JPS5924752A - Method for making thermoplastic resin flame-retardant - Google Patents

Abstract

PURPOSE:To impart high flame retardance safely and easily, by blending a specified amount of a flame-retardant compsn. consisting of a styrene/acrylonitrile copolymer and red phosphorus powder which has been impregnated with a thermosetting resin and then cured, with a thermoplastic resin. CONSTITUTION:Styrene and acrylonitrile are copolymerized in such an amount as to give an acrylonitrile content of 10-40wt%, to which is added, pref., a rubber component such as polybutadiene to obtain a styrene/acrylonitrile copolymer (A). Red phosphorus powder having an average particle size of 0.1- 100mu is impregnated with a thermosetting resin such as phenolic resin, which is then cured. Component A and the resulting red phosphorus powder are mixed together in such a proportion as to give a red phosphorus content of 20-70wt% in terms of elementary red phosphorus. The resulting flame-retardant compsn. is blended with a thermoplastic resin such as polyester or polyamide in such an amount as to give a phosphorus content of 0.5-20wt% in terms of elementary red phosphorus, whereby the thermoplastic resin is made flame-retardant.

Description

[Detailed description of the invention]

The present invention relates to a method for flame retardant thermal iiJ plastic 4QJ fat. Synthetic resins (hereinafter referred to as "glasstic") have traditionally been highly valued due to their excellent physical properties and ease of molding.
In recent years, due to the demands for labor saving (productivity) and energy savings, soil has been used in a variety of ways for many purposes, including home appliances, machinery, automobiles, #4% construction, and other fields. It has made a major contribution to development. However, in fields such as electronics such as televisions, electromechanical parts, automobile parts, and construction materials, the demand for flame retardant plastic materials is becoming more severe year by year. Therefore, without compromising the original excellent properties of plastic, we have developed a high degree of separation that complies with, for example, the safety standard of UL-1410 (for televisions) UL-1410 (K) by Underwriters Laboratory in the United States. It has become necessary to impart flammability. Many methods of burning plastic have been proposed so far. For example, halogen-containing organic compounds, phosphorus-containing organic compounds, nitrogen-containing compounds, and inorganic compounds such as citron are known to be effective as flame retardants. However, in order to meet the above flame retardant standards with these compounds, it is first necessary to increase the additive grade, which not only impairs the excellent physical properties of plastics, but also requires uniform dispersion and kneading of a large amount of flame retardant. It is difficult and often has poor operability. Relatively recently, elemental phosphorus, especially red phosphorus, has become known as an effective flame retardant in small amounts for some plastics, but it has only been put into practical use because of its cross-contamination with liquid raw materials at around room temperature. Only some curable 461 resins can be molded. Red phosphorus has the risk of igniting and generating boss fins under high temperatures and mechanical stress. Therefore, Japanese Patent Publication No. 54-39200 describes a method of coating the surface of red phosphorus particles with a thermosetting resin. However, its resistance to high temperatures and mechanical shock is insufficient, and its application to high melting point thermoplastic resins has not been realized. Furthermore, the flame retardant effect of red phosphorus is not sufficient, and further improvements are still desired. The present inventors completed the present invention as a result of research to eliminate the defect Jv1. An object of the present invention is to provide a method for safely and easily making a thermoplastic resin with a high melting point flammable and increasing the flammability effect of red phosphorus. The method of the present invention uses a flame retardant composition consisting of a styrene-acrylonitrile copolymer and a red phosphorus powder impregnated with a thermosetting resin and cured to form a flame retardant composition for polyester, polyamide, polyurethane, polyester ether, polyamide ether, polyphenylene oxide, polycarbonate. and polyps

[It is characterized by being blended with at least one thermoplastic resin selected from '11p consisting of Tar W, and containing 0.5 to 20 M ML% of elemental red phosphorus. The styrene-acrylonitrile copolymer used in the present invention has a total of 1i1 of styrene and acrylonitrile,
It is a copolymer of 10 to 40% by weight of acrylonitrile, preferably 15 to 60% by weight, and the rubber component is the entirety (styrene, acrylonitrile and rubber component).
40% by weight or less, preferably 50% by weight or less, by mixing and/or copolymerization. Rubber components include polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-e-vinyl acetate copolymer, etc., but the blending method improves the impact resistance of the styrene-acrylonitrile copolymer tree IJi7. It is desirable that there be. So-called AB8 resin, As resin, etc. are preferably used. These styrene-acrylonitrile copolymers, such as polystyrene, polyethylene, polypropylene, polybutadiene, polyacrylic acid, etc., have the advantage of increasing the flame retardant effect of red phosphorus in the method of the present invention. The red phosphorus powder impregnated and hardened (coated) with a thermosetting resin used in the present invention usually has an average particle diameter of 0.1 to 10
0 micron (μ), preferably α5 to 30μ red phosphorus from the group consisting of so-called phenolic resins, melamine resins, urea resins, furfuryl alcohol resins, aniline resins, ketone resins, epoxy resins, unsaturated oropolyester resins. It is coated with selected phosphorus, and the coating content is usually 1 to 30% by weight based on red phosphorus. In general, a coating of 5 to 20 percent multiplication yields stabilized red phosphorus with less agglomeration between particles, and exhibits significant oxidation and impact suppression effects in air. The most preferred resins include phenol/aldehyde resins, urea aldehyde resins, melamine, and aldehyde resins. Geography using thermosetting resins is usually done by adding resin raw materials (including initial condensate) to an aqueous side liquid of red phosphorus, and processing the resin under the usual polymerization conditions for each resin under strong stirring. Red phosphorus, copper oxide, antimony oxide, lead oxide, molypran sulfide, zinc oxide, +1 acid? 11L lead, manganese oxide, cobalt oxide,
Magnesium hydroxide, activated carbon, melamine, stabilizers such as melamine/amerate, polyacrylonitrile powder, phosphine absorbers, flame retardant enhancers, or, if necessary, halogenated brominated diphenyl ethers, tripromophenol merigomer caps. Other fuel powders such as J-bale compounds can also be mixed and processed. As a phosphine absorbent! Antimony oxide is also good for j1ψ.
1, in that case 0.01 to 2 times h1 for red lean
Add within the range. Thermal ω1j conversion tree) 1ii Coding Red phosphorus blended into styrene-acrylonitrile copolymer, 20 to 70 quintillion 1% as elemental red phosphorus, based on the total JiJ composition.
Good iL< is set to 30 to 60%. Red phosphorus combination 1. Since the compounding operation can generally be carried out at low temperatures, L is 6 of the styrene-acrylonitrile copolymer.
It is best to select a material with good mobility, and the composition of the styrene-acrylonitrile copolymer described above is usually selected. Preferably, operating temperatures below 220°C are used. The blending operation is usually carried out by thoroughly dispersing the former into the latter using a melt kneader under an inert gas atmosphere such as nitrogen. In order to soften the mechanical impact on red phosphorus, some or all of the resin may be used in powder form. In addition, relatively soft and slippery inorganic fine powders such as talc and clay can also be used together. Further, at this time, powders such as the above-mentioned red phosphorus stabilizer, posphine absorbent, other flame retardants, and pigments can also be mixed and used. Preferred posphine absorbents and flame retardants include antimony oxide, melamine, and thecafrom diphenyl ether. The mixing ratio of these powders to be used in combination varies depending on the properties of each powder and the purpose of use, but it is usually 0 [11 to 2 times mm, preferably [ ], 05 to 1 times as much as red phosphorus. . Z) Polyesters applicable to the present invention include polyethylene terephthalate, polybutylated non-terephthalate,
Polyhegylene terephthalate, ho! I-p-hydrokine ethodipenzoate, poly 2.2'-bis-p-oxy7phenylpropane infertate, poly 2.2
'-bis-p-(β-hydroxy/j-togysiphenyl)
Polypanderephthalate, polybis-p-oxyphenylsulfone isophthalate, polybis-p-(β-hydroxyethoxyphenyl)sulfone terephthalate,
Examples include poly p, p'-cyclohexane dimetatool terephthalate, polybis-β-hydroxyethyloxybenzene terephthalate, polybutylene naphthalate, polyvivalolactone, poly-ε-caprolactone, polyethylene oxalate, polyethylene adipate, etc. . Of course, various copolymers, mixtures, and modified products of these may also be used, including copolymers partially using polyfunctional compounds such as pentaerythritol, pyromellitic acid, and trimellitic acid. In addition to the monomers constituting each of the above-mentioned polyesters, examples of monomers serving as copolymerization components include orthophthal 1], oxidibenzoic acid, p+T''-biphenyl dicarboxylic acid, tetrabromoterephthalic acid, and tetrabromide. Ornophthalic acid, tetodichlorophthal r2.
Sodium 4-sulfonate inophthalic acid, pimelic acid, speric acid, azelaic acid, globylene glycol,
These include neopentyl glycol, octanediol, diethylene glycol, triethylene glycol, and polyethylene glycol. Examples of the polyamide applicable to the present invention include so-called 4 nylon, 6 nylon, 7 nylon, 9 nylon, 11 nylon, 12 nylon, 6.6 nylon, 6.9 nylon, 6.10 nylon, 1-piperadiene/adipamide stop fat. Group polyamides, polymethaxylylene adipamide, polyundecamethylene terephthazimide, polydodecamethylene lenticin.Of course, various copolymers, mixtures, and modified products of these are also used. as,
In addition to the 11 constituent units of each of the polyamides mentioned above, ethylenediamine, -tramethylenediamine, octamethylenediamine, nonamethylenediamine, histo-γ-aminopropyl ether, varaginlylenediamine, etc., and the polyesters (111 Various types of polyurethane can be used for polyurethane. A prepolymer obtained by reacting a high-molecular European polyol with an aliphatic or/and aromatic diisocyanate is polymerized using a Ni chain extender. Typical polyols include: Polyethylene adipate, polyptylene/adipate, poly-ε-cabrolactone, polynib-L/glycol, polypropylene glycol, polybutramethylene glycol, etc. are used as the di-f-nocyanate, and examples thereof include 4,4'-diphenylmethylene glycol.・F-socyate, toluylene diisocyanate, hegylene diisocyanate, etc., and LL agents in chain 1 include ethylene glycol, 1,4-butane diol, bis-β-
Hydroxyethoxybeni/-hin, tJ-methyljetanolamine, N. Examples include IJ' dimethylhexamethylene diamine, hexamethylene diamine, ethylene diamine, NIN' diC methyl ethylene diamine m-1 or P-quinlylene diamine. The polyester ether or polyamide ether to be applied to the present invention includes the aforementioned raw material monomers (or oligomers) of the polyester or polyamide, and polyethylene glycol, polypropylene glycol, polybutylene glycol of various degrees of combination, or these. Examples include random or block copolymers which can be used in combination with polyether diamine in which the terminal hydroquine group has been changed to an amino group. The droxyl group of the polyol undergoes an 11-nitrile addition reaction (・/'f noethylation).
After that, the nitrile group can be converted into an amino group by ice water conversion-I, also known as IiC. Polyethylene glycols include sulfur, f-ethylene glycol, and triethylene glycol:/
It is possible to use everything from low-molecular IU molecules such as 11-call to several hundred to tens of thousands of molecules. The father, other polyols, are also the same HA. . The polyphenylene A oxide that can be applied to Kinoe Akikata UC is one obtained by oxidative polymerization of 2,6-xylenol to obtain -C, or one in which the dielectric layer is modified with polystyrene or the like. Ru. Modification methods include the 5L blending method and the grafting method. Polycarbonate is obtained by reacting an aromatic diol such as 12.2'-bis-P-hydroxyphenylpropane with diphenyl carbonate or phosgene, or it is obtained by modifying these with polyester, polyolefin, polystyrene, etc. Examples of polyacetals include polymigidimethylene and copolymers thereof with ethylene oxide, etc. Thermoplastic resins to be made flame retardant by the method of the present invention also include mixtures of the above-mentioned polymers. It is also made of polyester.
Ramides, polyester amide ethers, etc. can also be effectively made flame retardant by the method of the present invention. In the method of the present invention, a composition of styrene-acrylonitrile copolymer (usually in the form of chips) containing highly concentrated red phosphorus coated with thermosetting 4Q fat is blended into the thermoplastic 4Q fat, thereby safely and efficiently. However, the content of elemental red phosphorus should be 05 to 20% by weight, preferably 1 to 15% by weight of the total.[If it is less than 15% by weight, it will have a flame retardant effect. is insufficient, and on the other hand, even if it exceeds 20%, the flammability will not be further improved, but rather the physical properties of the resin will be impaired.The blending operation can be continuous or discontinuous.
! The crosstalk machine, father, can be carried out by each fili forming machine, in which case each replenishment agent, n1° (
additives, stabilizers, reinforcing phases, other flame retardants, phosphine absorbers,
Modifiers such as lubricants can be added as appropriate! ! ! Z. Well known: IG 1. G, a- or high pour point heat ij4 plastic resin polyethylene terephthalate)
−? 66 Nylon, polycarbonate, modified polyphenylene oxytide, polyphenylene oxide, etc. can be directly kneaded with red phosphorus, without the risk of ignition, decomposition of red phosphorus, or generation of large rivers of phosphine, a toxic gas. Because it's easy,
Even in the case of red phosphorus coated with a thermosetting resin, it was difficult to put it to practical use, but the method of the present invention can safely, economically, and with a thermosetting ratio of 1'' (☆1 fat protection I'A). However, the high concentration red phosphorus-containing styrene-acrylonitrile copolymer of the present invention almost impairs the physical properties of the flame-retarding symmetrical resin of the present invention: Red phosphorus with other polymers as a matrix exhibits a superior M combustion effect than when red phosphorus is directly blended. Ki It is something that is limited
I/'1o Also, "part" indicating the unit before use in the examples
, or "%" unless otherwise noted, lI! Relative viscosity, which is a measure of the degree of polymerization (molecular weight) of a polymer, is measured in dimethyl formamide for polyurethane, and in a gamma-containing bath of phenol and dichloroethane for its oil. and in1 at a concentration of 1%]
It has been established. In addition, the tensile strength of the S molded product is A8
'I' M D-668, the impact (notched) is in accordance with the same D-256, and the flammability is 611 in accordance with the American Underwriters Laboratory standard LIL-94.
It was fixed at 1. Actual) 61! /su1 Rubber component 20M1% obtained by polymerizing styrene and acrylonitrile in the coexistence of polybutadiene latex
Table-1
The mixture was melted and kneaded to give a red phosphorus concentration (elemental red phosphorus conversion η) shown in . For the mixing operation, a two-axis continuous mixing machine was used, the cylinder temperature was about 190° C., nitrogen gas was flowed through the raw material supply port, red phosphorus powder was quantitatively added to the molten ABS resin, kneaded, cooled, and chipped. The obtained ABS resin chips with various red phosphorus concentrations were mixed with polyethylene terephthalate (PET) having a relative viscosity of 1.85, and mechanical property test pieces and flammability test pieces were produced using an injection molding machine. The red phosphorus concentration is constant at 2.5%, and the molding machine cylinder temperature is
The temperature was 265 to 270°C and the mold temperature was 130°C. -For comparison, 2.9% of the above red phosphorus powder (2.5% as elemental red phosphorus) was added to the same polyethylene terephthalate-1.
), the same red phosphorus powder was diluted to a red phosphorus concentration of 25% with titanium powder with an acid ratio of 105y;, respectively.
The mixture was directly melt kneaded in a bath at 270°C and injection molded in the same manner. 1
As an example, the same polyethylene phthalate was injection molded as is. Each 6L A'FM and the injection molding operation were smooth, but in the comparative example where the kneading temperature was high, the raw material supply port, extrusion port (die), mold, and the resulting chips were The molded product had a strong phosphine odor and continued operation was difficult. This is thought to be due to the large 1jtIIW of the red phosphorus 7 enol resin film due to impact and high temperature. The physical properties and flame retardance of each test piece obtained are shown in Table 1 along with the red phosphorus-containing nap manufacturing conditions. It can be seen that the flammability and physical properties are excellent, the occurrence of boss fins is very small, and the safety is directly at t1. Example 2 In addition to the AB8 resin used in Example 1, styrene-acrylonitrile copolymer (so-called AS resin) of rylonitrile 25X', Boristine, 4&degree polyethylene, and polypropylene were used, and phenolic resin coating red Phosphorus (red phosphorus content: 86%) powder and Example 1 were melted and mixed in the same manner as in Example 1. However, the red phosphorus temperature (elemental red phosphorus conversion) T) is constant at 1135%, and the crosstalk temperature is 1 d.
The temperature was 170 to 200°C. The operation was smooth and there was almost no phosphite odor. 17 parts of each of the Id 41] red phosphorus-containing resin chips were mixed with 83 parts of polyhexamethylene adipamide (66 nylon) having a relative viscosity of 2.2, and molded into mechanical property test pieces by an injection molding machine. A test piece for combustibility was prepared. Molding machine cylinder temperature 26 S r, mold temperature 65
℃, but the molding operation was smooth and there was almost no phosphine odor. For comparison, 7 parts of the phenolic resin-coated red phosphorus powder was bath-melted and kneaded with 93 parts of the 66-silon to obtain red phosphorus master chips having an elemental red phosphorus concentration of 45%. The crosstalk operation was smooth and there was no phosphine odor. The obtained red phosphorus master chip was mixed with each of the following polymer chirags so as to have the red phosphorus concentration shown in Table 3, and a mechanical property test piece and a flame retardant test piece were produced using an injection molding machine. Although the molding temperature conditions were different for each polymer as shown in Table 3, each molding operation was smooth and there was no or very slight phosphine odor. Polymer made flame retardant with the above red phosphorus master chip
- is 55 parts of polytetramethylene glycol with a molecule of 11,800,! :, a polyurethane resin with a relative viscosity of 1.9 obtained by combining 25 parts of 4.4'-diphenylmethane diisocyanate and 6 parts of chain extender bis-β-hydroxyethoxybenzene, commercially available polyester ether resin R HELPLEN P150BJ (manufactured by Toyobo Co., Ltd.), commercially available polyamide ether (α1 resin “Diamide PAE-B65TL
J (manufactured by Daicel Hyporus), commercially available polyphenylene oxide resin [Noryl 731-JJ (manufactured by Engineering Plastics Co., Ltd.), commercially available polycarbonate resin "Panlite L-1225j (manufactured by Yondai Kasei Co., Ltd.), and commercially available polyacetal Resin Utenac 5'010 J
(manufactured by Asahi Kasei Corporation), low-density polyethylene “Yukalon MY-
503 (manufactured by Mitsubishi Yuka Co., Ltd.), but for comparison, 15%
The same concentration of red phosphorus master chips (elemental red phosphorus concentration: 45%) obtained by melt-kneading red phosphorus powder coated with paraffin wax with A S (JJ fat) was blended with TonoL et al.'s resin chips. When the same paraffin wax-coated red phosphorus was melt-kneaded directly into the resin of this company and the resulting chip was injection molded, the 1ffl resin of the company was further The results of injection molding without adding a flame retardant are also shown in Table 5. ``AS resin master coated with phenolic resin and using red phosphorus powder, which is one of the thermosetting adhesives.'' For chips.”
It can be seen that the flame retardant method is significantly superior in terms of handling (phosphine generation). Also,
Red phosphorus master chip of As resin except in the case of polyethylene Example 4 Styrene-acrylonitrile copolymer (so-called A u 467 fat) with 25% acrylonitrile, phenolic resin coated red phosphorus powder (red phosphorus index 86%),
Antimony oxide powder and decabromodiphenyl ether powder were melt kneaded in a bath to obtain an elemental red phosphorus concentration of 30%, an antimony oxide by-product of 7%, and decabromodiphenyl ether 2.
An 8% AIL refueling composition was obtained. Crosstalk operation is approximately 200℃
However, there was no small sphine odor at circle rη. For comparison, a composition containing 7f monteca from diphenyl ether oxide with the same degree of harshness as above but without phosphorus was prepared. 1U of the flame retardant composition was mixed with a commercially available polycarbonate chip "Panlite L-1225J (manufactured by Yondai Kasei Co., Ltd.)" to form each red phosphorus VT Arashi shown in Table 4, and these were injected. Mechanical property test pieces and Jll (flammability test pieces) were prepared using a molding machine.The molding temperature was set at 290°C, but the operation was yen juice I, and there was no phosphin odor.Table 5 shows the physical properties and The flammability measurement results are shown, and it is preferable that the redness/intensity be 1% or more (it can be seen that below 15%, the flammability is insufficient). However, A S 4i°rJ fat red phosphorus master chips with an elemental red phosphorus concentration of 55% and an antimony oxide concentration of 3%, which were obtained by using antimony oxide powder in combination, were mixed with commercially available glass fiber reinforced polyacetal resin "Tenasoku GA520 J". It was blended and injection molded.Table-
The measurement results of mechanical property test pieces and flame retardant test pieces obtained at each red phosphorus concentration in 5 show that at red phosphorus concentrations of 20% or more, the physical properties deteriorate sharply and there is no improvement in flammability. It shows.

Claims (1)

[Scope of Claims] (1) A flame retardant composition consisting of a styrene-acrylonitrile copolymer and red phosphorus powder impregnated with a thermosetting resin and hardened is applied to polyester, polyamide, polyurethane, polyester ether, polyamide ether, At least 1.1 selected from the group consisting of phenylene oxide, polycarbonate and polyaceter 1 to ff.
jJiO thermoplastic resin is blended with elemental red phosphorus from 05 to
A thermoplastic TL characterized by containing 20% by weight of kernels.
/ J-i fat and flame retardant method. (2) Styrene/acrylonitrile copolymer is 10
2. The method according to claim 1, which contains up to 40% acrylonitrile. (5) The method according to claim 1 or 2, wherein the styrene-acrylonitrile copolymer contains a rubber component. (4) The content of elemental red phosphorus in the flame retardant composition is 20~
70% weight-M. The method according to claim 1. (5) The method according to claim 1, wherein the thermosetting resin is a phenol/aldehyde resin, a urea/aldehyde resin, or a melamine/aldehyde resin. (6) 1 to 30% thermosetting resin to elemental red phosphorus
Special T that gives nail amount%? The method according to item 1 of the scope of search. (7) The method described in item 1 of the patent, wherein the red phosphorus powder impregnated and cured with a thermosetting resin has an average particle size of 01 to 100 μm.