JPS58180661A - Vinyl chloride resin nonwoven fiber structure - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a vinyl chloride resin nonwoven fiber structure.

Conventionally, nonwoven fiber structures made of resins such as polypropylene, polyethylene, and nylon have been known, but they have drawbacks in flame retardancy and coloring, so nonwovens made of vinyl chloride resin, which has excellent flame retardancy and is easy to color, have been used. The fiber structure is striking. PVC resin foam sheets, which are flame-retardant and easy to color, are widely used in automobile interiors and other applications, but they are not breathable.
Sheet-like nonwoven fiber structures made of vinyl chloride resin are also in demand in fields where breathability is required.

Due to its characteristics, vinyl chloride resin releases hydrochloric acid and easily decomposes, requiring stabilizers such as metal compounds.However, conventional techniques for processing resins such as polypropylene and polyethylene into non-woven fiber structures do not use vinyl chloride resin. It was difficult to process it into nonwoven fibrous structures.

An object of the present invention is to provide a breathable nonwoven fiber structure made of vinyl chloride resin that has excellent flame retardancy and is easy to color.

As a result of repeated research aimed at obtaining a breathable vinyl chloride resin non-woven fiber structure, the present inventors changed the type and content of the metal compound contained during foam extrusion molding of vinyl chloride resin. The properties of the foamed sheet obtained by this process change greatly, and uniform fine bubbles are generated depending on the combination and content ratio of specific metal compounds, and the generated bubbles collapse, making the vinyl chloride resin non-woven. They discovered that it can be made into a fibrous sheet and completed the present invention.

That is, according to the present invention, one or more metal compounds selected from the group consisting of zinc compounds and barium compounds (hereinafter referred to as metal compound A), and one or more types selected from the group consisting of tin compounds and calcium/ium compounds. contains a metal compound (hereinafter referred to as metal compound B), and the content ratio of metal compound A and metal compound B is o. oooi~100
An opened vinyl chloride resin nonwoven fiber structure is obtained.

The vinyl chloride resin nonwoven fiber structure of the present invention is produced by foaming and extruding vinyl chloride resin in the presence of metal compound A and metal compound B using a foaming agent such as azodicarbonate, as described later. You can get it.

The feature of the present invention lies in the combination of metal compounds and their content ratios that are included when vinyl chloride resin is foamed and extruded.

The combination of metal compounds used in the present invention is one or more metal compounds A selected from the group consisting of zinc compounds and barium compounds, and one or more metals selected from the group consisting of tin compounds and calcium compounds. It is compound B, and it is not possible to obtain a vinyl chloride nonwoven fiber structure having the desired fine and uniform fiber diameter with only one of them. For metal compound A alone, the foam extrusion molding temperature (
Foaming decomposition occurs at temperatures below 180 to 250°C, and the diameter of the opened fibers becomes insufficiently fine and non-uniform. Furthermore, if the metal compound B is used alone, foaming and opening are suppressed, and the vinyl chloride resin does not become a nonwoven fiber structure.

The compounds used as metal compound A are (1) a zinc compound and (2) a barium compound.・(1) Examples of zinc compounds include zinc acetate, zinc probioate, zinc valerate, zinc caproate, zinc laurate, zinc myristate, zinc harmitate, zinc stearate, zinc oleate, zinc ricinoleate. , salts of aliphatic or aromatic carboxylic acids such as zinc naphthenate, zinc 2-ethylhexoate, zinc benzoate, zinc succinate, zinc carbonate, salts of phenol derivatives, and zinc white.

(2) Examples of barium compounds include barium acetate, barium probionate, barium valerate, barium cabroate, barium laurate, barium myristate, barium palmitate, barium stearate, barium oleate, barium ricinoleate, Examples include salts of aliphatic or aromatic carboxylic acids and salts of phenol derivatives such as barium naphthenate, barium 2-ethylhequinoate, barium benzoate, barium malonate, and barium carbonate.

The appropriate amount of metal compound A to be used is 0.00001 to 5 parts by weight, preferably 0.00001 to 5 parts by weight, per 100 parts by weight of vinyl chloride resin.
0002-3 parts by weight, more preferably (1.OO1-3
Parts by weight. If the amount of metal compound A used exceeds 5 parts by weight per 100 parts by weight of vinyl chloride resin, foaming decomposition will occur below the foaming extrusion molding temperature, and the diameter of the opened fibers will not be sufficiently fine and non-uniform. A vinyl chloride resin nonwoven fiber structure cannot be obtained. Also, if metal compound A is not substantially included, foaming occurs. Spreading is suppressed and the vinyl chloride resin does not become a nonwoven fiber structure.

The compounds used as the metal compound B are (3) a tin compound and (4) a carunium compound.

(3) Examples of tin compounds include salts of aliphatic or aromatic carboxylic acids such as tin valerate, tin 2-ethylhexoate, tin laurate, tin stearate, tin benzoate, and tin carbonate, and phenol derivatives. Alkyl or alkaline salts such as dibutyltin dilaurate, dibutyltin laurate malate, dibutyltin bismethyl maleate, dibutyltin maleate, dibutyltin laurate methyl maleate, dioctyltin dinonylate, dioctyltin dilaurate, tribenzyltin laurate, etc. and salts of aliphatic or aromatic carboxylic acids of tin, alkyl or allyltin sulfur-containing compounds such as dibutyltin dilauryl merbutide, diptyltin β-mercaptogropionate, dibutyltin pisisooctylthioglyconate, dioctyltin sulfide Q,
Examples include alkyl-containing compounds such as dibutyltin oxide and dibutyltin octyl oxide laurate.

(4) Examples of calcium compounds include calcium valerate, carunium 2-ethylhexylinate, calcium laurate, carunium oleate, calcium linoleate, carunium stearate, calcium maleate, calcium benzoate, calcium phosphate, etc. C
Examples include aliphatic or aromatic carboxylates of 4 to CZa and salts of phenol derivatives.

The appropriate amount of metal compound B to be used is 0.00001 to 20 parts by weight per 100 parts by weight of vinyl chloride resin, preferably O.
．． OO01-10 parts by weight, more preferably 0.05-5
Parts by weight. If the amount of metal compound B used exceeds 20 parts by weight, problems such as blooming will occur. Furthermore, if metal compound B is not substantially contained, foam decomposition occurs below the foam molding temperature, resulting in insufficient and non-uniform refinement of the diameter of the opened fibers.

In the present invention, it is necessary that metal compound A and metal compound B be contained at the same time, and their content is as described above, but in order to form the vinyl chloride resin into a nonwoven fiber structure, they are necessary. It is necessary to keep the content ratio within a specific range. That is, the content ratio of metal compound A and metal compound B is O. OOO is required to be 1 to 100, preferably 0.0005 to 20, and more preferably O.O.O. OO1-5. The content ratio is 0.
If it is less than 0001, fiber opening will be suppressed and the vinyl chloride resin will not form a nonwoven fiber structure. Furthermore, if the content ratio exceeds 100, foaming and opening cannot be well controlled, and the resulting vinyl chloride resin nonwoven fiber structure becomes a non-uniform coarse network and cannot be used.

In other words, by coexisting metal compound A and metal compound B in a specific quantitative ratio, the foaming extrusion molding of vinyl chloride resin is controlled, and the generated extremely fine bubbles are further collapsed to form a fibrous form. However, the vinyl chloride resin can be made into a nonwoven fiber structure.

The vinyl chloride resins used in the present invention include polyvinyl chloride, vinyl acetate based on vinyl chloride, vinylidene chloride, diethyl maleate, methylmethacrylate,
It is a copolymer with vinyl compounds such as butyl acrylate, ethylene, and propylene.

These vinyl chloride resins can be obtained by already known methods such as emulsion polymerization, suspension polymerization, and solvent polymerization, and those obtained by any method can be used.

No special method or apparatus is required for producing the vinyl chloride resin nonwoven fiber structure of the present invention, and any ordinary method or apparatus for producing structures by extruding vinyl chloride resin can be used. That is, in the presence of metal compound A and metal compound B, a foaming agent such as azodicarponamide or latoluenesulfonyl semicarnodide is added, and vinyl chloride is produced by an already known method such as extrusion through a circular gouer, T-die, etc. A resin nonwoven fibrous structure is produced.

As the blowing agent used in the present invention, any foaming agent used for foam molding of vinyl chloride resin can be used, but particularly preferable ones include azodicarbonamide, dinitro 4
Pentamethylenetetramine, balatoluenesulfonyl semihydrazine, trihydrazine triazine, P,P'-
Oxybisbenzenesulfonyl semi-rubazide, hydrado dicarbonamide, barium azodicarboxylate, etc. can be obtained. Of course, the amount of blowing agent used can be changed depending on the type of blowing agent, extrusion conditions, type and content of metal compound, etc., but for azopiscarbonamide, paratoluenesulfonyl hydrazide, etc., 100 parts by weight of vinyl chloride resin is used. It is preferably 901 to 10 parts by weight.

In addition to Metal Compound A and Metal Compound B, it is of course possible to use vinyl chloride resin stabilizers such as Namari-based and cadmium-based metal compounds, epoxy compounds, ultraviolet absorbers, organic phosphorus compounds, and organic sulfur compounds. It is.

Furthermore, it goes without saying that the vinyl chloride resin used in the present invention may contain additives such as plasticizers, lubricants, colorants, fillers, etc., if necessary.

The present invention will be explained below with reference to Examples. It goes without saying that this example is merely an example, and does not limit the technical scope of the present invention.

Examples 1 to 9 Polyvinyl chloride 100 parts by weight Octyl phthalate (plasticizer) 30 Azodicarbonamide (foaming agent) 2 Methylene bisstearamide (lubricant) 2 #Metal compound A
For compound names and amounts used, see Table 1 Metal Compound B. The above-mentioned mixture was extruded through a flat die (slit gap 1.0111) at 220 to 250°C and rolled up at room temperature at a stretching ratio of 10. The obtained fiber had a sufficiently fine diameter when opened and had a uniform nonwoven fiber structure.

The results obtained are shown in Table-1.

Photographs of representative nonwoven fiber structures produced are shown in FIGS. 1 to 3.

Notes on Table-1 Note 1) The symbol shown in the compound name indicates the following compound.

Zn-La: zinc laurate, Ba-St: x barium stearate, ZnO: zinc white, Zn-Ac: zinc acetate,
Ba-Na: barium naphthenate DBTDLS: diptyltin dilauryl mercaptite, Ca-St: calcium stearate, Sn-St:
Tin stearate, DOTDLa: dioctyl dilaurate, Ca-La: calcium laurate Note 2) Content (phr) indicates parts by weight per 100 parts by weight of vinyl chloride resin. In addition, A (or B)-1 and A (or B)-2 are the contents of the compounds described in A (or B)-1 and A (or B)-2 of the compound name, respectively, and the total is A (or B) Shown in total.

Comparative Example 1 A sheet-like product was obtained in the same manner as in Example 1 except that the metal compound A was not included. This sheet-like material had insufficient foaming and opening to form a non-woven fiber structure (see Figure 4).

Comparative Example 2 A sheet-like product was obtained in the same manner as in Example 1, except that 0.0001 part by weight of barium stearate (metal compound A) was included.

This sheet-like material was similar to Comparative Example 1 and did not have a nonwoven fiber structure.

Comparative Example 3 7- was prepared in the same manner as in Example 4 except that metal compound B was not included.
An attempt was made to obtain a sheet-shaped product, but foaming and decomposition occurred before entering the flat die, and molding was not possible.

Comparative Example 4 An attempt was made to obtain a sheet-like material in the same manner as in Example 4 except that 0.005 parts by weight of carunium stearate (metal compound B) was included, but foaming and decomposition could not be controlled, and the same as in Comparative Example 3 was obtained. could not be formed into

Comparative Examples 5 to 7 Polyvinyl chloride 100 parts by weight Octyl phthalate (plasticizer) 30 Azodicarbonamide (foaming agent) 2 Methylene pistearamide (lubricant) 2 Metal compound A
6〃Metal compound B5,}11m. A sheet-like product was obtained using the above formulation in the same manner as in Example 1.

In this product, the diameter of the opened fibers was insufficiently refined and non-uniform, and did not have a non-woven fiber structure. A photograph of a typical example obtained is shown in FIG.

Even if the content ratio is appropriate at 12 as in Comparative Examples 5 to 7, if the metal compound A is contained in excess of 100 parts by weight of vinyl chloride resin, a good nonwoven fiber structure cannot be obtained. I understand.

Table 1 shows the results obtained for Comparative Examples 1 to 7.

Example 10 A nonwoven fibrous structure was obtained in the same manner as in Example 1, except that ethylene-vinyl chloride copolymer (5% ethylene) was used instead of polyvinyl chloride. The diameter of the opened fibers in this product was sufficiently fine and uniform, and was similar to that obtained in Example 1.

Example 11 A nonwoven fiber structure was obtained in the same manner as in Example 1, except that 50 parts by weight of 2-ethylhexyl adipate was used instead of octyl phthalate and 2 parts by weight of butyl stearate was used instead of methylene bisstearamide. Ta. As in Example 1, the fiber diameter of this product was sufficiently fine and uniform.

Example 12 A nonwoven fibrous structure was obtained in the same manner as in Example 1, except that 1 part by weight of paratoluenesulfonyl semicarbazide was used instead of azodicarbonamide. Although this product had a slightly higher bulk density, it was almost the same as Example 1.

As shown above, a breathable non-woven fiber structure made of vinyl chloride resin which has excellent flame retardancy and is easily colored can be obtained.

The nonwoven fiber structure thus obtained is used as a heat insulating material, a thermal adhesive, a cushioning material, an electrical insulating material, and the like.

Furthermore, the sheet-like material can be used for a variety of purposes by being used alone or by laminating it with other resins.

[Brief explanation of the drawing]

Figures 1 to 3 are photographs illustrating the vinyl chloride resin nonwoven fiber structure produced according to the present invention. FIGS. 4 and 5 are photographs showing a vinyl chloride resin nonwoven fiber structure manufactured in a comparative example.

Claims (1)

[Claims] 1 containing one or more metal compounds A selected from the group consisting of zinc compounds and barium compounds, and one or more metal compounds B selected from the group consisting of tin compounds and calcium compounds, and A spread vinyl chloride resin nonwoven fiber structure in which the content ratio of compound A and metal compound B is 0.0001 to 100.