JP3345836B2 - Chlorine-containing resin foam - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a chlorine-containing resin foam,
More specifically, it relates to a chlorine-containing resin foam obtained by adding a plasticizer, a metal silicate, and a pyrolytic organic foaming agent to a chlorine-containing resin, which has no cell roughness, has a small coloring, and has an improved plate-out property. is there.

[0002]

BACKGROUND OF THE INVENTION Chlorine-containing resins are relatively inexpensive and have good physical and chemical properties.
It is a suitable material for application to furniture products such as cushioning materials, automobile products, and the like.

[0003] Such foamed products are generally blended by adding a foaming agent, a stabilizer and the like to a vinyl chloride resin and molded by calendering, extrusion, injection molding, or the like, or a foaming agent and a stabilizer are added to a paste resin. Add and blend
After coating on paper or cloth, it is manufactured by applying heat and gelling and foam molding. The foaming process is
Since the heating is performed at a high temperature for a short time, there are problems such as coloring, cell roughening and plate-out.

A method of adding a cell conditioner such as an acrylic resin or a methacrylic resin has also been proposed for the purpose of preventing the above-mentioned cell roughness, but this method can provide a relatively uniform foam cell, The effect of preventing plate-out cannot be obtained.

For this reason, attempts have been made to solve these problems by changing the formulation of the stabilizer. For example, JP-A-60-197744 discloses the addition of hydrotalcites or zeolites. However, when these are added, the state of the foamed cells is improved to some extent, but the improvement of the coloring property is still insufficient, and the effect of improving the plate-out property is particularly unsatisfactory. Therefore, further improvement has been demanded.

[0006]

In view of the above situation, the present inventors have conducted various studies to obtain a chlorine-containing resin foam having no cell roughness, small coloring and improved plate-out properties. As a result, it has been found that the above problems can be solved by using a chlorine-containing resin in combination with a plasticizer, a metal silicate and a chemical blowing agent, and that the initial expansion ratio can be increased, and the present invention has been completed.

Namely, the present invention is 100 parts by weight of chlorine-containing resin, (b) a plasticizer 30 to 100 parts by weight, (b) following one
0.01 to 5 parts by weight of a magnesium or aluminum silicate compound represented by the general formula (I) ; (c) 0.01 to 10 parts by weight of a pyrolytic organic blowing agent; zinc neocarboxylate
0.01 to 10 parts by weight and barium neocarboxylate
The present invention provides a chlorine-containing resin foam obtained by adding 0.01 to 10 parts by weight and then heating and foaming. M (O) _a (OH) _b · nSiO ₂ · xH ₂ O (I) (wherein M represents magnesium or aluminum,
n represents a number from 0.3 to 20, x is 0 or any positive
A and b are numbers that satisfy the following condition:
You. 0 ≦ a ≦ 1.5, 0 ≦ b ≦ 3.0, 2a + b = 2
Or 3)

Hereinafter, the chlorine-containing resin foam of the present invention will be described in detail.

The plasticizer (A) of the chlorine-containing resin foam of the present invention is not particularly limited as long as it is a usual plasticizer used for chlorine-containing resins. For example, di-n-phthalic acid is used. Butyl, di-n-octyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, octyldecyl phthalate, diisodecyl phthalate,
Dialkyl C ₇ -C ₉ phthalates, phthalic plasticizers such as butylbenzyl phthalate, di-2-ethylhexyl isophthalate, di-2-ethylhexyl adipate, diisodecyl adipate, di-2-ethylhexyl azelate , Fatty acid ester plasticizers such as dibutyl sebacate, di-2-ethylhexyl sebacate, and phosphate ester plasticizers such as tributyl phosphate, tri-2-ethylhexyl phosphate, tricresyl phosphate, and trixylyl phosphate; chlorination Examples include chlorine plasticizers such as paraffin and chlorinated fatty acid esters, epoxy plasticizers, polyester plasticizers and the like, and one or more of these can be used in combination.

The amount of the component (a) is 30 to 100 parts by weight, preferably 50 to 80 parts by weight, based on 100 parts by weight of the chlorine-containing resin.

The magnesium or aluminum silicate compound (b) of the chlorine-containing resin foam of the present invention comprises :
A compound represented by the following general formula [Formula 1] (I).

[0012]

## STR1 ## _{M (O) a (OH)} b · nSiO 2 · xH 2 O (I) ( wherein, M represents magnesium or aluminum,
n represents a number from 0.3 to 20, x represents 0 or any positive number, and a and b represent numbers satisfying the following condition. 0 ≦ a ≦ 1.5, 0 ≦ b ≦ 3.0, 2a + b = 2 or 3)

When n in the general formula (I) is less than 0.3, the coloring property is adversely affected, and when n is more than 20, the effect of preventing plate-out tends to be reduced. Further, those having n of 1 to 10 have excellent effects.

[0014] The (b) as a magnesium or silicate compounds of aluminum component may be a naturally occurring silicate compounds in silicate compound of synthetic, OH belt magnesium silicate, magnesium metasilicate, magnesium four silicate, O <br / > Aluminum orthosilicate, aluminum metasilicate, nonaluminum disilicate and the like.

The average particle size of the silicate compound is not particularly limited, but it is more preferable to use one having a particle size of 100 μm or less.

The amount of the component (b) is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the chlorine-containing resin.

Examples of the decomposable organic foaming agent of the component (C) of the chlorine-containing resin foam of the present invention include N, N'-dinitropentamethylenetetramine, azodicarbonamide, p, p'-bis (benzenesulfonyl) Hydrazide)
Examples thereof include ether and p-toluenesulfonyl hydrazide, and azodicarbonamide and p, p'-bis (benzenesulfonyl hydrazide) ether are particularly preferable. The above-mentioned p, p'-bis (benzenesulfonylhydrazide) ether is used alone or in combination with azodicarbonamide because of its excellent coloring property, but its use is restricted due to its poor plate-out property. In the chlorine-containing resin foam of the present invention, by using the above-mentioned component (b) in combination, it is possible to obtain a chlorine-containing resin foam having further improved colorability and excellent plate-out properties.

The amount of the component (C) is 0.01 to 10 parts by weight based on 100 parts by weight of the chlorine-containing resin.

The chlorine-containing resin in the present invention includes vinyl chloride homopolymers, vinyl chloride-vinyl acetate copolymers, vinyl chloride-ethylene copolymers, vinyl chloride-ethylene-vinyl acetate copolymers, and the like. Copolymer;
Examples include a vinyl chloride-based graft copolymer obtained by graft-polymerizing vinyl chloride onto an ethylene-vinyl acetate copolymer or an ethylene-propylene-based copolymer. Those having an average degree of polymerization (JIS K-6721) in the range of 600 to 1800 are preferred.

The chlorine-containing resin foam of the present invention comprises the above components (A), (B) and (C) and neocarboxylic acid
It is formed by heating and foaming a chlorine-containing resin containing lead and barium neocarboxylate by an ordinary method.

The chlorine-containing resin foam of the present invention preferably further contains zinc oxide, hydroxide, chloride, bromide, organic acid salt and the like.

Examples of the organic acid constituting the organic acid salt of zinc include carboxylic acids, phenols, and organic phosphoric acids.

As the carboxylic acid, for example, acetic acid,
Propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, neodecanoic acid, 2-ethylhexyl acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearin Acid, 12-hydroxystearic acid, behenic acid, montanic acid, elaidic acid, oleic acid, linoleic acid, linolenic acid, thioglycolic acid,
Mercaptopropionic acid, octylmercaptopropionic acid, benzoic acid, monochlorobenzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-ditertbutyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid Monohydric carboxylic acids such as ethylbenzoic acid, cumic acid, n-propylbenzoic acid, acetoxybenzoic acid, salicylic acid, p-tert-octylsalicylic acid, oxalic acid,
Malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid, aconitic acid, thiodipropionic acid, phthalic acid,
Bivalent carboxylic acids such as isophthalic acid, terephthalic acid, oxyphthalic acid, chlorophthalic acid or monoesters or monoamide compounds thereof, butanetricarboxylic acid, butanetetracarboxylic acid, hemi-mellitic acid, trimellitic acid, melophanic acid, pyromellitic acid And di- or triester compounds of trivalent or tetravalent carboxylic acids.

Examples of the phenols include phenol, cresol, xylenol, methyl propyl phenol, methyl tertiary octyl phenol, ethyl phenol, isopropyl phenol, tertiary butyl phenol, n-butyl phenol, diisobutyl phenol,
Isoamylphenol, diamylphenol, isohexylphenol, octylphenol, isooctylphenol, 2-ethylhexylphenol, tertiary octylphenol, nonylphenol, dinonylphenol, tertiary nonylphenol, decylphenol, dodecylphenol, octadecylphenol, cyclohexylphenol, phenylphenol, etc. No.

The organic phosphoric acids include, for example, mono- or di-octyl, -decyl, -dodecyl, -tridecyl, -tetradecyl, -hexadecyl, -octadecyl, -phenyl, -tolyl, -xylyl, -octylphenyl,- Nonylphenyl, phosphoric acid, pyrophosphoric acid, phosphorous acid and the like can be mentioned.

The organic acid salt of zinc may be an acid salt, a neutral salt, a basic salt, or an overbased complex obtained by neutralizing a part or all of a base of a basic salt with carbonic acid.

The amount of the organic acid salt of zinc is preferably 0.01 to 10 parts by weight, particularly preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the chlorine-containing resin.

The chlorine-containing resin foam of the present invention contains an organic acid salt such as an alkali metal such as potassium and sodium, and an alkaline earth metal such as magnesium, calcium and barium, which are used as a stabilizer for a normal chlorine-containing resin. can do. Examples of the organic acid constituting the organic acid salt include the same organic acids constituting the organic acid salt of zinc exemplified above.

The amount of the metal organic acid salt is preferably 0.01 to 10 parts by weight, particularly preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the chlorine-containing resin.

An excellent synergistic effect is exhibited by using an organic phosphite compound and / or an epoxy compound in combination with the chlorine-containing resin foam of the present invention.

Examples of the organic phosphite compound include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, Tris (mono and di mixed nonylphenyl) phosphite, diphenyl acid phosphite, 2,
2'-methylenebis (4,6-di-tert-butylphenyl)
Octyl phosphite, diphenyl decyl phosphite, phenyl diisodecyl phosphite, tributyl phosphite, tri (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, trilauryl Trithiophosphite,
Bis (neopentyl glycol) · 1,4-cyclohexanedimethyldiphosphite, bis (2,4-ditertbutylphenyl) pentaerythritol diphosphite,
Distearyl pentaerythritol diphosphite, phenyl-4,4'-isopropylidene diphenol pentaerythritol diphosphite, tetra (C ₁₂ -C
₁₅ mixed alkyl) -4,4'-isopropylidenediphenyldiphosphite, hydrogenated-4,4'-isopropylidenediphenol polyphosphite, bis (octylphenyl) bis [4,4'-n-butylidenebis ( 2-
Tert-butyl-5-methylphenol)] • 1,6-hexanediol • diphosphite, tetratridecyl •
4,4'-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl)
-1,1,3-tris (2-methyl-5-tert-butyl-
4-hydroxyphenyl) butane triphosphite and the like.

The amount of the organic phosphite compound added is
0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the chlorine-containing resin.

The epoxy compounds usable in the present invention include, for example, epoxidized soybean oil, epoxidized linseed oil, epoxidized fish oil, epoxidized tall oil fatty acid ester, epoxidized tallow oil, epoxidized castor oil, Epoxidized safflower oil, epoxidized linseed oil fatty acid butyl, methyl epoxide stearate, -butyl, 2-ethylhexyl or -stearyl, tris (epoxypropyl) isocyanurate, 3- (2-xenoxy)-
1,2-epoxypropane, epoxidized polybutadiene, bisphenol-A diglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexyl-6
-Methylepoxycyclohexanecarboxylate and the like.

The amount of the epoxy compound to be added is preferably from 0.01 to 20 parts by weight, particularly preferably from 0.5 to 10 parts by weight, based on 100 parts by weight of the chlorine-containing resin.

Various fillers can be added to the chlorine-containing resin foam of the present invention, if necessary. As the filler,
Calcium carbonate, silica, clay, glass beads, mica, sericite, glass flake, asbestos, wollastonite, potassium titanate, PMF, gypsum fiber, zonotolite, MOS, phosphate fiber, glass fiber, carbon fiber, aramid fiber, etc. No.

The amount of the filler to be added is as follows.
It is preferably 50 to 250 parts by weight with respect to 0 parts by weight, and is appropriately determined within the above range depending on the use.

If a light stabilizer is added to the chlorine-containing resin foam of the present invention, the light stability can be improved, and these can be appropriately selected and used according to the purpose of use. These include benzophenones, benzotriazoles, salicylates, substituted acrylonitriles, hindered amines, various metal salts or metal chelates, especially nickel or chromium salts or chelates.

If necessary, the chlorine-containing resin foam of the present invention may contain, for example, a crosslinking agent, a pigment, an antistatic agent, a plate-out inhibitor, a surface treating agent, a lubricant, a fluorescent agent, a fungicide, and a bactericidal agent. Agents, photodegradants, non-metal stabilizers, processing aids, release agents and the like.

[0039]

Next, the stabilizing effect of the chlorine-containing resin foam of the present invention will be specifically described by way of examples. However, the present invention is not limited by the following examples.

[Example 1] The following compound was kneaded with an Ishikawa-type raikai machine, and then subjected to vacuum de-treatment.
A uniform paste sol was made. Place the sol on paper.
Apply with a thickness of 2mm, 6 in a gear oven at 150 ° C
Heating was performed for 0 seconds to obtain a gelled sheet. Using the gelled sheet, in a gear oven at 250 ° C. for 10
Foamed sheets were foamed for seconds, 20 seconds and 40 seconds, and the expansion ratio of the obtained sheets was measured (shown as "foamability" in the table). Further, the yellowness of the foamed sheet for 20 seconds was also measured.

Further, at 140 ° C., 150 ° C. and 160 ° C.
Plate out test was performed. This involves placing the gelled sheet on a ferro-plate, preheating in a gear oven at a predetermined temperature for 1 minute, pressing the sheet onto a roll, and further heating in a gear oven for 5 minutes. The same operation was repeated five times, and the fogging on the ferro-plate was visually evaluated.
In the evaluation, 1 indicates that there is no haze at all, and it indicates that the value increases as the numerical value increases.

The results are shown in Table 1 below.

[Combination] Parts by weight Vinyl chloride resin (PSL-280 manufactured by Kanegafuchi Chemical) 100 Calcium carbonate (H) 100 Titanium dioxide (R) 15 Di-2-ethylhexyl phthalate 60 Mineral spirit 7 C9-10 Neocarboxylic acid Zinc 1.5 C9-10 barium neocarboxylate 1.0 azodicarbonamide 1.5 p, p'-bis (benzenesulfonylhydrazide) 1.5 ether test compound 1.0

[0044]

[Table 1]

Example 2 The same test as in Example 1 was conducted using the following compound.

The results are shown in Table 2 below.

[Combination] Parts by weight Vinyl chloride resin (PSL-280 manufactured by Kanegafuchi Chemical) 100 Calcium carbonate (H) 100 Titanium dioxide (R) 15 Di-2-ethylhexyl phthalate 60 Mineral spirit 8 C9-10 Neocarboxylic acid Zinc 1.5 C9-10 Barium neocarboxylate 1.0 p, p'-bis (benzenesulfonylhydrazide) 3 ether Test compound 1.0

[0048]

[Table 2]

As shown in Tables 1 and 2, when the vinyl chloride resin does not contain the component (b) of the chlorine-containing resin foam of the present invention, the foamability is small, , Plate out is great. In addition, zinc oxide and the like, which are generally known as foaming accelerators, have the drawback that, although the foaming property is improved, coloring occurs and plate-out becomes rather large. Further, instead of the component (b) of the present invention, a compound other than a silicate of an alkaline earth metal, such as magnesium oxide, may be added, or zeolite which is a silicic acid or a silicate compound other than the component (b) of the present invention may be used. When added, some effect of improving foaming properties is observed, but little effect is observed on improvement of coloring properties and plate-out.

On the other hand, it can be seen that the chlorine-containing resin foam of the present invention not only has improved foaming properties and coloring properties, but also has improved plate-out properties.

[0051]

Industrial Applicability The chlorine-containing resin foam of the present invention has low coloring, excellent foamability, and suppressed plate-out.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-1-299840 (JP, A) JP-A-4-236246 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08J 9/04-9/10

Claims (1)

(57) [Claims] 1. 100 parts by weight of a chlorine-containing resin, (a) 30 to 100 parts by weight of a plasticizer, and (b) a compound represented by the following general formula (I).
Silicate compounds 0.01 to 5 parts by weight of magnesium or aluminum is, (c) thermal decomposition type organic foaming agent 0.0
1 to 10 parts by weight , zinc neocarboxylate 0.01 to 10 times
Parts and barium neocarboxylate 0.01 to 10 weight
A chlorine-containing resin foam obtained by heating and foaming after containing a part . M (O) _a (OH) _b · nSiO ₂ · xH ₂ O (I) (wherein M represents magnesium or aluminum,
n represents a number from 0.3 to 20, x is 0 or any positive
A and b are numbers that satisfy the following condition:
You. 0 ≦ a ≦ 1.5, 0 ≦ b ≦ 3.0, 2a + b = 2
Or 3)