JPH11189668A - Liquid stabilizer for preparation of chlorine-containing resin foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liquid stabilizer excellent in preventing permanent set in fatigue and plateout in emboss processing without damaging properties of foam molded articles by containing a (basic) zinc aromatic monocarboxylate, an aromatic monocarboxylic acid (salt) and a solvent having a boiling point of a specific temperature or higher. SOLUTION: The objective stabilizer contains 10-85 wt.% of (A) one of (A1 ) a zinc aromatic monocarboxylate, (A2 ) a basic A1 and (A3 ) a composition of A1 and A2 , 3-45 wt.% of (B) one of (B1 ) an aromatic monocarboxylic acid having 7-19 carbon atoms, (B2 ) at least one compound selected from Li, Na, K, Ca, Ba, Sr, Mg and organic tin salts of B1 , (B3 ) at least one compound selected from Ca, Ba, Sr, Mg and organic tin salts of a basic aromatic monocarboxylic acid having 7-19 carbon atoms and (B4 ) at least two of B1 , B2 and B3 and 8-60 wt.% of (C) a hydrocarbon solvent or an alcoholic solvent which have a boiling point of 100 deg.C or higher or a mixture thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid stabilizer used for producing a chlorine-containing resin foam, and more particularly to a liquid stabilizer suitably used for forming an uneven pattern on the surface of a chlorine-containing resin foam. is there.

[0002]

2. Description of the Related Art A chlorine-containing resin foam is excellent in tensile strength, elongation, tear strength, compression resistance, water resistance, chemical resistance, solvent resistance, and the like, and is easily flame-retardant. It is widely used for general leather, wall coverings or furniture products.

[0003] The method for producing these chlorine-containing resin foams is generally such that a plastisol comprising a chlorine-containing resin mixed with a stabilizer, a foaming agent, a plasticizer, a filler, a pigment and the like is uniformly coated on flame-retardant paper to form a gel. After performing the treatment, necessary printing is performed, and this is heated at a high temperature of 200 to 300 ° C., whereby the foaming agent, for example, azodicarbonamide contained in the plastisol is decomposed by heat to generate gas, thereby forming a gas bubble structure. To have a foam.

Various stabilizers have been proposed for use in the production of such chlorine-containing resin foams. Japanese Patent Publication No. 45-11429 proposes a combination of a basic zinc salt and a potassium salt using a carboxylic acid having 8 to 14 carbon atoms, and Japanese Patent Publication No. 49-21419 and Japanese Patent Laid-Open No. 54-1.
No. 29057 proposes a combination of a zinc-barium salt of a carboxylic acid or a zinc-potassium salt of a carboxylic acid, wherein the zinc salt uses a basic salt.

According to these methods, the above-mentioned basic zinc salt accelerates the decomposition action of the foaming agent and significantly increases the rise of foaming, as compared with conventionally used zinc carboxylate, for example, zinc stearate. Improve, but still not satisfactory.

[0006] From such a thing, Japanese Patent Publication No. 53-29,
Japanese Patent Publication No. 57-307 and Japanese Patent Publication No. 62-19777 show that a zinc compound such as zinc oxide, activated zinc oxide or zinc hydroxide is used as a foaming accelerator together with a metal salt of a carboxylic acid as a foaming stabilizer. It has been proposed to improve foaming rise. Furthermore, Japanese Patent Publication No. 53-2179
Discloses a method using melamine or urea, which is disclosed in
No. 133433 discloses a method using a reaction product of zinc chloride and a hydroxyamine or an alkylamine, and Japanese Patent Application Laid-Open No. 61-22123 uses urea and paraformaldehyde. It proposes ways to further improve the rise.

According to these methods, the decomposing action of the blowing agent is excellent, but it is difficult to uniformly mix and disperse the raw materials because the components used here are powder or crystalline. There was a problem. As another problem, a so-called embossing process for forming a textured pattern on the surface of the foam in order to enhance the texture when the foam is formed into a product by secondary processing is performed. In this process, the gas inside the foam escapes and the thickness of the foamed sheet decreases due to the gasket phenomenon, which reduces the thickness of the foamed sheet. There was a problem that desired embossing could not be performed on the sheet surface.

Further, in the same process as described above,
There is a problem that a foaming agent, a pigment, a filler, other additives or their decomposition products transferred from the foam adhere to the concave portions on the surface of the embossing roll, and a so-called plate-out that causes clogging of the concave portion of the roll occurs. Was. Due to these two phenomena, the unevenness of the product becomes thinner, and the appearance of the product becomes inferior due to the lack of the three-dimensional effect, and the trouble that the commercial value is greatly reduced frequently occurs.

[0009]

DISCLOSURE OF THE INVENTION In the production of a chlorine-containing resin foam, the present invention provides a foam having an excellent effect of accelerating the decomposition of a chemical foaming agent, having a high magnification and a good hue and feeling. An object of the present invention is to obtain a liquid stabilizer for producing a chlorine-containing resin foam, which can be obtained and has an excellent effect of preventing set-out and plate-out during embossing.

[0010]

The present invention comprises (a) 10 to 85% by weight, (b) 3 to 45% by weight and (c) 8 to 60% by weight, ) Is a zinc salt of an aromatic monocarboxylic acid, a zinc salt of a basic aromatic monocarboxylic acid, or one of a zinc salt of an aromatic monocarboxylic acid and a zinc salt of a basic aromatic monocarboxylic acid, and (b) is (B
-1), (b-2), (b-3) and (b-4), wherein (b-1) is an aromatic monocarboxylic acid having 7 to 19 carbon atoms, (b- 2) lithium, sodium, potassium, aromatic monocarboxylic acid having 7 to 19 carbon atoms;
At least one or more selected from calcium, barium, strontium, magnesium and organotin salts; (b-
3) is a composition containing at least two or more selected from the group consisting of calcium, barium, strontium, magnesium, and organotin salts of a basic aromatic monocarboxylic acid having 7 to 19 carbon atoms; b-1), (b-2)
And (b-3) or more, and (c) has a boiling point of 1
A liquid stabilizer for producing a chlorine-containing resin foam, which is a hydrocarbon solvent, an alcohol solvent or a mixed solvent thereof having a temperature of 00 ° C. or higher.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS (a) One of the constituent molecules of the liquid stabilizer of the present invention is a zinc salt of an aromatic monocarboxylic acid,
It is any one of a basic zinc salt of an aromatic monocarboxylic acid and a composition of a zinc salt of an aromatic monocarboxylic acid and a zinc salt of a basic aromatic monocarboxylic acid. These have 7 to 7 carbon atoms
It can be produced by a method of reacting an aromatic monocarboxylic acid of No. 19 with zinc oxide.

[0012] To further explain, this reaction is carried out with 7 to 1 carbon atoms.
A zinc salt of aromatic monocarboxylic acid obtained by reacting 1 mole of zinc oxide with 2 moles of aromatic monocarboxylic acid of No. 9 and an excess amount of zinc oxide with respect to the same amount of carboxylic acid. And any one of the above-mentioned basic aromatic zinc monocarboxylic acid salts and compositions of these aromatic zinc monocarboxylic acid salts and basic zinc aromatic monocarboxylic acid salts.

The structural formula of the zinc salt of aromatic monocarboxylic acid is a general formula

[0014]

Embedded image (In the formula, R ¹ and R ² are the same or different and represent an aromatic monocarboxylic acid residue having 7 to 19 carbon atoms.)

The basic aromatic monocarboxylic acid zinc salt is represented by the general formula:

[0016]

Embedded image (In the formula, R ³ and R ⁴ are the same or different and represent an aromatic monocarboxylic acid residue having 7 to 19 carbon atoms.) The aromatic monocarboxylic acid having 7 to 19 carbon atoms used when producing the component (a) includes, for example, benzoic acid, m-toluic acid, o-isopropylbenzoic acid, pt-butylbenzoic acid , P-nonylbenzoic acid, p
-Dodecylbenzoic acid, salicylic acid, p-methoxybenzoic acid, o-aminobenzoic acid, p-nitrobenzoic acid, o-acetylbenzoic acid or a mixed carboxylic acid thereof, and the benzene nucleus of the aromatic carboxylic acid described above. The position of each of the substituents bonded to may be at any of the o, m and p positions, and the type of the substituent is not limited thereto. The liquid stabilizer of the present invention includes a zinc salt of an aromatic monocarboxylic acid as the component (a) shown above,
Any one of 10 to 85% by weight, preferably 20% by weight of the basic aromatic zinc monocarboxylate, or the composition of the zinc zinc aromatic monocarboxylate and the basic zinc zinc salt of aromatic monocarboxylate.
Use ８０80% by weight. If the content is less than 10% by weight, foaming is insufficient and a high foam is not obtained. Also, this is 8
If the content exceeds 5% by weight, foaming is promoted, but a liquid stabilizer having fluidity cannot be obtained, and it becomes difficult to uniformly mix this with a plastisol.

(B) which is one of the constituents of the liquid stabilizer of the present invention includes (b-1), (b-2), (b-2),
(B-3) or (b-4), wherein (b-1) is an aromatic monocarboxylic acid having 7 to 19 carbon atoms, and (b-2) is an aromatic monocarboxylic acid having 7 to 19 carbon atoms. Lithium carboxylic acid,
At least one selected from the group consisting of sodium, potassium, calcium, barium, strontium, magnesium and organotin salts; (b-3) is a basic aromatic monocarboxylic acid having 7 to 19 carbon atoms, such as calcium, barium, strontium and magnesium. And at least one selected from organic tin salts, (b-4) is the above (b-1),
At least two of (b-2) and (b-3).

When the above component (b) is produced, the carbon number is 7 to 7 as in the case of producing the above component (a).
19 aromatic monocarboxylic acids are used. In the liquid stabilizer of the present invention, the component (b) is contained in an amount of 3 to 45% by weight, preferably 5 to 45% by weight.
Used in the range of ３０30% by weight. If the amount is less than 3% by weight, the thermal stability is not good, and if it exceeds 45%, foaming is suppressed. Component (c) of the present invention has a boiling point of 1
A hydrocarbon solvent, an alcohol solvent or a mixed solvent thereof at a temperature of 00 ° C. or higher.

The boiling point of one of the components (c) of the present invention is 10
Xylene, boiling point 1
Odorless kerosene at 49 to 343 ° C. Examples of the odorless kerosene include alkene L, 56N, and Hisol SAS
-295, SAS-296 or SAS-LH (the above names are trade names of Nippon Petrochemical Co., Ltd.), Ipsol 100, 1
50, IP solvent 1016, IP solvent 1620, IP solvent 202
8 or 2835 (trade names of Idemitsu Petrochemical Co., Ltd.), Loose (trade name of Shell Chemical Co., Ltd.), Exsol D-40, D-80 or D-100 (all are Exxon Chemical Co., Ltd.) (Trade name), liquid paraffin, Nagara LP-30 (trade name of Chuo Kaseihin Co., Ltd.), Cosmo White P-70 (trade name of Cosmo Oil Co., Ltd.), Christol 70, 85, 90 , 100 or 145
(The above are trade names of Exxon Chemical Co., Ltd.). If the boiling point of the hydrocarbon solvent is less than 100 ° C., the volatility is high, handling is not preferable, and the foaming property is adversely affected.

Examples of the alcohol solvent as one of the components (c) include monohydric to polyhydric alcohols and derivatives thereof. For example, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, t-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2 -Methyl-1-pentanol, 4-methyl-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2
-Ethyl-1-hexanol, 1-nonanol, 3,
5,5-trimethyl-1-hexanol, 1-decanol, cyclohexanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol Ethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol, polyethylene glycol, propylene glycol, propylene glycol monomethyl ether,
Dipropylene glycol, dipropylene glycol monobutyl ether, tripropylene glycol, polypropylene glycol, 1,4-butanediol, 3-methoxybutanol and glycerin.

The above alcohol has a high volatility when the number of carbon atoms is less than 5, and has a high clay content when it has more than 13, which is not preferable in handling. The liquid stabilizer of the present invention uses the component (c) at 8 to 60% by weight. If it is less than 8% by weight, liquefaction is not sufficient, and if it exceeds 60% by weight, the effect as a stabilizer is inferior.

As described above, the liquid stabilizer of the present invention comprises:
(A) a zinc zinc aromatic monocarboxylate, a basic zinc zinc aromatic monocarboxylate, or a specific amount of any of the zinc aromatic monocarboxylate and the basic zinc zinc aromatic monocarboxylate composition; (B) an aromatic monocarboxylic acid having 7 to 19 carbon atoms, lithium, sodium, potassium, calcium, barium of an aromatic monocarboxylic acid having 7 to 19 carbon atoms,
At least one or more selected from strontium, magnesium and organic tin salts, and at least one or more selected from calcium, barium, strontium, magnesium and organic tin salts of aromatic monocarboxylic acids having 7 to 19 carbon atoms, or at least two of them. A composition consisting of a specific amount of a composition containing at least one or more species and (c) a specific amount of (a), (b), (c) of a hydrocarbon-based solvent, an alcohol-based solvent or a mixture thereof having a boiling point of 100 ° C. or higher. Things.

The amount of the liquid stabilizer used for producing a chlorine-containing resin foam is preferably 1.0 to 10 parts by weight based on 100 parts by weight of the chlorine-containing resin. Further, to the liquid stabilizer of the present invention, if necessary, other stabilizing aids, cell preparation agents and the like can be appropriately added. Examples of the stabilizing aid used here include organic phosphites, organic phosphates and metal salts thereof.

Examples of the organic phosphite include triphenyl phosphite, triisooctyl phosphite, tristridecyl phosphite, diphenyl monooctyl phosphite, diphenyl monodecyl phosphite, and 4,4. - isopropylidene diphenyl alkyl (C ₁₂ ~C ₁₅₎ diphosphite and the like. Examples of the organic phosphate and its metal salt include diisooctyl acid phosphate, bistridecyl acid phosphate, zinc or potassium diisooctyl acid phosphate, and zinc or potassium salt of bistridecyl acid phosphate.

Examples of the cell preparation include a surfactant and an acrylic polymer. Examples of surfactants include, for example, sodium, barium, calcium or zinc salts of lauryl alcohol sulfonate,
Examples include sodium, potassium, barium, calcium or zinc n-dodecylbenzenesulfonate, sodium dodecylphenoxypolyoxyethylenesulfonate, and the like.

Examples of the acrylic polymer include butyl methacrylate polymer, isobutyl methacrylate polymer, t-butyl methacrylate polymer, and methacrylic acid polymer having a degree of polymerization in the range of 100 to 2,000. Examples include isooctyl ester polymer, methacrylic acid-2-ethylhexyl ester polymer, methacrylic acid isodecyl ester polymer, and methacrylic acid lauryl ester polymer.

In the production of a chlorine-containing resin foam, a chlorine-containing resin, a foaming agent, the liquid stabilizer of the present invention, and, if necessary, a foaming accelerator, a plasticizer and other various additives may be appropriately compounded. it can.

The production of the chlorine-containing resin is not particularly limited to a polymerization method such as emulsion polymerization, suspension polymerization and bulk polymerization.
Chlorine-containing resins are, for example, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene,
Chlorinated polypropylene, 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-urethane copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride −
Methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-various vinyl ether copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile terpolymer Chlorine-containing resins such as vinyl chloride-vinylidene chloride-vinyl acetate terpolymers, and their blends or other chlorine-free synthetic resins such as acrylonitrile-styrene copolymers, ethylene-vinyl acetate copolymers. And a blended product of an ethylene-ethyl (meth) acrylate copolymer and a polyester; a block copolymer; a graft copolymer; and the like.
In particular, a vinyl chloride homopolymer is preferable, and polyvinyl chloride for base processing having fine particles having an average particle diameter of 0.1 to 5 μm obtained by an emulsion polymerization method or a microsuspension method (suspension polymerization method) is preferred. preferable.

Examples of the foaming agent include azo foaming agents which are thermal decomposition type chemical foaming agents, nitroso foaming agents, hydrazide foaming agents, carbazide foaming agents, and triazine foaming agents. Dicarbonamide,
A hydrazide p, p'-oxybis (benzenesulfonyl hydrazide) or a combination thereof is preferred. Examples of the azo foaming agent include azodicarbonamide, azobisisobutylnitrile, diazoaminobenzene, diethylazodicarboxylate, diisopropylazodicarboxylate, and azobis (hexahydrobenzonitrile).

Examples of the nitroso foaming agent include N,
N'-dinitroterephthalamine, N, N'-dinitropentamethylenetetramine and the like. As the hydrazide-based blowing agent, for example, benzenesulfonyl hydrazide,
3,3'-disulfone hydrazide phenyl sulfone, toluene disulfonyl hydrazone, thiobis (benzenesulfonyl hydrazide), p, p'-oxybis (benzenesulfonyl hydrazide) and the like. Examples of the carbazide-based blowing agent include p-toluenesulfonyl semicarbazide and 4,4'-oxybis (benzenesulfonyl semicarbazide). Examples of the triazine-based blowing agent include trihydrazinotriazine and 1,3-bis (o-biphenyltriazine). Examples of the foaming accelerator include urea, zinc oxide, oxalic acid, tartaric acid,
Sodium, calcium, barium or zinc salts of perchloric acid and glycol complexes thereof.

Examples of the plasticizer include phthalate plasticizers such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, and diisononyl phthalate; adipate plasticizers such as dioctyl adipate, diisononyl adipate; di (butyl diglycol) adipate; Examples thereof include phosphate plasticizers such as zyl phosphate, polyester plasticizers, chlorinated paraffin plasticizers, trimellitate plasticizers, pyromellitate plasticizers, and biphenyltetracarboxylate plasticizers.

As other additives, there may be mentioned those usually used for chlorine-containing resins such as polyvinyl chloride, for example, synthetic hydrotalcite, synthetic zeolite,
Partial ester of dipentaerythritol and adipic acid, polyols and tris (2-hydroxyethyl)
Heat-resistant assistants such as isocyanurate, epoxy compounds such as epoxidized soybean oil and epoxidized resin, coloring inhibitors such as sulfolene and β-diketone compounds, antioxidants such as phenol-based or sulfur-based, hindered amine-based light stabilizers, UV absorbers, fillers, pigments, flame retardants, lubricants, antistatic agents, plateout inhibitors, fungicides, antibacterial agents, antioxidants, vulcanization accelerators, crosslinkers, matting agents, improved rebound resilience Agents, sol viscosity reducing agents, silicon, titanium or aluminum based coupling agents, phosphorus based surfactants, metal deactivators, release agents, surface treatment agents and the like.

[0033]

EXAMPLES (Synthesis Examples 1 to 3 and Comparative Examples 1 to 3) Here, Synthesis Examples 1 to 3 are components (a) of the examples of the present invention, and Comparative Examples 1 to 3 are components (a) This is a case in which no aromatic monocarboxylic acid was used. In this synthesis, the component (c) was used as a reaction solvent.

A specific amount of the solvent and the aromatic monocarboxylic acid (other kinds of carboxylic acids in the comparative example) shown in Table 1 were
The mixture was weighed in a 00 ml three-necked flask, and dissolved by stirring while heating. To this, a specific amount of zinc oxide was added at 70 ° C. or lower, and the temperature was raised to 100 ° C. while gradually heating, followed by a reaction for 30 minutes. The reaction was completed while further heating and 12
Water was sufficiently distilled off under reduced pressure at 0 ° C. to obtain 70 g of a transparent oily zinc salt of an aromatic monocarboxylic acid, a basic zinc salt of an aromatic monocarboxylic acid, or a mixture thereof. Table 1 shows the obtained stabilizer component (a).

[0035]

[Table 1] However, * in the above Table 1 is the component (c), and the carboxylic acids used in the synthesis examples of the present invention are all aromatic monocarboxylic acids. (Synthesis Examples 4 to 6, Comparative Examples 4 to 6) Synthesis Examples 4 to 6 here
Are the components (b) of the examples of the present invention, and Comparative Examples 4 to 6.
Fig. 4 shows a case where the aromatic monocarboxylic acid was not used in the component (b). In synthesizing these, the component (c) was used as a reaction solvent.

A specific amount of a solvent and an aromatic monocarboxylic acid (other kinds of carboxylic acids or alkylphenols in the case of the comparative example) shown in Table 2 were weighed in a 300 ml three-necked flask, and dissolved by stirring while heating. Was. To this, a specific amount of barium hydroxide (octahydrate) is added at 80 ° C. or lower, the temperature is gradually increased to 120 ° C., and water is sufficiently distilled off under reduced pressure to complete the reaction. There was obtained 30 g of a barium salt of an aromatic monocarboxylic acid, a barium salt of a basic aromatic monocarboxylic acid, or a mixture thereof. Table 2 shows the obtained stabilizer component (b).

[0037]

[Table 2] However, * in Table 2 above is the component (c), and the carboxylic acids used in the synthesis examples of the present invention are all aromatic monocarboxylic acids. (Synthesis Examples 7 to 10 and Comparative Examples 7 to 10) Here, the component (a) of the present invention synthesized in the synthesis example shown in Table 1 and the (b) of the present invention synthesized in the synthesis example shown in Table 2 ) A liquid stabilizer was synthesized using the components and the synthetic products of Comparative Examples. First, as shown in Table 3, the stabilizer components (a) to
Each of the specific amounts of (c) was weighed, and these were weighed at 90 ° C. for 3 hours.
Stir for 0 minutes and mix thoroughly to obtain a uniform oily stabilizer 10
0 g was obtained. The liquid stabilizer thus obtained is shown in Table 3.

[0038]

[Table 3] However, * -1 in Table 3 above corresponds to the component (b-1) of claim 1, * -2 corresponds to the component (b-2) of claim 1, *-
3 corresponds to the component (c) of claim 1. * -4 is a non-aromatic carboxylic acid, and * -5 is a non-aromatic calcium carboxylate. In the synthesis examples of the present invention, the carboxylic acids used are all aromatic monocarboxylic acids.

(Examples 1 to 3, Comparative Examples 1 to 3) Chlorine-containing resins to which the liquid stabilizer of the present invention and the comparative liquid stabilizer were added were prepared as follows, and then foams were formed. In this example, polyvinyl chloride (average degree of polymerization: 800) obtained by emulsion polymerization is used with a plasticizer, a foaming agent, a cell preparation agent (cell stabilizer), a filler, a pigment, a diluent, a flame retardant plasticizer, and the like. The liquid stabilizer of the present invention and the liquid stabilizer of the comparative example were added to the following basic compound consisting of the following components and mixed well with a mixer to obtain a uniform plastisol compound.

Basic Formulation Polyvinyl chloride (chlorine-containing resin) 100 parts by weight Dioctyl phthalate (plasticizer) 48 parts by weight Azodicarbonamide (blowing agent) 4 parts by weight Isobutyl methacrylate polymer 0.5 part by weight (cell preparation agent) ) Heavy calcium carbonate (filler) 100 parts by weight Rutile type titanium oxide (pigment) 15 parts by weight White kerosene (diluent) 10 parts by weight 45% chlorinated paraffin (flame retardant plasticizer) 8 parts by weight Liquid stabilizer ( (Described in Table 4) The above sol was uniformly coated on a flame-retardant paper as a base with a doctor knife so as to have a thickness of 0.2 mm. This is 150
The sheet was placed horizontally in a heating furnace heated to ° C. and left for 60 seconds to gel to form a sheet, which was used as an original sheet. A part of the original sheet was sampled to prepare a test piece, which was placed in a foaming furnace heated to 240 ° C. for a predetermined time to foam. The foaming state at this time, particularly the foaming speed (rising of bubbles), whiteness, uniformity and fineness of bubbles, surface smoothness, etc. were examined.

The size of the bubbles showing the uniformity and fineness of the bubbles was measured by using a microscope of 40 times magnification, and the cut surface of the foamed sheet was observed. The plate-out test was performed as follows. Three 30 × 30 mm sheet pieces are collected from the above-mentioned original sheet, and one sheet is placed on a ferro plate so that the coating surface is in contact with the sheet, placed in a heating furnace at 110 ° C., taken out after 5 minutes, and immediately pressed with a roller. After that, the sheet was removed.
Next, a new sheet piece was placed on the ferroplate at the same position as the previous pressure-bonded surface, and the same operation was performed. This operation was repeated three times. By repeating this operation, plate-out, which is the amount of contaminants (degree of contamination) adhering to the mirror surface on the ferro plate, was observed. The results were determined as follows.

With respect to the foaming rate, whiteness, surface smoothness and plate-out, a 5-grade evaluation was given, which was extremely excellent: 5, excellent: 4, normal: 3, slightly poor: 2, poor: 1. . The size of the bubble is measured with a microscope, and the diameter is 5 when the bubble diameter is less than 200 μm and 4 or 2 when the bubble diameter is 200 to less than 250 μm.
The five-level display is indicated by 3 when the length is less than 50 to 350 μm; If the numerical value is 4 or more in these five-stage display, there is no problem in industrial implementation.

Next, the foamed sheet was placed in a foaming furnace heated to 225 ° C. for a predetermined time, and the degree of settling due to reheating during embossing was examined. The results are shown in Table 4. In addition, the judgment of the result was shown in percentage by the following formula.

(Thickness of foam sheet reheated) / (thickness of foam sheet) × 100 = severity If this value is 80 or more, there is no hindrance to embossing due to a decrease in sheet thickness, and industrial implementation is possible. There is no problem at all.

[0045]

[Table 4] As is clear from Table 4, according to the present invention, extremely excellent results are shown in prevention of settling and plate-out during embossing, which is a problem to be solved by the present invention. On the other hand, in the comparative example, in both of the above two performance items, the result was several steps inferior to the present invention. (Examples 4 to 6 and Comparative Examples 4 to 5) In this example, a combination agent and a stabilizer having extremely low toxicity are added in combination.

Basic Formulation Polyvinyl chloride (chlorine-containing resin) 100 parts by weight Diisononyl adipate (plasticizer) 50 parts by weight Azodicarbonamide (blowing agent) 3 parts by weight p, p -Oxybis (benzenesulfonyl hydrazide) (foaming agent) 1.5 parts by weight Isobutyl methacrylate polymer 0.4 part by weight (cell preparation) Sodium n-dodecylbenzenesulfonate 0.3 part by weight (cell preparation) weight Calcium carbonate (filler) 100 parts by weight Rutile-type titanium oxide (pigment) 15 parts by weight n-dodecylbenzene (diluent) 100 parts by weight Liquid stabilizer (described in Table 4) The above composition is sufficiently mixed with a mixer. Mix to form a uniform plastisol compound. The following tests were performed using this sol under the same method and conditions as in Examples 1 to 3 and Comparative Examples 1 to 3 described above. The determination method was also performed in the same manner as in Examples 1 to 3 and Comparative Examples 1 to 3 in Table 4. The results are shown in Table 5.

[0047]

[Table 5] As is clear from Table 5, according to the present invention, extremely excellent results are shown in prevention of settling and plate-out during embossing, which is a problem to be solved by the present invention. On the other hand, in the comparative example, in both of the above two performance items, the result was several steps inferior to the present invention.

[0048]

The chlorine-containing resin composition to which the liquid stabilizer for producing a chlorine-containing resin foam of the present invention is added is a carboxylic acid or a carboxylic acid used for a metal thereof as shown in Synthesis Examples and Examples. Are all aromatic monocarboxylic acids, so they have excellent prevention of settling and plate-out during embossing without impairing the various properties required for foamed molded products. A foamed product is obtained.

Claims (1)

[Claims] (1) 10-85% by weight of (a) shown below:
(B) is contained in an amount of 3 to 45% by weight and (c) in an amount of 8 to 60% by weight, and (a) is a zinc salt of an aromatic monocarboxylic acid, a zinc salt of a basic aromatic monocarboxylic acid, and a zinc salt of an aromatic monocarboxylic acid. Any one of the salt and the basic aromatic monocarboxylic acid zinc salt composition, wherein (b) is the following (b-1), (b-2), (b-3) and (b-4) Wherein (b-1) is an aromatic monocarboxylic acid having 7 to 19 carbon atoms, and (b-2) is lithium, sodium, or potassium of an aromatic monocarboxylic acid having 7 to 19 carbon atoms. , Calcium, barium, strontium, magnesium and organic tin salts, and (b-3) is a basic aromatic monocarboxylic acid having 7 to 19 carbon atoms, such as calcium, barium, strontium, magnesium and organic tin. Less selected from salt One or more than, (b-4) are of the (b-1), (b-
2) and at least two kinds of (b-3), (c) is a hydrocarbon-based solvent, an alcohol-based solvent or a mixed solvent thereof having a boiling point of 100 ° C. or more, for producing a chlorine-containing resin foam. Liquid stabilizer.