JP3333543B2 - Chlorine-containing resin foam - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a chlorine-containing resin foam,
Specifically, the chlorine-containing resin contains a plasticizer, zinc stannate or zinc hydroxystannate, and a pyrolytic organic foaming agent, and is foamed by heating to form a low-toxic chlorine-containing resin foam having improved flame retardancy. It is about.

[0002]

BACKGROUND OF THE INVENTION Chlorine-containing resins are relatively inexpensive and have good physical and chemical properties.
It is a suitable material for application to furniture products such as cushioning materials, automobile products, and the like.

[0003] Such a foamed molded product is generally blended with a chlorine-containing resin by adding a plasticizer, a foaming agent, a stabilizer, a filler, a coloring agent, and the like, and then molded by calendering, extrusion, injection molding, or the like. Or, it is manufactured by adding a plasticizer, a foaming agent, a stabilizer, etc. and, if necessary, a filler, a colorant, etc. to the paste resin, blending the resultant, coating on paper or cloth, and applying heat to form a gel. You.

[0004] However, since a large amount of a plasticizer is contained in order to provide elasticity, when a fire or the like occurs, it is liable to burn, and there are problems such as smoking and generation of toxic gas. Therefore, flame retardants such as antimony trioxide and aluminum hydroxide are used. However, when these flame retardants are used, there is a large amount of smoke generated, and there is a problem of toxicity with antimony trioxide. There was a disadvantage that the sol viscosity during paste processing was increased.

[0005] Further, zinc compounds such as zinc borate are generally known as flame retardants having a smoke suppressing effect at the time of combustion. However, the flame retarding effect is still insufficient. Development was requested.

[0006]

In view of the above situation, the present inventors have conducted various studies to obtain a low-toxic chlorine-containing resin foam having improved flame retardancy.
The present inventors have found that the above problems can be solved by using a plasticizer, a specific zinc-based flame retardant and a chemical foaming agent in combination, and have completed the present invention.

That is, according to the present invention, (a) 30 to 100 parts by weight of a plasticizer, (b) 3 to 10 parts by weight of zinc stannate and / or zinc hydroxystannate, and (c) An object of the present invention is to provide a chlorine-containing resin foam which contains 0.01 to 10 parts by weight of azodicarbonamide and is foamed by heating.

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

The plasticizer (A) of the chlorine-containing resin foam of the present invention is not particularly limited as long as it is a usual plasticizer used for chlorine-containing resins. For example, di-n-phthalic acid is used. Butyl, di-n-octyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, octyldecyl phthalate, diisodecyl phthalate,
Dialkyl C ₇ -C ₉ phthalates, phthalic plasticizers such as butylbenzyl phthalate, di-2-ethylhexyl isophthalate, di-2-ethylhexyl adipate, diisodecyl adipate, di-2-ethylhexyl azelate , Fatty acid ester plasticizers such as dibutyl sebacate, di-2-ethylhexyl sebacate, and phosphate ester plasticizers such as tributyl phosphate, tri-2-ethylhexyl phosphate, tricresyl phosphate, and trixylyl phosphate; chlorination Examples include chlorine plasticizers such as paraffin and chlorinated fatty acid esters, epoxy plasticizers, polyester plasticizers and the like, and one or more of these can be used in combination.

The amount of the component (a) is 30 to 100 parts by weight, preferably 50 to 80 parts by weight, based on 100 parts by weight of the chlorine-containing resin.

The zinc stannate and zinc hydroxystannate of the component (b) of the chlorine-containing resin foam of the present invention are represented by the following general formulas (I) and (I), respectively.
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 from the latter.

[0012]

Embedded image ZnSnO ₃ (I)

[0013]

Embedded image ZnSn (OH) ₆ (II)

The above zinc stannate and zinc hydroxystannate are:
Although there is no particular limitation on the particle size and the like, in applications where transparency is required, transparency can be improved by using particles having a particle size of 1 μm or less.

The amount of the component (b) is 3 to 10 parts by weight based on 100 parts by weight of the chlorine-containing resin.

The above component (b) has a sufficient effect as a flame retardant, but if necessary, may be used in combination with another flame retardant.

The azodicarbonamide as the component (c) of the chlorine-containing resin foam of the present invention is a pyrolytic organic blowing agent .

The amount of the component (C) is 0.01 to 10 parts by weight based on 100 parts by weight of the chlorine-containing resin.

The chlorine-containing resin in the present invention includes vinyl chloride homopolymers, vinyl chloride-vinyl acetate copolymers, vinyl chloride-ethylene copolymers, vinyl chloride-ethylene-vinyl acetate copolymers, and the like. Copolymer;
Examples thereof include a vinyl chloride graft copolymer obtained by graft-polymerizing vinyl chloride onto an ethylene-vinyl acetate copolymer or an ethylene-propylene copolymer, and the average degree of polymerization (JIS K-6721) is 600 to 1800. Are preferred.

The chlorine-containing resin foam of the present invention is obtained by foaming a chlorine-containing resin containing the above-mentioned components (a), (b) and (c) by heating in a usual manner.

The chlorine-containing resin foam of the present invention may contain a metal organic acid salt used as a stabilizer for a normal chlorine-containing resin.

As the acid radical of the metal organic acid salt, carboxylic acids, phenols and organic phosphoric acids are preferred.

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-ditert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid Monohydric 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,
Bivalent carboxylic acids such as isophthalic acid, terephthalic acid, oxyphthalic acid, chlorophthalic acid or monoesters or monoamide compounds thereof, butanetricarboxylic acid, butanetetracarboxylic acid, hemi-mellitic acid, trimellitic acid, melophanic acid, pyromellitic acid And di- or triester compounds of trivalent or tetravalent carboxylic acids.

Examples of the phenols include phenol, cresol, xylenol, methyl propyl phenol, methyl tertiary octyl phenol, ethyl phenol, isopropyl phenol, tertiary butyl phenol, n-butyl phenol, diisobutyl phenol,
Isoamylphenol, diamylphenol, isohexylphenol, octylphenol, isooctylphenol, 2-ethylhexylphenol, tertiary octylphenol, nonylphenol, dinonylphenol, tertiary nonylphenol, decylphenol, dodecylphenol, octadecylphenol, cyclohexylphenol, phenylphenol, etc. No.

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

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 the metal organic acid salt is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the chlorine-containing resin.

An excellent synergistic effect is exhibited by using an organic phosphite compound and / or an epoxy compound in combination with the chlorine-containing resin foam 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-didaisanbutylphenyl) octyl phosphite, diphenyldecyl phosphite, phenyldiisodecyl 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 added is
Preferably, 0.0 parts by weight based on 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.

The epoxy compounds include epoxidized soybean oil, epoxidized linseed oil, epoxidized fish oil,
Epoxidized tall oil fatty acid esters, epoxidized 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 and the like.

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

Various fillers can be added to the chlorine-containing resin foam of the present invention, if necessary. As the filler,
Calcium carbonate, silica, clay, glass beads, mica, sericite, talc, glass flake, asbestos, wollastonite, potassium titanate, PMF, gypsum fiber, zonotlite, MOS, phosphate fiber,
Glass fibers, carbon fibers, aramid fibers, and the like are included.

The amount of the filler to be added is as follows.
It is preferably 50 to 250 parts by weight with respect to 0 parts by weight, and is appropriately determined within the above range depending on the use.

If a light stabilizer is added to the chlorine-containing resin foam 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.

If necessary, the chlorine-containing resin foam of the present invention may contain, for example, a crosslinking agent, a pigment, an antistatic agent, a plate-out inhibitor, a surface treating agent, a lubricant, a fluorescent agent, a fungicide, and a bactericidal agent. Agents, photodegradants, non-metal stabilizers, processing aids, release agents and the like.

[0037]

Next, the stabilizing effect of the chlorine-containing resin foam of the present invention will be specifically described by way of examples. However,
The present invention is not limited by the following examples.

Example 1 Using the following mixture, the mixture was roll-kneaded at 150 ° C. for 10 minutes and the sheet was raised to 0.4 mm. Using the sheets, foam sheets were prepared in a gear oven at 220 ° C. for 1 minute, 2 minutes, and 3 minutes, respectively, and the expansion ratio (foamability) of the obtained sheets was measured. The whiteness of the foamed sheet was measured for 2 minutes.

Further, the rolled sheet was bonded and pressed, and a flame retardancy test was performed in accordance with UL-94. The smoke emission at that time was also observed.

The results are shown in Table 1 below.

[Compound] Parts by weight Vinyl chloride resin (degree of polymerization 1050) 100 Calcium carbonate 50 Titanium oxide 15 Di-2-ethylhexyl phthalate 60 Adekastab OF-23 ^{* 1} 2.5 Azodicarbonamide 3 Test compound ([Table 1 (See [Table 1]) * 1: Ba / Zn-based powder stabilizer manufactured by Asahi Denka Kogyo

[0042]

[Table 1]

Example 2 Using the following mixture, the mixture was mixed for 20 minutes with a stirrer to prepare a uniform paste sol. The viscosity of this paste sol immediately after mixing and after standing for one day was measured with a B-type viscometer. Further, the paste sol was applied on flame-retardant paper so as to have a thickness of 0.18 mm, and was semi-cured in a 140 ° C. gear oven. Then, the mixture was heated in a gear oven at 220 ° C. for 60 seconds to foam. At that time, the expansion ratio (expandability), yellowness and cell state were measured, and the flame retardancy was evaluated in the same manner as in Example 1.

The cell state was evaluated by visual observation, and was evaluated on a three-point scale: ：: good, Δ: slight variation, ×: large variation.

The results are shown in Table 2 below.

[Combination] Parts by weight PVC paste resin (polymerization degree 800) 100 Di-2-ethylhexyl phthalate 60 Calcium carbonate 60 Titanium oxide 15 Adekastab FL-44 ^{* 2} 3.0 Azodicarbonamide 2 bis (benzenesulfonyl hydrazide) Ether 2 Mineral spirit 6 Test compound (See [Table 2]) (See [Table 2]) * 2: Ba / Zn liquid stabilizer manufactured by Asahi Denka Kogyo

[0047]

[Table 2]

From the results shown in Tables 1 and 2, from the results obtained by adding a plasticizer, a pyrolytic organic foaming agent, a flame retardant, and the like to a chlorine-containing resin to produce a foam, three flame retardants were used. When antimony oxide is used, although the flame retardant effect is excellent, the amount of smoke generated is very large, and when zinc borate and aluminum hydroxide are used, the flame retardant effect is insufficient and it is necessary to add a large amount. Not only that, the foaming properties, coloring properties, and cell uniformity, which are important as foaming materials, are reduced, and the sol viscosity, which affects the processability during paste processing, is increased.

On the other hand, as the flame retardant, the above (b)
The chlorine-containing resin foam of the present invention using the components has not only an excellent flame-retarding effect and a smoke-suppressing effect, but also a foam-promoting effect, and furthermore, the coloring property and the cell uniformity are almost reduced. It is clear that the increase in sol viscosity is small.

[0050]

Industrial Applicability The chlorine-containing resin foam of the present invention has excellent flame retardancy and emits little smoke even in the event of burning, so that it is useful as a foam material for wallpaper, automobile interior materials and the like.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-52-136243 (JP, A) JP-A-57-147552 (JP, A) JP-A-2-215850 (JP, A) JP-A-4- 366153 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08J 9/00-9/42 C08K 3/00-13/08 C08L 1/00-101/16

Claims (1)

(57) [Claims] 1. 100 parts by weight of a chlorine-containing resin, (a) 30 to 100 parts by weight of a plasticizer, (b) 3 to 10 parts by weight of zinc stannate and / or zinc hydroxystannate, and (c) azodica
A chlorine-containing resin foam containing 0.01 to 10 parts by weight of rubonamide and foamed by heating.