JP3133484B2 - Chlorine-containing resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chlorine-containing resin composition having reduced smoke emission during combustion, and more particularly, to a chlorine-containing resin containing zinc stannate or zinc hydroxystannate and a phosphate ester-based flame retardant. The present invention relates to a chlorine-containing resin composition which is excellent in flame retardancy and smoke suppressing properties.

[0002]

2. Description of the Related Art Chlorine-containing resins are very flame-retardant because they are linear and contain a large amount of chlorine in the resin. In the chlorine-containing resin composition, the flame retardancy is reduced because it contains a large amount of a plasticizer, a polyene is formed during dehydrochlorination accompanying combustion, and various complicated aromatic combustible gases are generated. There was a drawback that it caused intense smoke.

[0003] In order to make a chlorine-containing resin flame-retardant, a phosphate ester-based flame retardant is usually used, furthermore, chlorinated paraffin is used as a secondary plasticizer, or an inorganic compound such as antimony trioxide is used. However, when these compounds are used, the effect of improving the flame retardancy can be seen, but the smoke emission tends to worsen. Also conceived.

For this reason, it has been proposed to use an inorganic zinc compound such as zinc oxide, zinc borate, zinc stannate, etc. as a flame retardant having improved smoke generating properties and less dripping.
The use of only these zinc-based flame retardants has insufficient flame retarding effects, and further improvement has been demanded.

[0005] Accordingly, an object of the present invention is to provide a chlorine-containing resin composition having excellent flame retardancy, smoke suppression and drooling prevention.

[0006]

As a result of various studies, the present inventors have achieved the above object by using a chlorine-containing resin in combination with a specific zinc-based flame retardant and a phosphate ester-based flame retardant. We have found that we can achieve this and completed the present invention.

That is, according to the present invention, there are provided (a) 0.01 to 20 parts by weight of zinc stannate and / or zinc hydroxystannate and (b) a phosphate ester-based flame retardant per 100 parts by weight of a chlorine-containing resin. The present invention provides a chlorine-containing resin composition to which at least one selected from 0.1 to 30 parts by weight is added.

Hereinafter, the chlorine-containing resin composition of the present invention will be described in detail.

The zinc stannate and the zinc hydroxystannate of the component (a) used in the composition of the present invention are represented by the following general formulas (I) and (II), respectively. The latter can be easily produced by metathesis of sodium stannate and zinc chloride, and the former can be easily produced by dehydrating by heating from the latter.

[0010]

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These zinc stannates and hydroxyhydroxystannates are not particularly limited in terms of particle size, but in applications where transparency is required, use of particles having a particle size of 1 μm or less improves transparency. Can be done.

The above zinc stannate and zinc hydroxystannate are added in an amount of 0.1 to 100 parts by weight of the chlorine-containing resin.
It is from 0.01 to 20 parts by weight, preferably from 0.1 to 15 parts by weight.

Further, (b) used in the composition of the present invention
As the phosphate ester-based flame retardant of the component, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate,
Trischloroethyl phosphate, trisdichloropropyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, trixylenyl phosphate, octyl diphenyl phosphate, xyenyl diphenyl phosphate, tris isopropyl phenyl Phosphate and the like.

The amount of the phosphate ester-based flame retardant added is 0.1 to 30 parts by weight based on 100 parts by weight of the chlorine-containing resin.
Parts by weight, preferably 1 to 25 parts by weight.

Examples of the chlorine-containing resin used in the present invention include polyvinyl chloride, post-chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, chlorinated rubber, and vinyl chloride-vinyl acetate. Polymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-
Vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-alkyl, cycloalkyl or arylmaleimide copolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer Copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylate copolymer, vinyl chloride-maleate Chlorine-containing resins such as copolymers, vinyl chloride-methacrylate copolymers, vinyl chloride-acrylonitrile copolymers, vinyl chloride-urethane copolymers, and the above chlorine-containing resins and polyethylene, polypropylene, polybutene, poly-3- Α- such as methylbutene
Polyolefins such as olefin polymers or ethylene-vinyl acetate copolymers, ethylene-propylene copolymers and their copolymers, polystyrene, acrylic resins, styrene and other monomers (for example, maleic anhydride, butadiene, acrylonitrile, etc.) ), An acrylonitrile-butadiene-styrene copolymer, a methacrylate-butadiene-styrene copolymer, a blend with polyurethane, and the like.

The composition of the present invention contains Li, K, Na, Mg,
By adding organic acid salts, oxides and hydroxides of metals such as Sr, Ca, Ba, Zn, Cd, Sn, and Pb, and organic tin compounds, the stabilizing effect is remarkably improved.

Carboxylic acids, phenols, organic phosphoric acids, and the like are useful as the organic acid residues of the above-mentioned organic acid salts of metals.

As the carboxylic acid, for example, acetic acid,
Propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, neodecanoic acid, 2-ethylhexyl acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearin Acid, 12-hydroxystearic acid, behenic acid, montanic acid, elaidic acid, oleic acid, linoleic acid, linolenic acid, thioglycolic acid,
Mercaptopropionic acid, octylmercaptopropionic acid, benzoic acid, monochlorobenzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-ditertbutyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid , Monovalent carboxylic acids such as ethylbenzoic acid, cumic acid, n-propylbenzoic acid, acetoxybenzoic acid, salicylic acid, p-tert-octylsalicylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid , Suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid, aconitic acid, thiodipropionic acid, phthalic acid, isophthalic acid, terephthalic acid, oxyphthalic acid, chlorophthalic acid, etc. Carboxylic acids or their monoesters or Noamaido compounds, butane tricarboxylic acid, butane tetracarboxylic acid, hemimellitic acid,
Examples thereof include di- or triester compounds of trivalent or tetravalent carboxylic acids such as trimellitic acid, melophanic acid, and pyromellitic acid.

Examples of the phenols include phenol, cresol, xylenol, methylpropylphenol, methyl tert-octylphenol, ethylphenol, isopropylphenol, tertbutylbutyl, n-butylphenol, diisobutylphenol, isoamylphenol, diamylphenol Phenol,
Isohexylphenol, octylphenol, isooctylphenol, 2-ethylhexylphenol, tertiary octylphenol, nonylphenol, dinonylphenol, tertiary nonylphenol, decylphenol,
Dodecylphenol, octadecylphenol, cyclohexylphenol, phenylphenol and the like can be mentioned.

The organic phosphoric acids include, for example, mono- or di-octyl, -decyl, -dodecyl,
-Tridecyl, -tetradecyl, -hexadecyl, -octadecyl, -phenyl, -tolyl, -xylyl, -octylphenyl, and -nonylphenyl phosphoric acid, pyrophosphoric acid, and phosphorous acid.

The metal salt may be an acid salt, a neutral salt, a basic salt, or an overbased complex obtained by neutralizing a part or all of a base of a basic salt with carbonic acid.

The addition amount of these metal salts is preferably from 0.01 to 10 parts by weight, particularly preferably from 0.1 to 5 parts by weight, based on 100 parts by weight of the chlorine-containing resin.

The above-mentioned organotin compounds include, for example, mono- or dialkyltin compounds such as mono- or dimethyltin compounds, mono- or dibutyltin compounds or mono- or dioctyltin compounds. Or sulfide, oxide or sulfide-oxide of dialkyltin; octoate, laurate, malate-laurate, stearate, isostearate, crotonate, oleate of dialkyltin;
Carboxylate such as basic laurate; cyclic malate or malate polymer of dialkyltin; ester malate such as butylmalate, octylmalate, malate-octylmalate, stearylmalate, oleylmalate, basic butylmalate of dialkyltin; Alkyl mercaptides such as mono- or dialkyltin octyl mercaptide, lauryl mercaptide, stearyl mercaptide; mono- or dialkyltin isooctyl thioglycolate, 2-ethylhexyl thioglycolate, tetradecyl thioglycolate, iso- Thioglycolic acid ester salts such as octylthioglycolate-sulfide; isooctylthiopropionate, 2-ethylhexylthiopropionate and tetraethyltin of mono- or dialkyltin Shi thiopropionic ester salts such as Lucio propionate; 2 mono- or dialkyltin
And mercaptoethanol ester salts such as mercaptoethyl oleate salts. Among these organotin compounds, particularly preferred are malate-based, ester malate-based and thiocarboxylic acid ester-based compounds.

The addition amount of these organotin compounds is preferably 0.01 to 10 parts by weight, particularly preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the chlorine-containing resin.

By adding a filler to the composition of the present invention, the effect of suppressing smoke emission is further improved.

Examples of the filler include calcium carbonate, silica, clay, glass beads, mica, sericite, talc, glass flake, asbestos, wollastonite, potassium titanate, PMF, gypsum fiber, zonotolite, MOS, and phosphate fiber. , Glass fiber, carbon fiber, aramid fiber and the like.

The amount of these fillers to be added is as follows.
The amount is usually 0.1 to 300 parts by weight, and preferably 10 to 150 parts by weight, in order to expect a synergistic effect.

An excellent synergistic effect is exhibited by further using an organic phosphite compound and / or an epoxy compound in combination with the composition of the present invention.

Examples of the organic phosphite compound include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, Tris (mono and di mixed nonylphenyl) phosphite, diphenyl acid phosphite, 2,
2'-methylenebis (4,6-di-tert-butylphenyl)
Octyl phosphite, diphenyl decyl phosphite, phenyl diisodecyl phosphite, tributyl phosphite, tri (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, trilauryl Trithiophosphite,
Bis (neopentyl glycol) / 1,4-cyclohexanedimethyldiphosphite, bis (2,4-ditertbutylphenyl) pentaerythritol diphosphite,
Distearyl pentaerythritol diphosphite, phenyl-4,4'-isopropylidene diphenol pentaerythritol diphosphite, tetra (C ₁₂ -C
₁₅ mixed alkyl) -4,4'-isopropylidenediphenyldiphosphite, hydrogenated-4,4'-isopropylidenediphenol polyphosphite, bis (octylphenyl) bis [4,4'-n-butylidenebis ( 2-
Tert-butyl-5-methylphenol)] • 1,6-hexanediol • diphosphite, tetratridecyl •
4,4'-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl)
-1,1,3-tris (2-methyl-5-tert-butyl-
4-hydroxyphenyl) butane triphosphite and the like.

The amount of the organic phosphite compound is 0.01 to 5 parts by weight based on 100 parts by weight of the chlorine-containing resin.
It is preferable that the amount be 0.1 parts by weight, especially 0.1 to 3 parts by weight.

The epoxy compounds usable in the present invention include epoxidized soybean oil, epoxidized linseed oil, epoxidized fish oil, epoxidized tall oil fatty acid ester, epoxidized tallow oil, epoxidized castor oil, and epoxidized safflower. Oil, epoxidized linseed oil fatty acid butyl, epoxy methyl stearate, -butyl, 2-ethylhexyl or -stearyl, tris (epoxypropyl) isocyanurate, 3- (2-xenoxy) -1,2-epoxypropane, epoxidation Polybutadiene, bisphenol-A diglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide,
3,4-epoxycyclohexyl-6-methylepoxycyclohexanecarboxylate and the like.

The addition amount of these epoxy compounds is preferably 0.01 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the chlorine-containing resin.

The composition of the present invention may be used with an ester plasticizer such as a phthalate plasticizer or an adipic ester plasticizer, a polyester plasticizer, a chlorine plasticizer, or other plasticizers. It can be used appropriately depending on the situation.

If a light stabilizer is added to the composition of the present invention, the light stability can be improved. Therefore, these can be appropriately selected and used according to the purpose of use. These include benzophenones, benzotriazoles, salicylates, substituted acrylonitriles, hindered amines, various metal salts or metal chelates, especially nickel or chromium salts or chelates.

In addition, if necessary, the composition of the present invention may contain, for example, a crosslinking agent, a pigment, a foaming agent, an antistatic agent, an antifogging agent, a plateout inhibitor, a surface treatment agent, a lubricant, a flame retardant, a fluorescent Agents, fungicides, bactericides, photodegradants, nonmetal stabilizers, processing aids, mold release agents, and the like.

The composition of the present invention can be used irrespective of the method for processing a chlorine-containing resin. For example, calendering, roll processing, extrusion molding, pressure molding, paste processing, powder processing, It can be suitably used for molding and the like.

The composition of the present invention may be used for hard type,
Regardless of soft materials, there are building materials such as wall materials, floor materials and ceiling materials, paints, automotive interior materials, water and sewer pipes, electric wire coating materials, leather, seats, toys and other miscellaneous goods.

[0038]

The following examples illustrate the stabilizing effect of the composition of the present invention. However, the present invention is not limited by the following embodiments.

Example 1 Roll kneading was carried out using the following ingredients, followed by press working to prepare a standard test piece. The limiting oxygen index (LOI) was measured according to BS 2782, and the smoke was measured according to BS 6401. The concentration was measured. Also,
According to UL-90, the sagging condition during combustion was observed.

In the evaluation of the degree of sag during combustion, the smaller the number, the better the evaluation.

The results are shown in the following [Table 1].

[Combination] Parts by weight Vinyl chloride resin (degree of polymerization 1300) 100 Calcium carbonate 100 Di-2-ethylhexyl phthalate 50 Epoxidized soybean oil 2 LZ-2116 ^{* 1} 0.8 Barium nonylphenate 0.2 Zinc steer Rate 0.5 Tricresyl phosphate 10 Test compound (See [Table 1]) (See [Table 1]) * 1: Overbased barium carboxylate manufactured by Lubrizol Co.

[0043]

[Table 1]

Example 2 Rolls were kneaded using the following ingredients, and then pressed to form a sheet having a thickness of 1 mm, and a heat stability test was performed in a 190 ° C. oven. Further, the limiting oxygen index (LOI) is the same as in Example 1.
Was measured.

The results are shown in Table 2 below.

[Combination] parts by weight Polyvinyl chloride resin (degree of polymerization: 1300) 100 di-2-ethylhexyl phthalate 80 epoxidized soybean oil 5 calcium stearate 1.0 zinc stearate 0.5 antimony trioxide 3 hydroxystannic acid Zinc 6 Test compound (see [Table 2]) 10

[0047]

[Table 2]

As is apparent from the above examples, when the phosphate ester-based flame retardant is used alone, the flame retardancy is insufficient, and when the flame retardant is used in combination with antimony trioxide. Has improved flame retardancy, but emits more smoke and drools. When zinc borate is used in combination, smoke generation and sagging are improved to some extent, but the flame retardancy is insufficiently improved, and the thermal stability tends to decrease.

On the other hand, in the case of the composition of the present invention in which zinc stannate or zinc hydroxystannate and a phosphate ester-based flame retardant are added to a chlorine-containing resin, the flame retardancy is remarkably improved. In addition, it is clear that smoke and dripping during combustion are significantly suppressed, and that thermal stability is also significantly improved.

[0050]

Industrial Applicability The chlorine-containing resin composition of the present invention is excellent in flame retardancy, smoke suppression and drooling prevention.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-52-136243 (JP, A) JP-A-2-215850 (JP, A) "Polymer Digest" Vol. 43, No. 1, No. 1991, p. 55-64 (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 27/04 C08L 23/28 C08K 3/24 C08K 5/521 CA, REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A method according to claim 1, wherein (a) zinc stannate and / or zinc hydroxystannate is used in an amount of 0.01 to 2 parts by weight per 100 parts by weight of the chlorine-containing resin.
A chlorine-containing resin composition comprising 0 part by weight and 0.1 to 30 parts by weight of at least one selected from (b) phosphate ester-based flame retardants.