JPS5930845A - Halogenated vinyl resin composition - Google Patents

Abstract

PURPOSE:To provide the titled composition having remarkably improved flame retardance and light stability without lowering the physical and mechanical properties, by compounding a resorcinol polyphosphate compound to a halogenated vinyl resin. CONSTITUTION:100pts.wt. of a halogenated vinyl resin is compounded with 5-70pts.wt., preferably 7-50pts.wt. of a polyphosphate compound of formula (R1 and R2 are H or lower alkyl; n is 1-5), and 0.1-10pts.wt., based on 1pt.wt. of the phosphoric acid ester, of a plasticizer, preferably dioctyl phthalate as a primary ester plasticizer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to halogenated vinyl resin compositions. 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 its physical and mechanical properties.

Since the halogenated vinyl resin has a high halogen content, it is itself nonflammable. Rigid vinyl halide resin compositions containing little or no plasticizer are usually self-extinguishing when 25% or more of flammable plasticizer and other modifying components are incorporated into the resin composition. The nonflammability of halogenated vinyl resins is generally lost.

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 phosphoric acid esters are relatively expensive and often have a detrimental effect on the physical and mechanical properties of the composition. I can't do it. For example, compositions containing triaryl phosphates such as tricresyl bosphate and cresyl diphenyl phosphate or alkyl diaryl phosphates such as 2-ethylhexyl diphenyl phosphate and isodecyl diphenyl phosphate usually have insufficient low temperature flexibility. Compositions containing trioctyl phosphate or other trialkyl phosphates that have good stability and thermal and light stability are often good? It has no processing characteristics. In order to eliminate these drawbacks of buemonophosphates, JP-A-49
-Tetraaryl glycol-
Diphosphates have been proposed. However, from 1K onwards, the bosphate compounds using glycols described in the same publication had a small flame retardant effect and did not have sufficient light resistance.

In Japanese Patent Application Laid-open No. 56-61446 and Japanese Patent Application Laid-open No. 57-55,947, polyphosphate compounds such as tetraaryl bisphenol A diphosphate are used as stabilizers for halogen-containing resins in amounts of 5 parts or less. It is stated that it is used. 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! won.

According to the present invention, when a halogenated vinyl resin or a certain type of resorcinol polyphosphate is mixed into the composition,
It has been found that a flame-retardant resin composition that has excellent photostability and is nonflammable or self-extinguishing can be obtained. That is, the resorcinol polyphosphate of the present invention is extremely effective as a refractor and plasticizer for the halogenated vinyl resin composition K WIG. The phosphoric esters of this invention, when used in the amounts required to provide flame retardance, have no deleterious effect on the physical or mechanical properties of the resin composition. Resorcinol polyphosphate is stable against heat and humidity, 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 (1) into a halogenated vinyl resin Ml.

Rt (In the formula, Rt and R2 each independently represent a hydrogen atom or a lower alkyl group, and n represents 1 to 5.) General formula (
In r), the lower alkyl group represented by R/ and ribs include methyl-ethyl, propyl, isopropyl, butyl, s'gc-butyl, isobutyl, t-butyl and the like.

Specific examples of phosphoric acid esters include phenyl-
Resorcin polyphosphate, cresyl abashi resorcin e
Polyphosphate, phenyl cresyl, resorcinol,
Polyphosphate, xylyl resorcinol polyphosphate, phenyl@p-1-butylphenyl resorcinol polyphosphate, phenyl isopropylphenyl resorcinol polyphosphate, cresyl xylyl resorcinol polyphosphate, phenyl isopropylphenyl diisopropylphenyl - Examples include resorcin and polyphosphate.

The amount of the phosphoric acid ester added in the present invention 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.
Heavy weight. If the amount added is less than 5 parts by weight, the flame retardant effect will be insufficient, and if it is added in an amount of 70 parts by weight or more, 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 plasticizer well known and commonly used in the prior art. It is preferable. A wide variety of plasticizers can be used in combination with phosphate esters. Monomers produced by the reaction of -hydric or dihydric alcohols with phthalic anhydride, trimellitic anhydride, fatty acids, adipic acid, azelaic acid, sevalenic acid, benzoic acid, citric acid, 3-'' and other acids. The best results were obtained using primary ester plasticizers that are -, di-, and triesters.

Among these secondary ester plasticizers, the most useful at 1°C are dialkyl phthalates such as dibutyl phthalate, diakyl phthalate, di-octyl phthalate, diisooctyl phthalate, di-2-ethylhexyl phthalate-dinonyl phthalate, and didodecyl. phthalates, and hexyl octyl phthalates; arylalkyl phthalates such as butylbenzyl phthalate; dialkyl sebacates such as dibutyl sebacate: t-' and di-2-ethylhexyl sebacate, dialkyl adipates such as di-ruoctyl adipate, diisooctyl adipate and diisodecyl. Adipates; dialkyl azelates such as diisooctyl azelate, trialkyl trimellitates such as tri-2-ethylhexyl trimellitate-tri-octyl trimellitate; citrates such as acetyl tributyl citrate; alkylphthalyl alkyl glycolates such as ethyl phthalyl ethyl glycolate and butylphthalyl butyl glycolate; and gelicol benzoates such as diethylene glycol dibenzoate and dipropylene glycol dipenzoate.

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 primary ester plasticizer per 1 M base of phosphate ester is used to obtain a plasticized composition having the desired properties of button mating.

The most satisfactory results were obtained when the nT plasticizer mixture contained 1 to 5 parts by weight of primary ester plasticizer per 1 part phosphate ester.

When using the plasticizer containing the resorcinol polyphosphate of the present invention, the halogenated vinyl resin composition has flame retardancy and low temperature flexibility. t, mo, and other important properties may range from about 5 to about 100 parts by weight, or more, per 100 parts by weight of the halogenated vinyl resin. In most cases.

About 30 to about 60 per 100 parts by weight of halogenated vinyl resin
An excellent combination of flame retardancy and physical and mechanical properties is obtained when heavy duty plasticizers are used.

For polyvinyl chloride compositions, best results are obtained when a plasticizer comprising a phosphate ester is used at a weight of 40 to 50 parts per 100 parts of the resin.

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 halides in the presence or absence of monocopolymerizable monomers. As used herein, the term "halogenated vinyl resin" includes halogenated vinyl homopolymers, such as polyvinyl chloride, polyvinyl bromide, and polyvinylidene chloride, as well as halogenated vinyl copolymers; are co-common with vinyl halides, such as vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl chloroacetate; vinylidene; vinyl alkyl sulfonates; vinyl ethers such as vinyl ethyl ether, vinyl isopropyl ether , trigrams and vinyl chloroethyl ether; cyclic unsaturated compounds such as styrene, chlorostyrene, coumaron, indene, vinylnaphthalene, vinylpyridine, '3
r- and vinylpyrrole; acrylic acid and its derivatives such as ethyl acrylate, methyl methacrylate, ethyl methacrylate, ethyl chloroacrylate, acrylonitrile, trigrams and methacrylonitrile; dialkyl fumarates and maleates; unsaturated hydrocarbons such as ethyl y-propylene, and isobutyne. ; allyl compounds such as allyl acetate-allyl chloride, and allyl edyl ether; and conjugated and bridged ethylenically unsaturated 11th compounds such as butadiene.

Isoprene, chlorbrene, and divinyl ketone: l
A mixture thereof is included in the formula. Copolymers that may be used in the practice of this invention are those containing at least 70% vinyl halide and 30% comonomer media.

The present invention can be applied to any mixture of a large proportion of halogenated vinyl resin and a small proportion of other synthetic resins, such as polyethylene, polypropylene, ABS-polyacrylate and polymethacrylate; Synthetic rubbers such as neoprene-silicon, nitrile,
Hexagram and SBR: polyurethane, polyamide, polystyrene, phenolic resin, urea resin - cellulose ester -
Contains epoxide, etc.

The compositions of the invention may contain stabilizers, fillers-pigments, dyes, skin thickeners and other additives commonly used for the above purposes.

The invention is further illustrated in the following example IAf;'ll. Some of these examples are all due to heavy use, and almost all percentages are heavy.

Example 1 A test piece was prepared according to the following formulation, and a thermal stability test by i-k at 175°C and a photostability test by irradiation with a xenon lamp were conducted. The results are shown in Table W.

(Blended 100 parts PVC! (il, -1,050) Phosphate ester 50 MARK-AC1,834 (Ba-ZyL-phosphite liquid stabilizer) Fang 1
Table) Example 2 A test piece was prepared using the following formulation and the oxygen content was measured according to JIS K72 (11).The results are shown in Table 2.

(Composition) PVC (;= 1300) 1 (10 parts'
F3a-Zn-Boss Fight fl141 cut 3
Stearic acid 0.5 Epoxidized soybean oil 5 Example 3 Test pieces were prepared from the following compounding buttons and various performance tests were conducted. The results are shown in Table 3.

(Composition) PVC (i-1300) 100 parts epoxidized dog bean oil 5 MARK AG-1832, 5 MARK1500 (Boss Fight Ikari Sai IJ)
0.5 Butyl stearate 0.5 Stearic acid 0.2 Trioctyl trimellitate 40 Phosphate ester
10

Claims (1)

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