JPH0157134B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a halogenated vinyl resin composition. More specifically, the present invention relates to a resin composition which is made by blending a resorcinol polyphosphate compound with a halogenated vinyl resin and has excellent flame retardancy and photostability without impairing physical and mechanical properties. Since halogenated vinyl resin has a high halogen content, it is itself non-flammable. Rigid halogenated vinyl resin compositions containing little or no plasticizer are typically self-extinguishing. The nonflammability of vinyl halide resins is generally lost when 25% or more of flammable plasticizers and other modifying ingredients are incorporated into the resin composition. It has been proposed to maintain the flame retardancy of plasticized vinyl halide resin compositions by using various phosphoric esters alone or in combination with other plasticizers. However, these resin compositions are not found to be completely satisfactory because the phosphoric esters are relatively costly and often have a deleterious effect on the physical and mechanical properties of the composition. For example, triaryl phosphate and cresyl diphenyl phosphate,
or compositions containing alkyl diaryl phosphates, such as 2-ethylhexyl diphenyl phosphate and isodecyl diphenyl phosphate, usually have insufficient low temperature flexibility and thermal and light stability; Compositions containing other trialkyl phosphates often do not have good processing properties.
In order to overcome these drawbacks of monophosphates, tetraaryl glycol diphosphates have been proposed in JP-A-49-40342. However, the phosphate compound using glycols described in the same publication had a small flame retardant effect and did not have sufficient light resistance. Also, JP-A-56-61446 and JP-A-57-
No. 55947 describes the use of a polyphosphate compound such as tetraaryl bisphenol A diphosphate in an amount of 5 parts by weight or less as a stabilizer for a halogen-containing resin. However, the compounds described in these publications have the disadvantage that they tend to bleed when used in relatively large amounts as flame-retardant plasticizers, and their flame-retardant effects are also small, making them unsatisfactory. According to the present invention, when a certain type of resorcin polyphosphate is mixed into a halogenated vinyl resin composition, a flame-retardant resin composition that has excellent photostability and is nonflammable or self-extinguishing can be obtained. It was discovered that That is, the resorcinol polyphosphate of the present invention is extremely effective as a flame retardant and plasticizer for halogenated vinyl resin compositions. The phosphoric esters of the present invention have no deleterious effect on the physical or mechanical properties of the resin composition when used in the amounts required to provide flame retardancy.
Resorcinol polyphosphate is stable to heat and moisture, and no decomposition is observed during the production and processing of the resin composition. These esters have low volatility and little tendency to migrate or leach, and compositions containing them maintain their flame retardant properties over long periods of time. The composition of the present invention can be obtained by mixing a phosphoric acid ester represented by the following general formula () into a halogenated vinyl resin composition. (In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a lower alkyl group, and n represents 1 to 5.) In the general formula (), as the lower alkyl group represented by R ₁ and R ₂ Examples include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl and the like. Specific examples of phosphoric acid esters include phenyl resorcin polyphosphate, cresyl resorcin polyphosphate, and phenyl resorcin polyphosphate.
Cresyl resorcin polyphosphate, xylyl resorcin polyphosphate, phenyl pt-butylphenyl resorcin polyphosphate, phenyl isopropylphenyl resorcin polyphosphate, cresyl
Examples include xylyl resorcinol polyphosphate, phenyl isopropylphenyl diisopropylphenyl resorcinol polyphosphate. The amount of the phosphoric ester of the present invention added is in the range of 5 to 70 parts by weight, preferably 7 to 50 parts by weight, per 100 parts by weight of the resin. If the amount added is less than 5 parts by weight, the flame retardant effect will be insufficient, and if it is added in excess of 70 parts by weight, the flame retardant effect will not be further improved and is actually unnecessary. Although the phosphoric esters of the invention may be used as the sole plasticizer in the compositions of the invention, they are usually used in combination with at least one commonly used plasticizer well known in the art. It is preferable. A wide variety of plasticizers can be used in combination with phosphate esters. Monohydric or dihydric alcohols and phthalic anhydride, trimethic anhydride, fatty acids, adipic acid, azelaic acid, sebacic acid,
Best results have been obtained using primary ester plasticizers, which are mono-, di-, and triesters made by reaction with benzoic acid, citric acid, and other acids. The most useful of these primary ester plasticizers are the dialkyl phthalates such as dibutyl phthalate, dihexyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, di-2-ethylhexyl phthalate, dinonyl phthalate, didodecyl phthalate, and hexyl phthalate. Octyl phthalate; arylalkyl phthalate such as butyl benzyl phthalate;
Dialkyl sebacates such as dibutyl sebacate and di-ethylhexyl sebacate, dialkyl adipates such as di-n-octyl adipate, diisooctyl adipate, and diisodecyl adipate; dialkyl azelates such as diisooctyl azelate, trialkyl trimellitates such as -2-ethylhexyl trimellitate, tri-n-octyl trimellitate; citrates such as acetyltributyl citrate;
Alkylphthalyl alkyl glycolates such as ethyl phthalyl ethyl glycolate and butylphthalyl butyl glycolate; and glycol benzoates such as diethylene glycol dibenzoate and dipropylene glycol benzoate. Particular preference is given to using dioctyl phthalate as primary ester plasticizer. In addition to the phosphoric ester and primary ester plasticizers, the compositions of the invention can contain smaller amounts of other plasticizers, such as epoxidized esters and chlorinated paraffins. from about 0.1 to about 10 parts by weight of phosphoric ester to obtain a plasticized composition with a desirable combination of properties.
Use parts by weight of primary ester plasticizer. The most satisfactory results were obtained when the plasticizer mixture contained 1 to 5 parts by weight of primary ester plasticizer per part by weight of phosphoric ester. In using a plasticizer comprising the resorcinol polyphosphate of the present invention, the amount of halogenated vinyl resin that can impart flame retardancy, low temperature flexibility, and other important properties to the halogenated vinyl resin composition is From about 5 to about 100 parts by weight per 100 parts by weight, or more. In most cases, flame retardancy and an excellent combination of physical and mechanical properties are obtained when from about 30 to about 60 parts by weight of plasticizer per 100 parts by weight of halogenated vinyl resin are used. For polyvinyl chloride compositions, 40 parts by weight of a plasticizer comprising a phosphate ester per 100 parts by weight of the resin.
Best results are obtained when used in amounts of ~50 parts by weight. The halogenated vinyl resin that can be present in the flame-retardant resin composition of the present invention is a resin composition obtained by polymerizing vinyl halide in the presence or absence of a copolymerizable monomer. It is. As used herein, the term "vinyl halide resin" includes halogenated vinyl homopolymers, such as polyvinyl chloride, polyvinyl bromide, and polyvinylidene chloride, as well as halogenated vinyl copolymers; are vinyl halides and comonomers such as vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl chloroacetate; vinylidene chloride; vinyl alkyl sulfonates; vinyl ethers such as vinyl ethyl ether, vinyl isopropyl ether,
and vinyl chloroethyl ether; cyclic unsaturated compounds such as styrene, chlorstyrene, coumaron, indene, vinylnaphthalene, vinylpyridine, and vinylpyrrole; acrylic acid and its derivatives such as ethyl acrylate, methyl methacrylate, ethyl methacrylate, ethyl chloroacrylate, Acrylonitrile and methacrylonitrile; dialkyl fumarates and maleates; unsaturated hydrocarbons such as ethylene, propylene, and isobutene; allyl compounds such as allyl acetate, allyl chloride, and allyl ethyl ether; and conjugated and crosslinked ethylenically unsaturated compounds such as butadiene , isoprene,
Included are chlorprene, and divinyl ketone; and mixtures thereof. Copolymers that can be used in the practice of this invention are those containing at least 70% vinyl halide and up to 30% comonomer units. The invention can also be applied to mixtures of large proportions of halogenated vinyl resins and small proportions of other synthetic resins, such as polyethylene, polypropylene, ABS, polyacrylates and polymethacrylates; Synthetic rubbers such as neoprene, silicone, nitrile, and
SBR: Includes polyurethane, polyamide, polystyrene, phenolic resin, urea resin, cellulose ester, epoxide, etc. The compositions of the invention may contain stabilizers, fillers, pigments, dyes, extenders and other additives in amounts commonly used for the above purposes. The invention is further illustrated by the following examples. In these examples, all parts are by weight and all percentages are percent by weight. Example 1 A test piece was prepared using the following formulation, and a thermal stability test at 175°C and a photostability test using xenon lamp irradiation were conducted. The results are shown in Table 1. (Composition) PVC (=1050) 100 parts Phosphate ester 50 MARK-AC183 4 (Ba-Zn-phosphite liquid stabilizer)

[Table] Example 2 A test piece was prepared using the following formulation, and the oxygen index was measured according to JISK7201. The results are shown in Table 2. (Composition) PVC (=1300) 100 parts Ba-Zn-phosphite liquid stabilizer 3 Stearic acid 0.5 Epoxidized soybean oil 5 Dioctylphthalate phosphate ester 45

[Table] Example 3 Test pieces were prepared using the following formulation and various performance tests were conducted. The results are shown in Table 3. (Composition) PVC (=1300) 100 parts Epoxidized soybean oil 5 MARKAC-183 2.5 MARK1500 (phosphite stabilizer) 0.5 Butyl stearate 0.5 Stearic acid 0.2 Trioctyl trimellitate 40 Phosphate ester 10

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Claims (1)

[Scope of Claims] 1 100 parts by weight of a vinyl halide resin and a polyphosphate compound represented by the following general formula () 5
A halogenated vinyl resin composition comprising ~70 parts by weight. (In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a lower alkyl group, and n represents 1 to 5.)