JPS60130629A - Vinyl chloride resin composition for foam - Google Patents

Abstract

PURPOSE:The titled composition which can give foam having a uniform and dense cell structure and excellent recovery, comprising a PVC resin, a chemical blowing agent, a polyunsaturated monomer, a Zn salt of an organic carboxylic acid, a K or Na salt of an organic carboxylic acid and an organotin compound. CONSTITUTION:A composition comprising a blowing agent, a polyunsaturated monomer, a zinc salt of an organic carboxylic acid, a potassium salt of an organic carboxylic acid and/or a sodium salt of an organic carboxylic acid, and organotin compounds of formulas I and/or II. Examples of the vinyl chloride resins include polyvinyl chloride and vinyl chloride/vinyl acetate copolymers. Examples of the chemical blowing agents include dinitrosopentamethylenetetramine and benzenesulfonyl hydrazide. Examples of the polyunsaturated monomers include ethylene glycol diacrylate and diallyl phthalate.

Description

[Detailed description of the invention] The present invention relates to a vinyl chloride resin composition for foam.

More specifically, it relates to a vinyl chloride resin composition that has a uniform and dense cell structure, and that even when foams are piled up, the cell structure does not get crushed and quickly returns to its original state, that is, a foam that has excellent recovery power is obtained. Vinyl resin foam is relatively inexpensive and has excellent elasticity and texture, making it extremely useful for applications such as leather, wall materials, and furniture products. I/Resin foams are generally obtained by uniformly kneading a blended composition in which the resin is blended with a stabilizer, a blowing agent, and, if necessary, a plasticizer, optical filler, or pigment, and then heated under low vortex. gelatinized at 18
A blowing agent in the composition is treated at a high temperature of 0 to 250"C,
For example, it is well known that a method of obtaining a polyvinyl chloride resin foam having a cell structure by dispersing a chemical abrasive agent such as azodicarbonamide and generating a gas has been carried out industrially.

When a foam is obtained using the above-mentioned blended composition, the cell structure is uniform and dense, and the cell structure does not get crushed even when the foam is piled up and quickly returns to its original state, that is, it has excellent recovery power. It is desirable and required in the market.

Various stabilizers have been proposed for the purpose of obtaining polyvinyl chloride resin foams. For example, fil Cd-Ba-
Zn, i21Cd-Ba-Pb, (31Ba-Zn
, (41Ca-Zn, (51K-Zn.

or acrylic polymer for (11 to (5)), and further (1
) to (51) have been proposed in combination with a foam stabilizer such as a flucansulfonate-based surfactant. When a stabilizer composition is used, the magnification and color are excellent, but there are drawbacks in terms of toxicity such as work environment hygiene. When using a stabilizer composition that reduces the density of the cell structure,
Inadequate hue, etc. Furthermore, the method of assembling an acrylic polymer into a metal soap system in fil~(5) does not provide sufficient density of the cell structure in the sieving box, which is approximately 10 times larger, and the vinyl chloride resin trap light filler, When a pigment or the like is used in combination, there is a drawback that the density of the cell structure further deteriorates.

By the way, as mentioned above, foamed products made of vinyl chloride resin have properties such as excellent physical properties such as elasticity and excellent texture, and therefore have a wide range of uses. In order to apply it to this wide variety of uses, it is strongly required that the cost be low. This is currently due to the filler, iiJ
There is a growing tendency to incorporate large amounts of plasticizers or pigments into the resin.
In addition, more sophisticated cell structures and higher magnification are required than ever before.

The stabilizer added is in the form of a bowl and is subject to strict regulations due to toxicity and pollution issues.

The inventors of the present invention have conducted various studies to meet the above-mentioned needs, and have found a composition that does not have the above-mentioned drawbacks, that is, a dense cell structure, a decrease in storage magnification during thermal history, and a foam that does not have the disadvantages described above. The cell structure is dense even when the foam is heated, so even if it is loaded with electricity, the cell structure will not be crushed and will return to its original state immediately, resulting in a foam with excellent resilience. The present invention provides a vinyl chloride resin composition for foams, comprising (I) and (at least 1 m17) of a 77-autoorganic tin compound selected from Shun.

The vinyl chloride resin (A) used in the present invention is polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-styrene copolymer. , vinyl chloride-vinylidene chloride copolymer, etc.

The chemical blowing agent [B) used in the present invention includes nitroso-based blowing agents, such as dinitron bentamethylenetetramine, N,N'-dimethyl-N, N'-dinitrosoterephthalimide, sulfohydrazide unexpanded agent, For example, benzenesulfonylhydrazide, P-4 luenesulfonylhydrazide), 4,4'-oxybisbenzenesulfonylhydrazide, trihydrazinotriazineacetone-P
-) luenesulfonylhydrazone, 'P-toluenesulfonylhydrazone, P-) luenesulfonyl azide, 2
．． 4-Toluene disulfonyl hydrazide, P-methylfuretane benzenesulfonyl hydrasite, hydrazone dicarbonamide, P-toluenesulfonyl semicarbazide, oxalyl hydrazide, azo blowing agents such as azobisisobutyronitrile, barium azodicarboxylate, diethyl Azodicarboxylate, nitrourea,
Examples include nitroguanidine and trinitrosotrimethylenetriamine.

In addition, the polyfunctional unsaturated monomer used in the present invention (C1 is a compound represented by (However, R, is +Ck1m+m
, C+ CHt+4, cu, cu, C(Cut
+s, He (Cut +t, n is 2 to 4 (
CHI-)m m is an integer from 1 to 8. ). For example, ethylene glycol noncyacrate, ethylene glycol methacrylate, propylene glycol cyacrate, glopylene glycol dimethacrylate, 1.4
Butanediol cyacrate, 1.4 butanediol dimethacrylate, 1.5 bentanediol cyacrate, 1.5bentanediol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane trimethacrylate, glycerin triacrylate,
Glycerin trimethacrylate, pentaerythritol, pentaacrylate, pentaerythritol trimethacrylate, diallyl phthalate, diallyl adipate,
Examples include diallyl sebacate.

The organic carboxylic acid zinc salt CD) used in the present invention has the formula (R4COO), Zn (R4 is 01 to Il+
is a saturated or unsaturated aliphatic hydrocarbon, or a C8~ alkylphenyl residue. ), examples of which include zinc acetate, zinc caproate, zinc caprylate, zinc laurate, zinc myristate, zinc stearate, zinc oleate, zinc isostearate, zinc benzoate, zinc toluate, and the like.

Potassium salt or sodium salt of an organic carboxylic acid used in the present invention (the odor is C,%), a potassium salt or sodium salt of a saturated or unsaturated aliphatic carboxylic acid or an aromatic carboxylic acid, Examples include potassium caproate, potassium caprate, potassium caprate, potassium laurate, potassium stearate, potassium octylate, potassium 2-ethylhexylate, potassium caprate, sodium canophosphate, sodium laurate, sodium decane, Examples include sodium oleate, sodium ricinoleate, and sodium toluate.

Organotin compound C represented by the formula (Il) used in the present invention
Examples of F+ include dimethyltin bisisooctylthioglycolate, dibutyltinbisisooctylthioglycolate, dioctyltinbisisooctylthioglycolate, dimethyltinbisisooctylthiopropionate, dibutyltinbisisooctylthioglycolate, Examples include dioctyltin bisisooctylthioglubionate.

Preferably, examples of the dibutyltin bis(inocty)U thioclicotin compound (k) represented by IIJ used in the invention include dimethyltin (bismonomethylmalate), dibutyltinbis(monomethylmalate), and dioctyltin. Tin bis (seven methyl malate),
Dibutyltin bis (monoethyl maleate), dibutyltin (monobutyl maleate), dibutyltin bis (mono-
2-ethylhexyl maleate), dibutyltin bis (monobenzyl maleate), dibutyltin bis (monocyclohexyl maleate), dibutyltin bis (monooleyl maleate), dioctyltin bis (monoethyl maleate), dioctyltin bis (motuptilma) dioctyltin bis(mono-2-ethylhexyl maleate), dioctyltin bis(monobenzyl maleate), dioctyltin bis(monocyclohexyl maleate), dioctyltin bis(monooleyl maleate), and the like. Preferably, dibutyltin bis(motuptyl maleate), dioctyltin bis(monoethyl maleate)theal.

Furthermore, it is possible to replace a part of the above organotin compound with the following organotin compound. Examples include dibutyltin dioletoate, dibutyltin dilaurate, dibutyltin dioleate, dibutyltin diisostearate, dibutyltin diisooleate, and the like.

The combination of the above compounds is based on the weight of organic carboxylic acid zinc salt/organic carboxylic acid potassium or/and) IJ
Organotin compound of (I) and/or (IIJ =
110.05 to 210.1 to 4, preferably 110.
2-1102-2, and the stabilizer of the combination of the compounds is blended with vinyl chloride resin, vinyl chloride resin 100
Ol-S*additional weight per part by weight, preferably 1 to 4N
It is a quantity part.

If it is more than 0.1 part, it is not effective as a stabilizer or can be sufficiently volatilized, and if it is more than 0.1 part, bloom may occur, which is not preferable. By using bath additives, you can make liquid one-buck from these stable oki. Solvents include turpentine, isoparaffinic hydrocarbons with a boiling point of 100°C or higher, toluene, xylene, dodecylbenzene, 2-ethylhexanol, decanol, tridecanol, dopanol 2
5 (Mitsubishi Yuka Products), oleyl alcohol, and cyclopyrene glycol sodium chloride, or a combination of two or more thereof can be used. Among these, combinations of turpentine or imparaffinic hydrocarbons and alcohols, or combinations of toluene, xylene, or dodecylbenzene and alcohols are particularly preferred.

Examples of the catalysts used in the present invention include t-butyl perbenzoate, t-butyl peracetate, di-tert-butyl, diverphthalate), 2,5-dimethylhexyl-2,5-di(peroxybenzoate), −))2
．． 5-dimethy/Iz-2,5-di(t-butylperoxy)hexane, dicumyl peroxide, di-tertiary
Butyl peroxide, 2,5-dimethylhexyl 2,5
Examples thereof include -dihydronox-oxide, cumene hatrobar oxide, P-menthanone hydrochloride oxide, and cyclohexanone hydrochloride oxide.

The amount of the catalyst is preferably 0.01 to 51% based on the polyfunctional unsaturated monomer. Further, the weight of the polyfunctional monomer is 01 to 50 parts by weight, preferably 1 part by weight, per 100 parts by weight of the vinyl chloride resin.
It is ~20 weight part.

The polyvinyl chloride resin composition for foams of the present invention can be used in many fields such as building materials such as walls, floors, ceilings, and synthetic leather.

Examples of plasticizers used in the present invention include dimethyl phthalate, dibutyl phthalate, dioctyl phthalate,
Examples include diindecyl phthalate, dioctyl adipate, dioctyl sepatate, tricridyl phosphate, epoxidized soybean oil, polyester plasticizers, and trioctyl trimellitate.

Furthermore, in addition to the above, optical fillers, flame retardants, colorants, antioxidants, ultraviolet absorbers, etc. can be used as necessary.

EXAMPLES Next, in order to specifically explain the present invention, the present invention will be explained in detail with reference to Examples. In addition, the part in the example shows one needle part.

Examples 1 to 7, Comparative Examples 1 to 3 In order to observe the foaming state of the vinyl chloride resin composition for foam according to the present invention, the formulations shown in Table 1 were added to 100 parts of vinyl chloride resin (emulsion polymer resin) as the basic formulation. In contrast, 100 parts of ground calcium carbonate, 10 parts of titanium oxide, 60 parts of DOP, 8 parts of azodicarbonamide, 10 to 20 parts of trimethylolpropane trimethacrynate, 2.5 parts of perhexine.
0.1 part of B and the stabilizer were mixed in a Raikai machine for 2 hours to prepare the oxic acid. This was then applied to the paper using a motorized aggregator. Put this in the gear open at 230℃ and check the foaming state during the required time, especially the uniformity of the cell structure.
Examples 1 to 7 and Comparative Examples 1 to 3 were observed for the foaming ratio and the time (seconds) for the RK body to return to its original state when pressed with a finger, that is, the recovery power. The results are shown in Table 1. The evaluation criteria for the uniformity of the cell structure were as follows.

Evaluation criteria 1) Foaming state (uniformity of cell structure) ○: The foam cells are uniform and the foam surface is also uniform.

×: The foam cells are non-uniform and the surface is uneven.

2) Expansion ratio The value obtained by dividing the thickness after foaming (am) by the thickness of the applied PVc compound (0.125).

3) Recovery power of foam After pressing the foam with a finger and placing a 100 g weight on it for 1 hour, the weight was removed and the time (seconds) until the surface returned to its original state was measured.

Claims (1)

[Scope of Claims] (A) Vinyl chloride resin, (Bl chemical blowing agent, (C1 polyfunctional unsaturated monosperm), (D) Zinc salt of W-carboxylic acid, (
Polyvinyl chloride for foams consisting of potassium or/and IJium salt of homogenized carboxylic acid, (F") at least one organotin compound selected from the following tIl and tU)] & Composition Things. Be1