JPS639539B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to liquid stabilizers for chlorine-containing resin foams. More specifically, it consists of a mixture of a low-toxic or non-toxic zinc organic acid salt, alcohol and zinc chloride, and a solvent, which promotes the decomposition of the blowing agent, that is, the establishment of the cell structure extremely quickly. The present invention relates to a liquid stabilizer for chlorine-containing resin foam, which is characterized by having a uniform and fine cell structure. As is well known, chlorine-containing resin foams have excellent physical properties. That is, tensile strength, elongation,
It has excellent tear strength, compression resistance, water resistance, chemical resistance, solvent resistance, etc., and can be easily flame-retardantly treated, making it extremely useful for general leather, wall covering materials, furniture products, etc. It is.
Generally, a method for obtaining such a foamed chlorine-containing resin is to homogeneously knead a composition in which the resin is mixed with a stabilizer, a blowing agent, and, if necessary, a plasticizer, filler, or pigment, and then gel it at a low temperature. The foaming agent contained in the composition, such as azodicarbonamide, is melted and then subjected to high-temperature treatment at a temperature of 180 to 280°C to decompose and generate gas, resulting in the foaming of a so-called chlorine-containing resin having a cell structure. The method of obtaining the body is being carried out industrially. Therefore, when obtaining the resin foam, it is desirable that the cell structure of the foam be uniform and fine, and that the foaming agent added should be rapidly decomposed to obtain a foam with a high magnification in a short time. is in strong demand in the market. Conventionally, various stabilizers have been proposed for the purpose of obtaining chlorine-containing resin foams. For example (1)Cd―
Ba-Pb, (2) Ba-Zn, (3) Ca-Zn or (4) K-Zn
It is a combination of metal parts such as. However, when using a stabilizer based on metal soap as described in (1) above, although it is excellent in terms of expansion ratio, hue, and fineness of cell structure, there are problems in terms of hygiene such as working environment hygiene and toxicity. There is. Also, (2) to (4)
When using a stabilizer based on metal soap, there are no problems such as toxicity, but there are drawbacks such as the cell structure not being sufficiently uniform and fine, and the expansion ratio and decomposition rate of the foaming agent being generally slow. . Therefore, so far, there have been methods for improving the cell structure by combining the above-mentioned metal soaps with an acrylic polymer or an alkylbenzene sulfonate;
Furthermore, a method has been proposed in which the metal soaps (2) to (4) are combined with a dialkyltin compound or zinc oxide to promote decomposition of the blowing agent. That is, US Pat. No. 3,399,107, US Pat.
The publication proposes a method for improving only the uniformity of the cell structure using a stabilizer consisting of a combination of the metals (1) and (2) and a single polymer of acrylate or methacrylate or a copolymer with acrylonitrile. There is. In addition, Japanese Patent Publication No. 49-21419 and Japanese Patent Publication No. 57-55734 disclose combinations of metal soaps (2) to (4) with alkanesulfonates or alkyl diphenyl ether disulfonates, and furthermore, Discloses a method for improving cell structure and hue using a stabilizer consisting of a combination of a surfactant and an acrylic polymer. However, recently, when the resin foam composition is foamed at high temperature and for a short time, even if the cell structure is sufficient, there is a major drawback that the decomposition time of the blowing agent, that is, the rise of the cells is slow. . Furthermore, (2)
The method of (4) using a basic salt or an overbased zinc salt in the metal series was reported in SPE Journal in 1967.
November issue, page 69, Special Publication No. 11429/1984 and No. 49-
This is proposed in Publication No. 21419. Since this method uses a stabilizer containing an activated zinc salt, it is a method that slightly improves the decomposition rate of the blowing agent and the rise of the cell structure, but is still insufficient. This method also has the disadvantage that the fineness and uniformity of the cell structure in the foam obtained by high-temperature processing is poor. Recently, however, compositions in which large amounts of compounding agents such as fillers, pigments, or flame retardants are added to the resin have been used, and on the other hand, in terms of performance, the stabilizers added to these compositions have a faster rise time. There is a need for fineness and uniformity of the cell structure, as well as a high temperature and short time foaming process. Therefore, there is a strong need for further improvements to the prior art as described above. Therefore, the present inventors have conducted various studies to meet the above-mentioned requirements, and have found that the blowing agent blended in the resin composition has an extremely fast decomposition rate, a high magnification, and a fine cell structure. This work has led to the completion of a new liquid stabilizer for chlorine-containing resin foams that does not reduce expansion ratio or discolor due to heat aging. That is, the present invention comprises (a) 3 to 60% by weight of zinc organic acid salt, (b) 3 to 60% by weight of alcohol and 3 to 60% by weight of zinc chloride.
This is a liquid stabilizer for chlorine-containing resin foams, which is composed of a mixture consisting of ~40% by weight and (c) 3~70% by weight of a solvent having a boiling point of 70°C or higher. Regarding zinc chloride in the liquid stabilizer component (b) of the present invention, for example, in JP-A-52-85245,
The present invention discloses a stabilizer comprising the metal soaps (1) to (4) above, zinc chloride dissolved in an organic hydrous acid group compound, and an organic phosphite. However, since the purpose is to thermally stabilize chlorine-containing resins, in particular to impart good hue, long-term thermal stability, and transparency, the technical problem of the present invention is to develop a foamed form of the resin, that is, a cell structure. This action and effect is completely different from the behavior such as uniform fineness and foam rise.
Further, JP-A-56-147833 discloses a blowing agent composition comprising azodicarbonamide, an inorganic zinc compound, and a fatty acid. However, the resin that is foamed is a polyolefin resin. Therefore, the subject matter of the present invention is different. The liquid stabilizer for chlorine-containing resin foam in the present invention, that is, the zinc organic acid salt as the stabilizer component (a) is generally referred to as zinc stabilizer,
The organic acid residue of such a set has 6 to 6 carbon atoms.
18 saturated or unsaturated aliphatic carboxylic acids or aromatic carboxylic acids containing 7 to 16 carbon atoms, such as hexanoic acid, octanoic acid, 2-ethylhexylic acid, decanoic acid, isodecanoic acid, neodecanoic acid, lauric acid, and Streic acid, oleic acid, ricinoleic acid, linoleic acid, linoleic acid, isostearic acid and benzoic acid, toluic acid, chlorobenzoic acid, p-tert-butylbenzoic acid, xylylic acid,
Examples include ethylbenzoic acid, p-octylbenzoic acid, and p-nonylbenzoic acid. Thus, the zinc organic acid salt bound to such an organic carboxylic acid residue may be an acidic salt or a neutral salt, and may be a basic salt or a super salt in which more than the total chemical equivalent of zinc metal in the salt is bound. It may also be a basic salt. The zinc organic acid salt is used as a component of the liquid stabilizer in an amount of 3 to 60% by weight, preferably 10 to 40% by weight. The alcohol as the component (b) in the liquid stabilizer of the present invention is, for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tertiary-butanol, etc.
Butanol, amyl alcohol, isoamyl alcohol, 3-pentanol, hexanol, isohexanol, 2-ethylbutanol, heptanol, isoheptanol, octanol, isooctanol, 2-ethylhexanol, 3, 5,
5-trimethylhexanol, nonanol, decanol, isodecanol, undecanol, dodecanol, isododecanol, tridecanol,
Also included are monohydric alcohols such as isotridecanol, tetradecanol, isotetradecanol, pentadecanol, isopentadecanol and cyclohexanol, 2-methylcyclohexanol, benzyl alcohol, and polyhydric alcohols and their derivatives. Ru. For example, ethylene glycol, ethylene glycol monoalkyl ether, diethylene glycol, diethylene glycol monoalkyl ether, triethylene glycol, triethylene glycol monoalkyl ether, polyethylene glycol, propylene glycol, propylene glycol monoalkyl ether, dipropylene glycol, dipropylene glycol monoalkyl ether , tripropylene glycol, tripropylene glycol monoalkyl ether, and 1.
Examples include alcohols such as 4-butanediol, glycerin, and glycerin monoacetate. Therefore, the above-mentioned alcohol may be a so-called hydrous alcohol containing water, and such alcohol may be used as a component of the liquid stabilizer of the present invention in an amount of 3 to 60% by weight, in order to dissolve a specific amount of zinc chloride.
Preferably it is 5 to 40% by weight. A mixture with such a specific amount is by its nature a clear liquid. Examples of the solvent having a boiling point of 70°C or higher for component (c) in the liquid stabilizer of the present invention include kerosene, benzene, toluene, xylene, ethylbenzene,
Hydrocarbon solvents such as diethylbenzene, dodecylbenzene, didodecylbenzene, liquid paraffin and mixed solvents thereof, and ester compounds such as phthalic acid diesters (diethyl, dibutyl,
Dihexyl, diheptyl, dioctyl, di-2-
ethylhexyl, butylbenzyl ester, etc.)
Examples include adipic diesters (diisobutyl, dioctyl, di-2-ethylhexyl, etc.), dibutyl sebacate, acetyl tributyl citrate, and butyl stearate, as well as solvents such as ethyl isobutyl ketone, dipropyl ketone, and diisobutyl ketone. Such a solvent is an important component for liquefying the stabilizer component and preventing precipitation. and 3 to 70% by weight, preferably 10 to 60% by weight as a component of the liquid stabilizer of the present invention.
It is. However, examples of hydrocarbon solvents include saturated hydrocarbon solvents such as IP Solvent 1016, 1620, and 2028 (manufactured by Idemitsu Petrochemical Co., Ltd.);
Liquid paraffin such as 70, 85, 90, 100, 145 (manufactured by Etsuso Standard Oil), Ipsol 100, 150
(manufactured by Idemitsu Petrochemical Co., Ltd.) and other unsaturated hydrocarbon solvents. The present invention is a liquid stabilizer for a chlorine-containing resin foam, which essentially consists of the three components (a) to (c) above, and the liquid stabilizer can be used for a long period of time. Even when stored, it does not become cloudy and/or precipitate, and because it is liquid, it has excellent dispersibility in the resin, and during foaming processing, it promotes the decomposition of the blowing agent, that is, the action of raising bubbles is remarkable, and it is uniform and fine. It is possible to obtain a foam with an excellent cell structure and high magnification. Therefore, the liquid stabilizer for chlorine-containing resin foam of the present invention can be prepared by adding or using a known stabilizer or stabilizing aid in addition to the three components (a) to (c) above. The hue of the structure, processability, and thermal stability are further improved. Such useful stabilizers or stabilizing aids include, for example, organic acid salts of Ba, Ca, Mg, K, Na or dialkyl tins, such as benzoic acid, toluic acid, p-tert-butylbenzoic acid. , 2-
Ethylhexylic acid, isodecanoic acid, lauric acid,
Organic acids such as oleic acid and stearic acid.
Also useful as thermal stabilizing aids are organic phosphites and epoxy compounds. Such organic phosphites include, for example, triphenyl phosphite, triisodecyl phosphite, phenyl diisooctyl phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, tribenzyl phosphite, and 4. Examples include 4'-isopropylidene diphenyl alkyl (C ₁₂ -C ₁₅ ) phosphite. Examples of the epoxy compound include epoxidized unsaturated oils and fats, epoxidized unsaturated fatty acid esters, epoxycyclohexane derivatives, and epichlorohydrin derivatives. In the present invention, known foaming aids can be used as appropriate.
That is, surfactants such as Ca of lauryl sulfonic acid or dodecyl sulfonic acid,
Examples include Ba, Na or Zn salts, polyoxyethylene (chain length 5-55) alkyl ( _C10 - _C13 ) phenyl ether phosphoric acid, and the like. Moreover, it is a methacrylic acid alkyl ester polymer,
For example, the alkyl residue may be ethyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, hexyl, heptyl, isooctyl, 2-ethylhexyl or lauryl. Other examples include dibutyltin oxide, dibutyltin sulfide, urea or urea derivatives, and metal oxides. Examples of chemical blowing agents used in the chlorine-containing resin foam of the present invention include azodicarbonamide,
Examples include azobisisobutyronitrile, benzenesulfonylhydrazide, p-toluenesulfonylhydrazide, p-toluenesulfonyl azide, and hydrazodicarbonamide. The chlorine-containing resins used in the present invention include polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, vinyl chloride-urethane copolymers, blends of ethylene-vinyl acetate copolymers and polyvinyl chloride, and block or graft copolymers. You can include combinations, etc. It has already been mentioned that the foam of the present invention is formulated with a plasticizer, a filler, a pigment, etc. in the chlorine-containing resin. Agents etc. can be used in combination. Next, in order to specifically explain the present invention, the present invention will be disclosed in detail using the following Examples and Test Examples. However, the present invention is not limited to these Examples in any way. Test Examples 1-1 to 9 and Comparative Examples 1-1 to 3 In these test examples, various alcohols were used to convert zinc chloride, which is the stabilizer component (b) of the present invention, into a transparent liquid. In addition, the liquefied mixture was placed in a closed container and observed for changes over time, especially for separation and precipitation. The results are shown in Table 1.

【table】

[Table] As is clear from the test results in Table 1 above, zinc chloride, the stabilizer component (b) of the present invention, is completely dissolved (complexed) only in alcohol, and each of the transparent liquids remains stable for more than 90 days. No separation and/or precipitation occurred even when the product was left sealed at room temperature. Examples 1-1 to 8 and Comparative Example 2-1 In this example, stabilizer components (a) to (c) of the present invention were stirred while heating to obtain each liquid stabilizer as shown in Table 2 below. Ta. Further, the stabilizer was placed in a sealed container and allowed to stand at room temperature to observe separation or formation of precipitate. The results are shown in Table 2.

【table】

[Table] Examples 2-1 to 10 and Comparative Examples 3-1 to 3 In order to examine the foaming state of the chlorine-containing resin composition to which the liquid stabilizer of the present invention was added, the following experiments were carried out. First, a vinyl chloride resin (average degree of polymerization of 800) obtained by emulsion polymerization was blended with each stabilizer shown in Table 3 to a basic composition consisting of a plasticizer, filler, etc. The composition was thoroughly mixed to form a completely homogeneous paste compound. Next, the compound was uniformly applied onto a base material of flameproof paper using a doctor knife to a thickness of 0.2 mm. Then, it was placed horizontally in a heating furnace at a temperature of 120°C and left to gel for 150 seconds to create a sheet. Furthermore, the sheet was placed in a foaming furnace at a temperature of 220°C and foamed for 30 to 100 seconds to form a foamed state.
In particular, we looked at the rise of the cell structure, that is, the decomposition rate of the blowing agent, the uniformity and fineness, the magnification, and the hue. In addition, the fineness of the cell structure (the size of the bubbles) can be determined by observing the surface and cross section of the foam using a microscope with a magnification of 40 times, and if the bubble size is 200μ or less and uniform, it is considered to have a good cell structure. did. The results are shown in Table 4. In judging the results, the symbols are: ◎ Very good 〇 Good △ Fair × Slightly bad × × Extremely bad. Basic blend vinyl chloride resin 100 parts by weight Dioctyl phthalate 60 〃 Azodicarbonamide 5 〃 Heavy calcium carbonate 50 〃 Titanium oxide (rutile type) 15 〃 Antimony oxide 5 〃 Rheohorse 65* 8 〃 Stabilizer (Table 3) *Ajinomoto Co., Ltd. organic phosphate flame retardant made by

【table】

【table】

【table】

Claims (1)

[Scope of Claims] 1. A mixture consisting of (a) 3 to 60% by weight of an organic acid salt of zinc, (b) 3 to 60% by weight of alcohol and 3 to 40% by weight of zinc chloride, and (c) a mixture having a boiling point of 70%. Solvent above ℃3
A liquid stabilizer for chlorine-containing resin foams consisting of ~70% by weight.