JPS63168460A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To provide a resin compsn. having improved transparency, heat resistance, etc., and greatly enhanced flame retardance, by blending a resin with specified antimony oxide. CONSTITUTION:A flame-retardant resin compsn. is obtd. by blending a synthetic resin such as PE, PP, ABS resin, with a dried product of aq. sol of Sb6O13 having a particle size of 1-100mmu. Antimony oxide has been used to obtain flame-retarded resins. However, when conventional antimony oxide having a particle size corresponding to that of pigment is blended, there are disadvantages that transparency, gloss and thermal stability are deteriorated. As a method of solving these problems, it is possible to use fine powder obtd. by heating and drying Sb2O5 colloid sol. However, only a hydrated product which is unstable at high temp. is formed so that a good flame-retardant resin compsn. cannot be obtd. The dried product of aq. Sb6O13 sol can be obtd. in an anhydrous form and does not cause thermal decomposition at high temp. so that an effect of imparting high flame retardance can be obtd. and a flame- retardant resin compsn. which is not foamed and has improved transparency and heat resistance can be obtd.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a tI flame-retardant resin composition, and more specifically to a tI flame-retardant resin composition containing a specific antimony oxide and having improved flame retardancy such as transparency and heat resistance. The present invention relates to a resin composition.

(Conventional technology) Polyethylene, polypropylene, polyester, ABS
Synthesis of resin etc! Although fats have excellent properties, they have the disadvantage of being easily combustible, and there is a growing demand for their flame retardance, depending on the purpose of use.

As a means for making such resins flame retardant, it is known to increase the flame retardancy by adding organic halogen compounds, organic phosphorus compounds, antimony oxide, etc., either alone or in combination, to the resin.

However, all conventional antimony oxides are large particles with a particle size comparable to that of pigments, so when they are blended into resins, they have the disadvantage of deteriorating the transparency, gloss, thermal stability, and other properties of the resins. Ta. In order to overcome these drawbacks, methods for obtaining finely divided antimony particles have been studied in recent years, and a method for producing antimony pentoxide (5bzOs) colloidal sol having a particle size of several tens of meters or more has been developed.
For example, Japanese Patent Publication No. 57-11848, Japanese Patent Application Publication No. 52-1
This method has been proposed in Publication No. 28997 and the like.

However, in order to blend 5bzOs colloid into resin, powdered 5b20s is desired, so 5bzOs
When colloid zo~ is heated and dried at a temperature of 100~200℃, 3bzOs hydrate is produced and only a product containing 5~10% water is obtained, and 5b20s is υ by heating.
Because it releases oxygen and decomposes, changing to 5b204,
5b20s has low flame retardant imparting efficiency and poor thermal stability, which causes foaming during melt molding of resin containing 8 ribs, resulting in problems such as deterioration of physical properties of molded products and damage to appearance. do.

In addition, antimony oxide (5b6
0t3) is also known, but even if such 5b6013 is pulverized, fine particles cannot be obtained, and the 5b601
The properties of the resin containing No. 3 will be impaired.

(Problems to be Solved by the Invention) Therefore, the present inventors have investigated the physical properties of foaming and molded products based on the fact that 5b205 is a hydrate unique to 5b205, and that it decomposes by releasing oxygen when heated. As a result of intensive studies on antimony oxide, which does not have problems such as deterioration, we first found a previously unknown 5b6013 aqueous solution with fine particles, high concentration, few impurities, thermal stability, and chemical stability. Discovered an aqueous sol with excellent properties, and filed a patent application in 1986-2.
66742 and Japanese Patent Application No. 60-266866.

In addition, even if the fine particles of the 5bsOta aqueous sol coalesce and become coarse during the drying process, when it is blended into the resin, they will be redispersed into secondary particles, resulting in deterioration of the transparency and color tone of the resin blended with them. We have discovered that there is no such thing, and have arrived at the present invention.

That is, the object of the present invention is to use the existing antimony trioxide (5b
It is an object of the present invention to provide a resin composition that has significantly improved flame retardancy without causing problems specific to zO3) and 5b20s.

(Means for Solving the Problems) The above object of the present invention is to provide a resin with a particle size of l to IQ Q m.
, u is achieved by a flame-retardant resin composition prepared by blending a dried 5b60x3 aqueous sol.

The present invention will be explained in detail below.

The resin used in the present invention includes resins such as thermoplastic resins, thermosetting resins, and thermoplastic elastomers with or without halogen and/or phosphorus, and one or more of them. It can also be a blend. Resin that does not contain halogen and/or phosphorus (
Examples of the halogen-incompatible resin include polyethylene,
Thermoplastic resins such as polypropylene, polyvinyl acetate, polystyrene, polybutene, polycarbonate, polyester, polysulfone; thermosetting resins such as epoxy resins, pheno-y resins, melamine resins, unsaturated polyester resins, silicone resins, etc. ;Natural rubber, butyl rubber,
Chloroprene rubber, styrene-propylene copolymer elastomer, ethylene-propyne copolymer elastomer, ethylene-vinyl acetate copolymer EFStomer, ethylene-propylene-diene! Examples include one-body elanuttomer, thermoplastic elastomer such as silicone rubber, and the like.

In addition, resins containing halogen and/or phosphorus (
Resins containing halogen, etc.) include vinyl halides or vinylidene halide such as vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, and vinylidene bromide; bis(
2-chloroethyl/L/) vinylphosphonate, bis(2
- Unsaturated phosphonic acid esters such as bromoethyl lv) vinylphosphonate, bis(2-chloroethyl/L/)methallylphosphonate, bis(2-promoethyl/L/)methallylphosphonate, diethylallylphosphonate, N-phosphonomethylacrylamide, etc. /' group i 2-hydroxyethyl methacrylate acidophosph Examples include polymers having at least one type of bond metal, or halogen specific gravity molecules such as halogenated polycarbonate, halogenated epoxy compound, polychlorostyrene, polybromostyrene, and poly(cypromov x nylene oxide).

In addition, when using a halogen-free resin, SbeO
It is preferable to use an organic halogen compound and/or an organic phosphorus compound together with the dried 1g aqueous sol. Examples of such organic halogen compounds include hexabromobenzene, hexachlorobenzene, penta)lebromobenzene, etc. , pentachlorotobaene, pen 7″ taglomophenol, pentachlorophenol, hexabromobiphenyl, decabromobiphenyl, tetrabromobutane, hexabromocyclototicane, perchloropentacyclodecane, decabromodiphenyl ether, octapromodiphenyl ether , hexabromodiphenyl ether, ethylene bis(tetrabromophthalimide), tetrachlorobisphenol A1 tetrabromobisphenol/VA, etc.; One example is merging.

Examples of organic phosphorus compounds include ammonium phosphate, tricresyl phosphate, triethyl phosphate, tris(β-chloroethyl Iv) phosphate, trischloroethyl phosphate, tris(β-chloropropyl)
phosphate, trisdichloropropyl phosphate,
Creshi tv! / phenyl phosphate, xylenyl diphenyl phosphate, ethylene bistris (2-cyanoethyl/L/) phosphonium bromide, tetrakis (
Hydroxymethyl)phosphonium sulfate −
To, trial report,
Examples include haloalkylboryline esters, phosphonic acid esters and condensates thereof, and polymers having the above-mentioned phosphorus monomers as a bond.

Of the above-mentioned organic halogen compounds and organic phosphorus compounds, 91 types or 2 or more types may be selected and used as desired, taking into consideration the properties of the resin used in the present invention and the use of the flame-retardant resin composition of the present invention. Even when a halogen-containing resin is used, an organic halogen compound and/or an organic phosphorus compound different from the resin may be used in combination.

Next, 5ba0 with a particle size of 1 to 100 m and u, which is an essential compound in the flame retardant resin composition of the present invention, is used.
13 The dried aqueous sol will be explained in detail.

First, as a method for producing 5b6013 aqueous zoy, the present inventors have already applied, for example, Japanese Patent Application No. 60-24 G 66%41! The No. 1 invention can be mentioned.

That is, 5b203, H2O2 and a specific alkali are mixed in l:t
, 25-1.8: 0.015-0.3 mol. The particle size of 5b203 may be approximately 100μ or less, but from the viewpoint of dispersibility in water, reactivity with H2O2, etc., it is particularly preferably 10 to 0.1μ. The concentration of 5bzO3 in the dispersion prepared by dispersing this 5b20s in an aqueous medium is 5 to 40% by weight, preferably 7% by weight.
~25% by weight.

The blending amount of H2O2 is 1°25~t, 8 mol per 1 mol of 5bzOa.
If it exceeds j, the chemical stability against electrolytes such as inorganic salts will decrease, and unreacted H2O2 will remain in the resulting aqueous sol, which is not preferable.

The alkali added to the 5bzO3 dispersion includes Li
It is necessary to selectively use an inorganic 7 /I/ potash substance such as OH, NaOH1Lt2CO3, NazCOs, etc. For example, even if KOH, Ca(OH)z, etc. are used, a fine particulate 5baO13 aqueous sol will not be generated. The amount of alkali added is 0.01 per mole of 5bzOs.
5 to 0°87ρ, preferably 0.02 to 0.2 mol; below the lower limit, the reaction slows down, so it is necessary to maintain the reaction temperature near the water line point or above the boiling point. Somehow, in a high concentration reaction system, the 5bsO obtained
When the particle size of u increases and exceeds the upper limit, 5b60
Not only is it not possible to selectively generate 13,
In a high concentration reaction system, the particle size becomes significantly coarse. Note that if a larger amount of alkali needs to be added in order to adjust the pH of the final product, it is possible to add the desired amount additionally at the final stage of the reaction.

There is no particular restriction on the order in which the above raw materials 5bzOs, H2O2 and alkali are mixed; for example, the three may be mixed at the same time, or H2O2 may be mixed into an aqueous dispersion of 5b203 and an alkali.

The temperature at which the aqueous dispersion is reacted is 30°C or higher, preferably 50 to 100°C, but the reaction can be started even at a low temperature of 50°C or lower, so the energy required to heat the reaction system is small. Most of the heat generated by the reaction is absorbed as heat to raise the temperature of the reaction system to the boiling point, and there is little need for external cooling.
There is almost no need to adjust the temperature to prevent bumping.

In this way 5-45% by weight, preferably 8-28%
5b6013 aqueous sol can be obtained. In addition, 5
The b6013 aqueous sol was previously treated by the present inventors with a specific organosilicon compound represented by the following general formula.
This is preferred because chemical stability is further improved.

R-8t-R2 Ra The 5b60+3 aqueous sol thus obtained is dried to produce powdered 5b6013.

Spray drying, drum drying, hot air drying, vacuum drying, etc. can be used as a drying method, but depending on operability, properties of the dried product, etc.
Spray drying and drum drying are preferred from the viewpoint of crushability, redispersibility into secondary particles, etc.

5b60+3+忰→ dried 5bsOx3 aqueous sol
When spray drying, the particle size of the powder becomes coarse, from 1 to 10, a, but the transparency is high, and this dried product can be easily dispersed in water, and the particle size before drying is 5b60.
] 3 Since the aqueous sol can be regenerated, for example, 5b6013 spray-dried at 180C or less is the agglomeration and coalescence of 5b6013 particles having a particle size of t-toomμ in the aqueous sol, and this 5b6
013 aggregates relatively easily during the blending process into resin4.
The coalescence is removed and the particles can be uniformly dispersed in the resin in the form of missing particles.

The flame-retardant resin composition of the present invention can be produced, for example, by the following method. First, resin and 5b601
When the type of resin is a thermoplastic resin or an elastomer, a conventional blending method can be used for the dry product of s and optionally an organic halogen compound and/or an organic phosphorus compound. 5bsO1s, optionally mixed with an organic halogen compound and/or an organic phosphorus compound, etc., and melt-mixed using a kneader, screw extruder, Banbury mixer, or mixing roll, etc., and can also be produced by thermosetting. In the case of a synthetic resin, it can be manufactured by mixing it with the resin raw material prior to curing.

The blending ratio of 5baOts dry matter to the resin should be selected in consideration of the type of resin used, its intended use, the required degree of flame retardancy, the type and amount of the organic halogen compound or organic phosphorus compound, etc. Although not particularly limited, it is preferably 0.02 to 80% by weight, preferably 0.05 to 20% by weight based on the resin. The blending amount is 0.02
If it is less than 80% by weight, the flame retardancy will be insufficient, and if it is more than 80% by weight, the flame retardance will increase, but the physical properties of the resin will be impaired.

Furthermore, if desired, the blending ratio of the organic halogen compound and/or organic phosphorus compound to be blended into the resin is 1 to 1 to
50% by weight is suitable.

The flame-retardant resin composition of the present invention may contain various antioxidants, ultraviolet absorbers, antistatic agents, color inhibitors, plasticizers, pigments, dyes, Lubricating βJ or a reinforcing agent can be added.

The flame-retardant resin composition of the present invention can be formed into films, tapes, ribbons, plates, tubes, pipes, fibers, foams, and other arbitrary shapes.

(Examples) Next, examples of the present invention will be shown, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

In addition, parts in Examples indicate parts by weight.

In addition, the test method in the examples is a combustion test conducted using the following method:
The test was carried out in accordance with the UL 94 combustion test method for glass materials (vertical method), and the flame was applied to the test piece for 10 seconds and the combustion time (in seconds) after the flame was removed was determined.

Weather resistance test @: The surface condition was observed after 400 hours of exposure using a Sunshine Super Long Life Weather Meter manufactured by Suga Test Instruments Co., Ltd.

Transparency test The transmittance of visible light was determined.

Example 1 A Milo flask (capacity: 1 g) with a stirrer was immersed in a 90° C. 1 warm water bath, and water, 5b203 (a degree 1
3% by weight, average particle size O, S, a > and NaOH
Water soluble (l (NaOH/ 5b203 = 0.1A/L
When the temperature of the contents reached 50°C, hydrogen peroxide (H2O2/5bzOs-IJ/1 molar ratio) was added and reacted for 1 hour to reduce the particle size to 1 to 20 m.
p, light transmittance 92%, chemical stability (5% Nacl@
Light transmittance when mixed) 88% 5b60ts: Z
Obtained Roid Sol.

The above 5beOts colloidal sol was heated to a drum surface temperature of 130
It was dried using a drum dryer at ℃ to obtain a scaly dried product. Next, this dried product was pulverized using an air jet mill to obtain a 5b60]3 dried product with an average particle size of 1.8 and a. When a part of this 5b6o13 dried material was dispersed in water using a homomixer so that the 5baOx3 concentration was 15%, the particle size was the same as that of the SbaO1g colloidal sol.

A spray-dried product of Lloyd sol was used.

Preparation of flame-retardant resin composition 100 parts of soft vinyl chloride resin manufactured by Toagosei Kogyo Co., Ltd., 60 parts of dioctyl phthalate as a plasticizer, Ba-Zn
3 parts of the system stabilizer and 3 parts of antimony oxide were mixed for 10 minutes at a temperature of 1750120 rpm using a two-roller hot roller mixer, and then mixed at a temperature of 150 rpm using a hot press molding machine.
A vinyl chloride/receipt with a thickness of 2H was prepared at #/d at 0c and a pressure of 150.

Table 1 shows the test results for flame retardancy, transparency and weather resistance of the obtained vinyl chloride sheet.

It is clear from the results in Table 1 that the product of the present invention has higher flame retardancy than the conventional 5b203.5bzOs product.
Excellent transparency and weather resistance.

(Effect of the invention) 5bsO]s blended in the flame retardant resin composition of the present invention is 1
= 100 m, which is obtained by drying an aqueous sol having a fine particle size of 5b2
Since it can be obtained as an anhydride different from 05, and it does not decompose even at the temperatures in the processing of various resins or in the high temperature range of various uses of resin products, it has a high flame retardant effect and can be used for foaming, etc. There is no deterioration in physical properties associated with
It can be uniformly dispersed in Ot3, thereby significantly improving the flame retardance without impairing the resin's original transparency or color tone, and improving the physical properties, processing performance, and processing performance of the resin with a smaller amount than conventional antimony oxide. The notable effects of the present invention are that it has become possible to provide a flame-retardant resin composition with excellent appearance.

Claims (1)

[Claims] 1. A flame-retardant resin composition comprising a resin and a dried aqueous sol of hexaantimony decathoxide having a particle size of 1 to 100 mμ.