentoxide colloid.

Various basic metals such as Ca, Ba, Zn, AI, and Sb (III) are added in the form of hydroxides, individually or in combination, and applied to a plasticized halogen-containing vinyl resin to heat it. Stability was measured.

As a result, it was found that a combination of alkali metals, alkaline earth metals, etc. is effective in improving thermal stability.

Although this alone cannot sufficiently prevent the initial yellow coloration, citric acid, malonic acid,
It has been found that the addition of phosphoric acid and water-soluble organic acids such as maleic acid, adipic acid, fucuric acid, and fumaric acid can significantly reduce initial coloration.

The present invention has been made based on the above-mentioned findings. That is, (A) the alkali metal has the general formula M20 (M=Na, K
) 3 to 15% by weight, (B) alkaline earth metal and/or zinc, lead (% formula % Pb) of 5 to 20% by weight, (C) organic acid 1 to 8% by weight, (D > Phosphoric acid and/or phosphoric acid alkali salt P2O5
It relates to a flame retardant for halogen-containing vinyl resins, which contains 0.5 to 3% by weight as a halogen-containing flame retardant, with the remainder consisting of (E) antimony pentoxide.

The antimony pentoxide used in the present invention is prepared by a method of oxidizing antimony trioxide (Japanese Patent Publication No. 57-11848), a method of dealkalizing alkali antimonate with an ion exchange resin (US Pat. No. 4,110,247), and other methods. Antimony pentoxide sol or antimony pentoxide suspension having a primary particle size of 200 mμ or less is obtained by acid-treating antimony pentoxide sol and sodium antimonate having a primary particle size of 5 to 100 mμ. Note that all of these antimony pentoxides have a tetrahydrate.

The flame retardant of the present invention is an alkali metal hydroxide (Na
OH, KOH), alkaline earth metals and/or zinc,
Soluble salts of lead (MgCI2゜CaCl2.BaCl2.
ZnCl2, ZnSO4Pb (NO3)2, etc.) or hydroxides (Mg(OH)2, Ca(OH)2
, Ba (OH)2.8H20, Zn (OH)2. P
b0-nH20, etc.), then add a water-soluble organic acid (citric acid, oxalic acid, malonic acid, tartaric acid, maleic acid, adipic acid, phthalic acid, fumaric acid, etc.),
It can be produced by further adding and mixing phosphoric acid and/or an alkali phosphate salt (the alkali salt is Na, NH3), and separating, drying, and pulverizing the obtained product.

Antimony pentoxide used in the present invention is a strong cation exchanger (Japanese Patent Publication No. 45-6695). Therefore, the added alkali metal ions and alkaline earth metal ions are strongly adsorbed and incorporated into the structure. Therefore, the cation exchange ability of antimony pentoxide can be blocked by adding an alkali metal hydroxide or a soluble salt of an alkaline earth metal to the antimony pentoxide sol and antimony pentoxide 1U suspension. And (M20 +M'O)
/5b205 retains the structure of antimony pentoxide tetrahydrate even when the molar ratio is 0.8 or more, and does not have a sodium or potassium antimonate structure. It is surprising that the cation exchange ability can be blocked even when a hydroxide with low solubility is used instead of the above-mentioned soluble salt. By adding an alkali, an alkaline earth metal compound, etc. as described above, the antimony pentoxide sol is micro-agglomerated to become a modified antimony pentoxide slurry. When salts are used, unnecessary anions such as chlorine cause a decrease in thermal stability and must be removed by deionization using an anion exchange resin. The modified antimony pentoxide slurry thus obtained has a pH of 8 to 11 because it contains a base having an ion exchange capacity or higher. An organic acid, phosphoric acid and/or an alkali phosphate salt are added to this slurry to adjust the pH to 6 to 9.

The organic acid, phosphoric acid, and/or alkali phosphate salt reacts with the alkaline earth metals, zinc, and lead in the slurry to form basic and normal salts, and forms a type of complex with antimony pentoxide.

In addition, the addition of organic acids, phosphoric acid and/or alkali phosphate salts such as alkali and alkaline earth metal compounds is carried out at room temperature for 10 minutes.
This is possible at 0° C., and strong stirring such as in a disper is preferable.

The antimony pentoxide-based flame retardant slurry thus obtained can be directly dried using a spray dryer, drum dryer, etc., or the slurry can be filtered by suction filtration, centrifugal filtration, etc., and after drying in a kiln, as necessary. The Iff refueling powder of the present invention can be obtained by grinding with a pin disc mill, shed o-mizer, etc.

In addition, this powder has a particle size of 0.2 to 10μ,
Even if it is 10μ or more, it has the characteristic that it can be easily pulverized using a Henschel mixer or the like.

The flame retardant of the present invention is a halogen-containing vinyl resin, a plasticizer, B
After mixing the a-Zn stabilizer with a Henschel mixer, 1
Two rolls at 70℃ with a thickness of 0. A wire sheet of 7 to 0.8 mm was produced.

The gear oven method was adopted as a test method for the thermal stability of this C.I. The oven temperature was set at 175°C, and thermal stability was evaluated based on the time taken for the test piece to blacken and the degree of initial coloration.

According to the above test method, initial coloring is smaller when an alkali metal and an alkaline earth metal and/or zinc or lead are mixed than when using an alkali metal alone. The amount added is 3 to 15% by weight of the alkali metal with the general formula M20 (M=NA, K);
Alkaline earth metals and/or zinc, lead in general 2M'O
(M'-Mg, Ca.

5 to 20% by weight as Sr, Ba, Zn, Pb), (
M20+M'O)/5b20s ratio is 0.8 to 0.8 in molar ratio
2.5 is preferred. If it is less than 0.8, it is insufficient to suppress the ion exchange ability of antimony pentoxide, and if it is more than 2.5, an excess of base remains and the basicity becomes extremely strong.
Promotes dehydrochlorination of halogen-containing vinyl resin, increasing initial coloring.

Furthermore, the addition of the above-mentioned organic acid has a remarkable effect on preventing initial discoloration, and the amount of addition of this organic acid is 1 to 8% by weight.
The M'0 ratio is preferably 0.05 to 0.5 in terms of molar ratio. 0.
If it is less than 0.5, the initial coloring cannot be made sufficiently small;
In the above case, although the initial coloring is reduced, the adhesion of the resin to the roll in the molding example is increased, and other disadvantages arise.

The addition of phosphoric acid and/or an alkali phosphate salt is also effective in preventing initial discoloration due to a different action from organic acids, and the amount of phosphoric acid and/or an alkali phosphate added is Pr.

5 is preferably 0.5 to 3 M%.

The thus obtained flame retardant of the present invention is mixed with a halogen, a vinyl resin, a plasticizer such as dioctyl phthalate, and Ba-Zn.
The method of blending with additives such as a system stabilizer and epoxidized soybean oil is a known method. For example, a halogen-containing vinyl resin, a powder stabilizer, and a flame retardant are mixed, and while stirring with a Henschel mixer, a liquid stabilizer is added. This is carried out by adding dioctyl phthalate (DOP) in which epoxidized soybean oil has been dissolved in advance and mixing the mixture until the temperature reaches 105°C to 115°C. At this time, the amount of the flame retardant of the present invention is 0.5 to 10 parts by weight per 100 parts by weight of the halogen-containing vinyl resin.

In the present invention, halogen-containing vinyl resin means vinyl chloride resin and copolymers thereof. Copolymers with vinyl chloride resin include ethylene, propylene, vinylidene chloride,
Vinyl acetate, vinyl alcohol, acrylic ester,
It is a copolymer with methacrylic acid ester, styrene, acrylonitrile, etc., and also includes a vinyl chloride graft copolymer, such as a graft copolymer with polystyrene, vinyl acetate, polyester, polyurethane, polystyrene, etc. A copolymer as used herein refers to a polymer containing two or more types of monomers.

The flame retardant of the present invention is a flame retardant for halogen-containing vinyl resins that does not impair the transparency of halogen-containing vinyl resins and does not deteriorate the thermal stability and cold resistance.

EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto.

The test methods adopted in the following examples are as follows, and the percentages in the compositions in Examples and Comparative Examples indicate weight percent.

Flame retardancy test: A press sheet with a thickness of 3.0 mm was prepared, and
The vertical test method of method L-94 was followed.

Bleed test: The test sheet was left at 80° C. and 99% humidity for 7 days, and visually observed to see if liquid oozed out onto the surface of a 1.0 mm thick press sheet.

Initial coloring property: The color difference due to reflected light of a 1.0 mm thick press sheet was measured, and the coloring property was expressed as Yl value (yellow value).

Transparency; 1. The transmittance (L value) of a pressed sheet having a thickness of OmrLl by transmitted light was measured.

Examples 1 to 5 and Comparative Examples 1 to 4 a) Production of flame retardant Example 1 Antimony pentoxide sol (S
b20slo%, Na2O0,57%.

PH=2.3) 720g to Zn (OH) 215g
.

After adding 2016 g of Ba (OH) 2 .8H and stirring with a disper for 2 hours, 3.0 g of maleic acid and 10
%H3PO4 aqueous solution was added and stirred for an additional 2 hours. The resulting slurry had a pH of 8°2. This slurry was filtered by suction filtration, the resulting wet cake was dried at 170° C. for 3 hours, and the dried product was pulverized using a pin disc mill. The average particle size of the obtained flame retardant powder was 3μ.

Example 2 Antimony pentoxide sol (S
b20512%,'Na2O0,80%.

PH=2.5) 600g and 3゜0g of NaOH (solid),
Zn(02()224g, Ba(OH)2 ・8H,
After adding 013[ and stirring with a disper for 3 hours, 4.5 g of maleic acid and 10 g of a 10% 83P04 aqueous solution were added, heated to 60° C., and further stirred for 3 hours. The pH of the resulting slurry was 7.5. The slurry was directly evaporated to dryness at -150'C for 5 hours, and then the solid was ground in a mixer and further finely ground in a jet automizer. The average particle size of the obtained flame retardant powder was 1 μ.

Example 3 Antimony pentoxide sol (Sb
20516%, Na2O0.98%.

PH=2.3) 460g and 3゜0g of NaOH (solid),
Mg (OH) 216g, Ba (OH)2 ・8H2
After adding 0Log and stirring with a disper for 2 hours,
5.8 g of adipic acid and 13 g of a 10% H3po4 aqueous solution were added, and the mixture was further stirred for 3 hours. P of the obtained slurry
H was 8.0.

This slurry was dried with a spray dryer.

The average particle size of the obtained flame retardant powder was 5μ.

Example 4 Antimony pentoxide/l/with a particle size of 20 to 50 mμ
(S b205 j2%, Na2O0,80%.

PH=2.5) 600g and 2゜0g of NaOH (solid)
, 20% Ca C12 aqueous solution 5.0 g, 20% ZnC
100 g of 12 aqueous solution was added and stirred with a disper for 1 hour. Next, 1000 g of anion exchange resin (Amberlite 410. Wet) was added to this slurry,
After dechlorination, the ion exchange resin was filtered off. Furthermore, 5.5 g of maleic acid and 15 g of 10% H3PO4 aqueous solution were added to this.
g was added thereto, and the mixture was further stirred for 2 hours. The pH of the obtained slurry was 6.2. This slurry was evaporated to dryness at 130''C, and then the dried product was ground with a pin disk mill. The average particle size of the resulting flame retardant powder was 3 microns.

Example 5 Antimony pentoxide sol (S
b20516%, Na20 1.0%, PH=2.3
) 460g and 12g of KQH (solid).

After adding 220 g of Ba (OH) 2 ・8H209, Og, Zn (0) and stirring with a disper for 2 hours,
Phthalic acid 4.2 [, 10% r-13P04 aqueous solution 17
g and warmed to 80'C and stirred for 2 hours. The resulting slurry had a pH of 8.8. The slurry was suction filtered and the wet cake was dried at 160° C. for 4 hours. Next, after coarsely pulverizing this dried material with a mixer,
It was ground in a pin disc mill. (The average particle size of the flame retardant powder obtained was 2μ.

Comparative Example 1 Antimony pentoxide/L with a particle size of 20 to 50 mμ,
(Sb2 o512%, Na20 0.80%.

PH-2,5) 4゜1g of NaOH (solid) to 600g,
2016 g of Ba(OH)2.8H was added and stirred with a disper for 4 hours. The pH of the obtained slurry was 8.8
Met. This slurry was suction filtered and the wet cake was dried at 150° C. for 4 hours. Next, this dried product was pulverized using a pin disc mill. The average particle size of the obtained flame retardant powder was 3μ.

Comparative Example 2 Antimony pentoxide sol (S
b20512%, 'j'Ja20 0.83%.

PH=2.3) 15g Na0flC solid) in 1000g
was added and stirred for 3 hours using a disper, then 3.5 g of maleic acid was added and further stirred for 2 hours. The resulting slurry had a Ptl of 8.5. This slurry was evaporated to dryness at 130°C and ground in a pin disc mill.

The average particle size of the obtained Ge 11 refueling powder was 3 μm.

Comparative Example 3 Sodium antimonate (1') crushed in a centrifugal ball mill
600 g of particle size 6 μ) was dispersed in 000 g of water, 60 g of a 10% 83P◯4 aqueous solution was added with stirring, and the slurry was then evaporated to dryness at 150° C. and ground with a mixer. The average particle size of the obtained N fuel powder was 6μ.

Comparative Example 4 Antimony pentoxide sol (Sb
20514%, Na20 0.82%.

PH-2,5) was spray-dried using a spray dryer.

The particle size of the obtained antimony pentoxide powder was 5.2μ
Met.

The compositions of the above Examples and Comparative Examples are shown in Table I.

b) Evaluation of flame retardants The nine types of flame retardants obtained in a) were further added with antimony trioxide (Comparative Example 5) as a comparative example, and sheets were made using the following two types of formulations (Table 2). They were prepared and evaluated for thermal stability, transparency, external combustibility, etc.

Note 1: Nissan Chemical Industries, Ltd. product, Nisozan Vinyl I-I
(I+-1000), Note 2; Kane Ace (B-22) Note 3; Product of Kanefuchi Chemical Co., Ltd.; Sho 4, Product of Nissan Ferro Co., Ltd.
;Adeka Argus product, 8DK fjZER0-
130P, Note 5; Sankyokisha product.

(5 TANN BM) The above mixture was mixed with a high speed mixer (Henschel mixer).
The compound was mixed for 0 minutes, and when the temperature rose to 105-115°C, the mixing was stopped, and the resulting compound was rapidly cooled to room temperature. A sheet with a thickness of 8 mm was prepared and subjected to a thermal stability test. In addition, after pressing the above sheet as it is or stacking several sheets at 180°C for 6 minutes, 1.0 mm and 3
．． A press sheet with a thickness of 100 nm was prepared and subjected to transparency, initial coloring, IF flammability, and bleedability tests. The results of combination recipe I are shown in Table 3, and the results of combination recipe H are shown in Table 4.Table 35As shown in Table 4, the flame retardant of the present invention is superior to flame retardants not shown in the comparative examples. . In particular, the flame retardant of the present invention is significantly superior to antimony pentoxide in terms of thermal stability. In addition, the flame retardant of the present invention is far superior to antimony trioxide in terms of transparency, and in terms of external flammability, antimony patent applicant Nissan Chemical Industries, Ltd.

Claims (1)

[Claims] 1) (A) The alkali metal is represented by the general formula M20 (M=Na,
(B) alkaline earth metal and/or zinc, lead in general formula M'0 (M'=M, g, Ca
, Sr, Ba, Zn, Pb) from 5 to 20% by weight, (
C) 1 to 8% by weight of organic acid, (D) 0.5 to 3% by weight of phosphoric acid and/or alkali phosphate as P2O5,
(E) A flame retardant for halogen-containing vinyl resins, the remainder of which is antimony pentoxide.