JPS60197744A - Preparation of halogen-containing foamed resin material - Google Patents

Abstract

PURPOSE:To prepare the titled foamed material with improved color, by incorporating a halogen-contg. resin with a chemical foaming agent and a particular inorg. metallic compd. and foaming by heating. CONSTITUTION:100pts.wt. halogen-contg. resin (e.g., PVC), 0.1-10pts.wt. chemical foaming agent (e.g., azodicarbonamide), 0.1-10pts.wt. one or more inorg. metallic compd. selected from among hydrotalcites and zeolites, 0.01-5pts.wt. zinc compd. (e.g., ZnO) if necessary, 0.01-5pts.wt. org. phosphite compd. (e.g., diphenyl decyl phosphite) and/or 0.01-10pts.wt. epoxy compd. (e.g., epoxy soybean oil), etc. are incorporated and foamed by heating.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a halogen-containing resin foam, and more particularly, a method for producing a halogen-containing resin foam, which is characterized by adding a chemical blowing agent and a specific inorganic metal compound to a halogen-containing resin, and then heating and foaming the foam. The present invention relates to a method for producing a halogen resin foam.

Halogen-containing resin foam is generally manufactured by adding blowing agents, stabilizers, fillers, plasticizers, pigments, etc. to resin, mixing it, and then heating and foaming it, and it is used for wall covering materials, leather, furniture products, etc. It is used.

Hitherto, various stabilizers have been used for the purpose of obtaining halogen-containing resin foams, and Ha--Zn type stabilizers are particularly commonly used.

However, when these stabilizers are used, the hue is insufficient, and it has been desired to improve the hue, especially when used in wall covering materials that require high whiteness. In the case of non-foaming formulations, whiteness can usually be improved to some extent by reducing the Ba component and increasing the color of the Znn component, but in the case of foaming formulations, increasing the Zn component may actually reduce the whiteness. Also, if the Zn component is reduced, the desired foaming ratio cannot be obtained (this is why methods such as the combined use of organic phosphites have been adopted, but even this method does not provide sufficient whiteness, and further improvement is required). was requested.

As a result of repeated studies to obtain a halogen-containing resin foam with improved hue, the present inventors added specific amounts of a chemical blowing agent and a specific inorganic metal compound to a halogen-containing resin, and then heated and foamed the halogen-containing resin. It has been found that a halogen-containing resin foam with particularly improved hue can be obtained by doing so, and the present invention has been achieved.

That is, in the present invention, (M
l A halogen-containing resin characterized by adding 0.1 to 10 parts by weight of a chemical blowing agent and 0.1 to 10 parts by weight of at least one selected from hydrotalcites or zeolites, followed by heating and foaming. A method of manufacturing a foam is provided.

The method for producing the halogen-containing resin foam of the present invention will be described in detail below.

Examples of the chemical blowing agent used in the present invention include azocabonamide, dinitrosopentamethylenetetramine, N,N'-dimethyl-N,N'-dinitrosoterephthalimide, benzenesulfonylhydrazide, p-)luenesulfonylhydrazide, 4. 4'-oxybis(
benzenesulfonylhydrazide), azobisisobutyronitrile, nitrourea, p-)luenesulfonyl azide, 2.4-)ruenedisulfonylhydrazide, trinitrosotrimethylenetriamine, p-toluenesulfonyl semicarbazide, oxalylhydrazide, nitroguanidine, hydra Examples include zodicarbonamide and trihydrazinotriazine.

The amount of these chemical blowing agents added is 0.1 to 10 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of the halogen-containing resin.
It is 5.

The hydrotalcites used in the present invention are hydrous double salt compounds consisting of magnesium and aluminum represented by the following general formula (I).

Mg 1-x Al x (OH) 2 A x/2-
mH20(,1) (In the formula, X is a real number in the range of Q<x≦0.5, A represents CO3, and m represents a real number.) Even if the above hydrotalcites are natural products It may also be a synthetic product. As a synthesis method, Japanese Patent Publication No. 46-2280, Japanese Patent Publication No. 50-30039, and Japanese Patent Publication No. 51-2912
A known method disclosed in Publication No. 9 and the like can be exemplified. Furthermore, in the present invention, the above-mentioned hydrotalcites can be used without being restricted by their crystal structure or crystal particle size. The surface of the above hydrotalcites is coated with higher fatty acids such as stearic acid, higher fatty acid metal salts such as alkali metal oleate, organic sulfonic acid metal salts such as alkali metal dodecylbenzenesulfonate, higher fatty acid amides, and higher fatty acids. Those coated with fatty acid ester or wax can also be used.

The zeolites used in the present invention are aluminosilicate compounds, examples of which include chabasite, mordenite, erionite, clinoptilolite, and zeolite A.
1 zeolite X, zeolite Y1 zeolite L.

The amount of the above hydrotalcites or zeolites added is 0.1 to 10 parts by weight per 100 parts by weight of the halogen-containing resin.
It is preferably 0.2 to 5 parts by weight.

In the method of the present invention, a halogen-containing resin foam can be obtained even when hydrotalcites or zeolites are used alone, but in order to improve foam rise, cell stability, expansion ratio, etc., a zinc compound is added. It is preferable to use them together.

These zinc compounds include zinc oxide, zinc hydroxide, zinc carbonate, zinc acetate, zinc octylate, zinc neodecanoate,
Examples include zinc laurate and zinc stearate.

The amount of these zinc compounds added is preferably 0.01 to 5 parts by weight, particularly 0.1 to 3 parts by weight, based on 100 parts by weight of the combined halogen resin.

In addition, in the method of the present invention, IasI[a, I[a
, F/as Group IVb metal or organotin oxide,
The effect can be further improved by using 0.1 to 5 parts by weight of a hydroxide or carboxylate based on the halogen-containing resin.

Examples of the carboxylic acids constituting the metal salts of the above carboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, neooctanoic acid, 2-ethylhexylic acid, pelargonic acid, capric acid, Undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid, 2-hydroxystearic acid, behenic acid, montanic acid, benzoic acid, monochlorobenzoic acid, P-tert-butylbenzoic acid, dimethyl hydroxy Benzoic acid, 3,5-ditert
-Butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cumic acid, n-propylbenzoic acid, aminobenzoic acid, N.

N-dimethylaminobenzoic acid, acetoxybenzoic acid, stylic acid, P-tert-octyl stylic acid, oleic acid, elaidic acid, linoleic acid, linuric acid, thioglycolic acid, mercaptopropionic acid, octylmercaptopropionic acid Monocarboxylic acids such as Cheryl acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid,
Speric acid, azelaic acid, sepacic acid, phthalic acid, isophthalic acid, terephthalic acid, oxyphthalic acid, chlorphthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, polyconic acid, aconitic acid,
Examples include divalent carboxylic acids such as thiodipropionic acid, or monoesters thereof.

In addition, the above Ia % I[a, ma s TVa
% ■ Group b metals include Na, K, Li+ Mg
, Ca+ Sr, Ba+^l.

Examples of the organic tin include Sn+Pb+Zr, and examples of the organic tin include dimethyltin, dibutyltin, and dioctyltin.

In the method of the present invention, an excellent synergistic effect is exhibited by the combined use of an organic phosphite compound and/or an epoxy compound.

The above organic phosphite compounds include diphenyldecyl phosphite, triphenyl phosphite, tris-
Nonylphenyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, tributyl phosphite, dilauryl acid phosphite, dibutyl acid phosphite, tris (dinonylphenyl) phosphite, trilauryl trithiophosphite,
trilauryl phosphite, bis(neopentyl glycol)-1,4-cyclohexane dimethyl phosphite, distearyl pentaerythritol diphosphite,
Diisodecylpentaerythritol diphosphite, diphenyl acid phosphite, tris(lauryl-2-
thioethyl) phosphite, tetratridecyl-1,1
,3-)lis(2°-methyl-5”-tert-butyl-4°
-oxyphenyl)butane diphosphite, tetra(C
12-CI5 mixed alkyl>4.4'-isopropylidene diphenyl diphosphite, tris(4-oxy-2
, 5-di-tert-butylphenyl) phosphite, tris(4-oxy-3,5-di-tert-butylphenyl) phosphite, 2-ethylhexyldiphenyl phosphite, tris(mono-, di-mixed nonylphenyl) phosphite, Hydrogenated-4,4'-isopropylidene diphenol polyphosphite, diphenyl bis[4,4'-n-butylidene bis(2-tert-butyl-5-methylphenol)]thioditanol diphosphite, bis( octylphenyl) bis(4,4'-n-butylidene bis(
2-tert-butyl-5-methylphenol))-1,6-
Hexanediol diphosphite, phenyl-4,4'
-isopropylidene diphenol/pentaerythritol diphosphite, phenyl diisodecyl phosphite, tetratridecyl-4,4”-n-butylidene bis(
Examples thereof include 2-tert-butyl-5-methylphenol) diphosphite and tris(2,4-di-tert-butylphenyl) phosphite.

The amount of these organic phosphite compounds added is 0.01 to 5 parts by weight, especially 0.01 to 5 parts by weight, based on 100 parts by weight of the halogen-containing resin.
．． The amount is preferably 1 to 3 parts by weight.

In addition, the above-mentioned epoxy compounds include epoxidized soybean oil, epoxidized linseed oil, epoxidized fish oil, epoxidized tall oil fatty acid ester, epoxidized raw tallow oil, epoxidized polybutadiene, epoxy methyl stearate, -butyl, -2 ethylhexyl, -Stearyl, tris(epoxypropyl) isocyanurate, epoxidized castor oil, epoxidized flower oil, epoxidized linseed oil butyl fatty acid, 3-(2-xenoxy)-1,2-epoxypropane, bisphenol-A diglycidyl ether , vinylcyclohexene dieboxide, dicyclopentadiene dieboxide, 3,4-epoxycyclohexyl-6-methylepoxycyclohexanecarboxylate, and the like.

The amount of these epoxy compounds added is 10% of the halogen-containing resin.
0.01 to 10 parts by weight, especially 0.5 to 10 parts by weight
Preferably, the amount is 5 parts by weight.

In the method of the present invention, phthalate plasticizers or other ester plasticizers, polyester plasticizers, phosphate plasticizers, chlorine plasticizers, other plasticizers, etc. are used as appropriate depending on the application. can.

Furthermore, in the method of the present invention, a light stabilizer can also be used in combination. The light stabilizers include benzophenone type, benzotriazole type, salicylate type, substituted acrylonitrile type, various metal salts or metal chelates, especially nickel or chromium salts or chelates, triazine type, piperidine type, etc.

Others as necessary, such as crosslinking agents, pigments, fillers, etc.
Antistatic agent, antifogging agent, plate-out prevention agent, surface treatment agent, lubricant, flame retardant, fluorescent agent, antifungal agent, bactericide, metal deactivator, photodegrading agent, processing aid, mold release agent , reinforcing agents, and the like.

Examples of the halogen-containing resin used in the present invention include:
polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride,
Polyvinylidene chloride, chlorine (bipolyethylene, chlorinated polypropylene, brominated polyethylene, 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
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,
Halogen-containing synthetic resins such as vinyl chloride-urethane copolymers and internally plasticized polyvinyl chloride, and the above halogen-containing resins and polyethylene, polypropylene, polyphene, polyethylene, etc.
α-olefin polymers such as 3-methylbutene, polyolefins such as ethylene-vinyl acetate copolymers, ethylene-propylene copolymers, and copolymers thereof, polystyrene, acrylic resins, styrene and other monomers such as anhydrous (maleic acid, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene copolymers, acrylic ester-butadiene-styrene copolymers, methacrylic ester-butadiene-styrene copolymers, blends with polyurethane etc. can be given.

Since the halogen-containing resin foam obtained by the method of the present invention has a markedly improved hue, it is particularly effective when high whiteness is required. In such cases, titanium dioxide is generally added in an amount of 1 to 50 parts by weight, preferably 5 to 30 parts by weight, per 100 parts by weight of the halogen-containing resin, so the method of the present invention contains titanium dioxide in the above proportion. It is particularly effective in producing foams.

In addition, when using foam as a wall covering material, filler such as calcium carbonate or aluminum hydroxide is added in a relatively large amount (10 to 200 parts by weight per 100 parts by weight of halogen-containing resin) to improve flame retardancy. However, in such cases, whiteness generally decreases. However, according to the method of the present invention, a halogen-containing resin foam with excellent whiteness can be obtained even in such cases. It is valid.

Next, examples of the present invention will be shown, but the present invention is not limited to these examples.

Example 1 The following formulation was kneaded at 155° C. for 10 minutes to prepare a sheet with a thickness of 0.4 mm. This sheet was placed in an oven at 230° C. and foamed for 120 seconds to create a foam, and the foaming ratio, cell condition, and whiteness were measured. Further, regarding the expansion ratio, the expansion ratio after heating and foaming for 90 seconds was also measured. The results are shown in Table-1.

Parts by weight of Ni-ichikin Polyvinyl chloride resin 100 Dioctyl phthalate 6 Titanium dioxide 20 Azocabonamide 3 Zinc stearate Table 1 Sample (Table 1) Table 1 The whiteness is the digital color manufactured by Tokyo Juishoku Co., Ltd. Measured with a meter.

Table-1 (gfl $1. $2 and *3: Synthetic hydrotalcite manufactured by Kyowa Chemical Industry Co., Ltd. *4: Foaming ratio after heat foaming for 90 seconds $5: Foaming ratio after heat foaming for 120 seconds■
=Additional amount of zinc stearate Example 2 A foam was prepared in the same manner as in Example 1 using the following formulation, and the expansion ratio, cell condition, and whiteness were measured. The results are shown in Table-2.

Ni-ichikin Part by weight Polyvinyl chloride resin 100 Dioctyl phthalate 6 Titanium dioxide 20 Azocicabonamide 3 DHT-4A 1 Zinc compound (Table 2) The amount of zinc compound added is 0.7 part by weight of zinc stearate. and zinc content were made to be the same.

Table 2 (Note) 1; Foaming ratio after heating and foaming for 90 seconds: $2:
Expansion ratio after heating and foaming for 120 seconds Example 3 The following formulation was kneaded at 155°C for 10 minutes to form a foam with a thickness of 0.5 m.
A sheet was created. This sheet was placed in an oven at 230°C and foamed for 120 seconds to create a foam.
The foaming ratio, cell condition and whiteness were measured in the same manner as above. The results are shown in Table-3.

Parts by weight of N-metallic polyvinyl chloride resin 100 Calcium carbonate 100 Dioctyl phthalate 8 Titanium dioxide 20 Azocicabonamide 3 Zinc stearate 0.7 Sample (Table 3') 1.3 Table 3 [Note] Koi+ 90 Foaming ratio after heating and foaming for seconds: $2:
Expansion ratio after foaming by heating for 120 seconds Example 4 By using an organic phosphite compound in the method of the present invention, the hue of the foam can be further improved.

In this example, in order to examine the combined effect of this organic phosphite compound, a foam was prepared in the same manner as in Example 1 using the following formulation, and its whiteness was measured.

The results are shown in Table 4.

1-One gold part by weight Polyvinyl chloride resin 100 Dioctyl phthalate 40 Chlorinated paraffin (CI content 840%) 20 Calcium carbonate 60 Titanium dioxide 20 Azocica-bonamide 3 Zinc oxide 0.8 DHT-4A 1.0 Organic phosphite compound (Table 4> 0.5Table 4 Example 5 The following formulation was mixed with a roll at 155°C for 10 minutes, and the thickness was 0.
．． I created a sheet of 4 cranes. This sheet was placed in an oven at 220° C. and foamed for 160 seconds to create a foam, and the foaming ratio and degree of coloring were measured. In addition, the foaming ratio was measured after heating and foaming for 80 seconds. The results are shown in Table 5.

Plate - Ichikin Part by weight Polyvinyl chloride resin 100 Dioctyl phthalate) 70 Polyisobutyl methacrylate 0.2 Azocicabonamide 3 Sample (Table 5) Table 5 The coloring was evaluated on a scale of 1 to 1 (white). □ Shows 5 (light brown) - 10 (brown).

Table-5 [Note] *l: Foaming ratio after heating and foaming for so seconds: $2:
Expansion ratio after heating and foaming for 160 seconds Example 6 The following formulation was roll-kneaded at 160°C for 15 minutes to give a thickness of 0.
．． A 3fi sheet was created and attached to cotton cloth. Thereafter, this was placed in an oven at 220° C. and foamed for 100 seconds to create a foam, and the foaming ratio and degree of coloring were measured. Further, regarding the expansion ratio, the expansion ratio after heating and foaming for 60 seconds was also measured.

The results are shown in Table-6.

[-Ichikin weight part Azoshika Bonamide 3 Zinc stearate 1.5 Sample (Table-5) 1.0 Table-6

Claims (1)

[Claims] 100 parts by weight of halogen-containing resin, (a) 0 chemical blowing agent,
A method for producing a halogen-containing resin foam, which comprises adding 0.1 to 10 parts by weight of at least one selected from hydrotalcites or zeolites, and then heating and foaming.