JPH05262942A - Chlorine-containing resin composition - Google Patents

Abstract

PURPOSE:To provide the chlorine-containing resin excellent in the flame retardancy, smoking resistance and dropping resistance and good in the thermal stability without employing a stabilizer containing a metal such as cadmium, lead or an organic tin compound having possibility to affect the environments. CONSTITUTION:The chlorine-containing resin composition of the invention is characterized by adding (A) 0.01-20 pts.wt. of zinc stannate and/or zinc hydroxystannate, (B) 0.01-10 pts.wt. of at least one of zinc carboxylates, and (C) 0.01-10 pts.wt. of at least one of the carboxylate and phenolate of an alkali metal or alkaline earth metal to 100 pts.wt. of a chlorine-containing resin composition.

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 in which smoke generation during combustion is suppressed, and more specifically, a chlorine-containing resin containing zinc stannate or zinc hydroxystannate, a carboxylate of zinc and an alkali metal. Further, the present invention relates to a chlorine-containing resin composition containing an alkaline earth metal carboxylate or a phenolate, which has suppressed smoke generation during combustion and improved flame retardancy and thermal stability.

[0002]

2. Description of the Related Art A chlorine-containing resin is a resin having excellent flame retardancy because it is a linear resin and contains a large amount of chlorine in the resin. In the chlorine-containing resin composition of, the flame retardance is decreased because it contains a large amount of plasticizer, polyene is formed during dehydrochlorination accompanying combustion, and various complicated aromatic flammable gases are generated, There was a drawback that it caused intense smoke.

In order to make a chlorine-containing resin flame-retardant, a phosphoric acid ester-based flame retardant is usually used, chlorinated paraffin is further used as a secondary plasticizer, and an inorganic compound such as antimony trioxide is used. Although it is used, it has the effect of improving flame retardancy, but it tends to worsen smoke emission, causing flapping from the burning part, and there is a risk of fire spread.

Therefore, it has been proposed to use an inorganic acid zinc compound such as zinc oxide, zinc borate, zinc stannate, etc. as a flame retardant having improved smoke emission and less dripping. When a large amount of a flame retardant is added, the thermal stability of the chlorine-containing resin tends to decrease, so zinc-based,
Lead-based and organotin-based stabilizers were used.

However, in recent years, due to environmental problems and the like,
The use of stabilizers containing metals such as cadmium, lead, and organic tin has become unfavorable, and these stabilizers have been converted to calcium / zinc-based or barium / zinc-based nontoxic or low-toxic stabilizers. Switching is strongly desired. However, since calcium / zinc-based stabilizers or barium / zinc-based stabilizers have a small stabilizing effect, it has been considered difficult to prevent deterioration of stability by using zinc-based flame retardants.

[0006]

In view of the above situation, the present inventors have proposed a flame-retardant method without using a stabilizer containing a metal such as cadmium, lead, or organotin, which may adversely affect the environment. Of chlorine-containing resin with specific zinc-based flame retardant and specific stabilizer as a result of various studies in order to obtain chlorine-containing resin with excellent heat resistance, smoke emission, and dripping prevention The present invention has been completed by finding that the above problems can be solved by using a combination of and.

That is, according to the present invention, 100 parts by weight of a chlorine-containing resin is added to 0.01 to 20 parts by weight of (a) zinc stannate and / or zinc hydroxystannate, and (b) at least one kind of carboxylate of zinc. 01 to 10 parts by weight and (C)
It is intended to provide a chlorine-containing resin composition obtained by adding 0.01 to 10 parts by weight of at least one kind selected from alkali metal or alkaline earth metal carboxylates and / or phenolates.

The chlorine-containing resin composition of the present invention will be described in detail below.

The zinc stannate and zinc hydroxystannate as the component (a) used in the chlorine-containing resin composition of the present invention are represented by the following general formulas (I) and (2), respectively. The latter is represented by (II), and the latter can be easily produced by metathesis of sodium stannate and zinc chloride, and the former can be easily produced by heating and dehydrating the latter.

[0010]

Embedded image ZnSnO ₃ (I)

Embedded image ZnSn (OH) ₆ (II)

The zinc stannate and zinc hydroxystannate are not particularly limited in particle size and the like, but in applications where transparency is required, use of particles having a particle size of 1 μm or less improves transparency. Can be made

The amount of zinc stannate and / or zinc hydroxystannate added is 0.01 to 20 parts by weight, preferably 0.1 to 15 parts by weight, based on 100 parts by weight of the chlorine-containing resin.

As the alkali metal constituting the carboxylate and phenolate of the alkali metal or alkaline earth metal of the component (c) used in the chlorine-containing resin composition of the present invention, potassium and sodium are preferable, and alkali is As the earth metal, magnesium, calcium and barium are preferable.

The zinc carboxylate of component (b) and the alkali metal or alkaline earth metal carboxylate and phenolate of component (c) used in the chlorine-containing resin composition of the present invention may be a normal salt. It may be a basic salt, or it may be one which forms an overbased complex with carbonic acid or the like.

Examples of the carboxylic acid and phenols constituting the carboxylate of the component (b) and the component (c) and the phenolate of the component (c) used in the chlorine-containing resin composition of the present invention include the following: There are things.

Examples of the carboxylic acid include acetic acid,
Propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, neodecanoic acid, 2-ethylhexylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid Acid, 12-hydroxystearic acid, behenic acid, montanic acid, elaidic acid, oleic acid, linoleic acid, linolenic acid, thioglycolic acid,
Mercaptopropionic acid, octyl mercaptopropionic acid, benzoic acid, monochlorobenzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-ditert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid , Ethylbenzoic acid, cumic acid, n-propylbenzoic acid, acetoxybenzoic acid, salicylic acid, p-tertiary octylsalicylic acid and other monocarboxylic acids, 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,
Divalent carboxylic acids such as isophthalic acid, terephthalic acid, oxyphthalic acid, chlorophthalic acid or their monoesters or monoamide compounds, butanetricarboxylic acid, butanetetracarboxylic acid, hemimellitic acid, trimellitic acid, melophanoic acid, pyromellitic acid And di- or triester compounds of trivalent or tetravalent carboxylic acids.

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

The amount of the carboxylate of zinc as the component (b) added is 0.1% with respect to 100 parts by weight of the chlorine-containing resin.
The amount is 01 to 10 parts by weight, preferably 0.1 to 5 parts by weight.

The amount of the alkali metal or alkaline earth metal carboxylate or phenolate as the component (c) added is 100 parts by weight of the chlorine-containing resin.
It is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight.

Examples of the chlorine-containing resin in the chlorine-containing resin composition of the present invention include polyvinyl chloride, post-chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, chlorinated rubber, vinyl chloride-vinyl acetate. Copolymer, 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 A cycloalkyl or aryl maleimide copolymer,
Vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer,
Vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, Chlorine-containing resins such as vinyl chloride-urethane copolymers and α-olefin polymers such as polyethylene, polypropylene, polybutene, poly-3-methylbutene or ethylene-vinyl acetate copolymers, ethylene-propylene copolymers with the above chlorine-containing resins Such as polyolefins and their copolymers, polystyrene, acrylic resins, styrene and other monomers (eg maleic anhydride,
Butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene copolymer, methacrylic acid ester-butadiene-styrene copolymer, blended products with polyurethane, and the like.

By adding a filler together with the chlorine-containing resin composition of the present invention, the smoke suppressing effect is further improved.

As the above-mentioned filler, calcium carbonate, silica, clay, glass beads, mica, sericite, talc, glass flakes, asbestos, wollastonite, potassium titanate, PMF, gypsum fiber, zonotolite,
MOS, phosphate fiber, glass fiber, carbon fiber, aramid fiber and the like can be mentioned.

The above-mentioned filler is added in an amount of the chlorine-containing resin 10
With respect to 0 parts by weight, preferably 0.1 to 300 parts by weight,
In order to expect a synergistic effect, more preferably 10 to 1
It is 50 parts by weight.

By adding an organic phosphite compound and / or an epoxy compound together to the chlorine-containing resin composition of the present invention, an excellent synergistic effect is exhibited.

Examples of the organic phosphite compound include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, Tris (mono, di mixed nonylphenyl) phosphite, diphenyl acid phosphite, 2,
2'-methylenebis (4,6-didaisanbutylphenyl) octylphosphite, diphenyldecylphosphite, phenyldiisodecylphosphite, tributylphosphite, tri (2-ethylhexyl) phosphite, tridecylphosphite, trilaurylphosphite , Dibutyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite,
Bis (neopentyl glycol) -1,4-cyclohexanedimethyldiphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite,
Distearyl pentaerythritol diphosphite, phenyl-4,4′-isopropylidene diphenol pentaerythritol diphosphite, tetra (C ₁₂ -C)
₁₅ mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, bis (octylphenyl) .bis [4,4'-n-butylidene bis ( Two
-Tert-butyl-5-methylphenol)], 1,6-hexanediol diphosphite, tetratridecyl
4,4'-butylidene bis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl)
* 1,1,3-tris (2-methyl-5-tert-butyl-
4-hydroxyphenyl) butane triphosphite and the like can be mentioned.

The amount of the organic phosphite compound added is
It is preferably 0.0 with respect to 100 parts by weight of the chlorine-containing resin.
It is 1 to 5 parts by weight, more preferably 0.1 to 3 parts by weight.

Examples of the epoxy compound include epoxidized soybean oil, epoxidized linseed oil, epoxidized fish oil, epoxidized tall oil fatty acid ester, epoxidized beef tallow oil, epoxidized castor oil, 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, epoxidized polybutadiene, bisphenol-A diglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexyl-6-methylepoxycyclohexanecarboxylate, etc. Is mentioned.

The amount of the above epoxy compound added is preferably 0.01 to 20 relative to 100 parts by weight of the chlorine-containing resin.
Parts by weight, more preferably 0.5 to 10 parts by weight.

The chlorine-containing resin composition of the present invention includes ester-based plasticizers such as phthalic acid ester-based plasticizers, trimellitic acid ester-based plasticizers, pyromellitic acid ester-based plasticizers, and adipic acid ester-based plasticizers. Polyester-based plasticizers, phosphate ester-based plasticizers, chlorine-based plasticizers, other plasticizers and the like can be appropriately used according to the application.

If a light stabilizer is added to the chlorine-containing resin composition of the present invention, the light stability can be improved. Therefore, it is possible to appropriately select and use these depending on the purpose of use. Examples of the light stabilizer include benzophenone-based, benzotriazole-based, salicylate-based, substituted acrylonitrile-based, hindered amine-based, various metal salts or metal chelates, particularly nickel or chromium salts or chelates.

In addition, if necessary, the chlorine-containing resin composition of the present invention may include, for example, a crosslinking agent, a pigment, a foaming agent, an antistatic agent, an antifogging agent, an antiplateout agent, a surface treatment agent, a lubricant, and a hardener. A flame retardant, a fluorescent agent, a mildew proofing agent, a bactericidal agent, a photodegradation agent, a non-metal stabilizer, a processing aid, a release agent and the like can be included.

Examples of the use of the chlorine-containing resin composition of the present invention include building materials such as wall materials, floor materials and ceiling materials, paints, automobile interior materials, electric wire coating materials, and miscellaneous goods such as toys.

[0033]

EXAMPLES Next, the stabilizing effect of the chlorine-containing resin composition of the present invention will be specifically shown by Examples. However, the invention is not limited by the examples given below.

[Example 1] Using the following [composition], the mixture was kneaded with a roll and then pressed to prepare a standard test piece, and the limiting oxygen index (LOI) was measured according to BS2782. The smoke density was measured according to BS6401. Further, according to UL-90, the degree of sagging at the time of combustion was observed.

The evaluation of the degree of sagging at the time of combustion indicates that the smaller the number in the five-level evaluation, the better.

The results are shown in Table 1 below.

[Compound] parts by weight vinyl chloride resin (polymerization degree 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 Test compound (See [Table 1]) * 1: Lubrisol overbased barium carboxylate

[0038]

[Table 1]

[Example 2] Rolls were kneaded and then pressed by using the following mixture [compound] to give a thickness of 1
mm sheets were prepared and subjected to a thermal stability test in an oven at 190 ° C. The limiting oxygen index (LOI) was measured in the same manner as in Example 1.

The results are shown in [Table 2] below.

[Composition] Parts by weight Polyvinyl chloride resin (polymerization degree 1300) 100 Di-2-ethylhexyl phthalate 80 Epoxidized soybean oil 5 Calcium stearate 1.0 Zinc stearate 0.5 Antimony trioxide 3 Test compound ( (See [Table 2])

[0042]

[Table 2]

[Example 3] The same test as in Example 2 was carried out using the following compounding composition.

The results are shown in [Table 3] below.

[Composition] Parts by weight Polyvinyl chloride resin (polymerization degree 1300) 100 Di-2-ethylhexyl phthalate 50 Epoxidized soybean oil 5 Barium stearate 1.0 Zinc stearate 0.5 Test compound ([Table 3] (Refer to [Table 3])

[0046]

[Table 3]

From the results of the respective examples, when antimony trioxide is used, the limiting oxygen index is large, but the smoke-producing property and the sagging-preventing property are inferior, and zinc borate is used even if it is a zinc-based flame retardant. If not, not only the oxygen index is small, but also the smoke generation and sagging prevention properties are not sufficient, and
It is clear that it is necessary to use a cadmium-based stabilizer because it tends to lower the thermal stability when blended in a large amount.

On the other hand, when zinc stannate or zinc hydroxystannate is used, not only the oxygen index is large, but also the smoke generation and the sagging prevention property are excellent, and even when a large amount is blended, it is thermally stable. Not only does it not deteriorate
On the contrary, it has the effect of improving thermal stability, and it is clear that it is not necessary to use a stabilizer containing a harmful metal.

[0049]

The chlorine-containing resin composition of the present invention, which is obtained by adding zinc stannate or zinc hydroxystannate, a carboxylate of zinc and a carboxylate or phenolate of an alkali metal or alkaline earth metal salt to a chlorine-containing resin, It is a non-toxic or low-toxic substance that is excellent in flame retardancy, smoke generation and sagging prevention properties, and has good thermal stability.

Claims (1)

[Claims] 1. To 100 parts by weight of a chlorine-containing resin, (a) zinc stannate or / and zinc hydroxystannate 0.01-2.
0 parts by weight, 0.01 to 10 parts by weight of (b) a carboxylate of zinc, and (c) at least one of 0.01 to 10 selected from a carboxylate and a phenolate of an alkali metal or an alkaline earth metal.
A chlorine-containing resin composition obtained by adding 1 part by weight.