JPH059322A - Foaming agent composition - Google Patents

Abstract

PURPOSE:To obtain the subject foaming agent composition, applicable to nondangerous articles by a pressure vessel test for class 5 under the Fire Protection Law, excellent in dispersibility and safety and useful for rubber, etc., by adding a specific amount of a rapid decomposition inhibitor such as magnesium hydroxide to azodicarbonamide. CONSTITUTION:The objective foaming agent composition is obtained by adding and mixing 0.1-5 pts.wt., preferably 0.5-4 pts.wt. rapid decomposition inhibitor composed of one or two or more of magnesium hydroxide, basic magnesium carbonate or magnesium salt of a fatty acid with 100 pts.wt. azodicarbonamide.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a foaming agent for producing a foam such as rubber, thermoplastic resin or asphalt, and is characterized by suppressing a rapid decomposition of the foaming agent during thermal decomposition. The present invention relates to an azodicarbonamide-based foaming agent composition, and more specifically, to a foaming agent composition which is a non-dangerous substance in the Class 5 Pressure Vessel Test of Dangerous Goods of the Fire Service Act.

[0002]

2. Description of the Related Art Zinc white or the like has been conventionally used as a decomposition aid for azodicarbonamide. However, in Japanese Examined Patent Publication No. 3-2894, a method in which fatty acid zinc and zinc hydroxide are used in combination and JP-B-60- No. 10539 discloses a method for adding a zinc organic carboxylate having 6 or less carbon atoms to obtain a vinyl chloride resin composition for foaming. However, when these known zinc compounds are used in combination with azodicarbonamide, the decomposition temperature is simply lowered, but there is no effect of suppressing the rapid decomposition, and it is simply slid to a low temperature region to perform low temperature decomposition, It cannot be rapidly decomposed and is classified as a dangerous substance in the dangerous substance confirmation test.

Regarding the content of the magnesium compound, JP-A-52-40577 discloses a foamable thermoplastic resin containing 5 to 10 parts of azodicarbonamide.
Thermoplastic resin composition for foam molding to which 0% by weight of magnesium compound is added, or azodicarbonamide as a foaming agent is added to thermoplastic resin in JP-A-50-77472, and foam molding is performed by an extrusion or injection molding machine. As a method for producing a product, a method of mixing magnesium stearate with the thermoplastic resin is disclosed. However, in the method of foam molding by adding azodicarbonamide to a thermoplastic resin as described above, magnesium hydroxide,
A method for producing a thermoplastic resin foam-molded article, which comprises mixing basic magnesium carbonate or magnesium stearate. That is, there is no content of a foaming agent composition in which azodicarbonamide and magnesium hydroxide, basic magnesium carbonate or magnesium stearate are mixed. Further, even if a few percent of filler such as silicon dioxide is added to azodicarbonamide, there is little tendency to be out of the dangerous substance confirmation test. Therefore, there has been a strong demand from consumers for the development of an azodicarbonamide-based blowing agent composition which is a non-dangerous substance substance with almost no change in the conventional use conditions.

What is the confirmation test for dangerous substances? Due to the partial revision of the Fire Service Act of 1989, self-decomposable substances are measured by the calorific value by the differential scanning calorific value (hereinafter abbreviated as DSC) measurement method and the measurement standard in the pressure vessel test. It will be confirmed and judged, but the DSC measurement value of pure azodicarbonamide does not apply,
The pressure vessel test (orifice diameter 1.0 mm) measurement value was confirmed to correspond to the two types of dangerous goods category 5. This is because it is necessary to deal with azodicarbonamide as a dangerous substance in the production, storage, transportation and handling by customers.

[0005]

In order to solve the above problems in the prior art, the inventor has added a commercially available inexpensive and safe compound to azodicarbonamide to accelerate the thermal decomposition initiation temperature to a low temperature range, In addition, as a result of intensive studies on additives that suppress a rapid thermal decomposition reaction, by adding a small amount of magnesium hydroxide, basic magnesium carbonate or magnesium fatty acid to azodicarbonamide, the thermal decomposition start temperature can be accelerated to a low temperature range. In addition, it was found that the composition was a non-dangerous substance composition in the above pressure vessel test by suppressing rapid thermal decomposition. Adding a small amount of this rapid decomposition inhibitor consisting of magnesium hydroxide, basic magnesium carbonate or magnesium fatty acid does not simply dilute, but accelerates the thermal decomposition start temperature to a low temperature range and suppresses the rapid thermal decomposition reaction. , Which controls the decomposition rate. Further, this foaming agent composition has good storage stability, good dispersibility in rubber or resin at the time of use, and when the foam is produced, it has no surprising effect that uniform fine bubbles are formed without coloring and contamination. Heading out, the present invention has been completed.

[0006]

DISCLOSURE OF THE INVENTION The inventor aims to provide a foaming agent composition in which a rapid decomposition inhibitor made of magnesium hydroxide, basic magnesium carbonate or magnesium fatty acid is added to azodicarbonamide. Hereinafter, the present invention will be described in detail. The azodicarbonamide used in the present invention is not necessarily limited, and is produced by a conventionally known method of oxidizing hydrazodicarbonamide with chlorine, hypochlorite, dichromate, hydrogen peroxide or the like, It is azodicarbonamide. The magnesium hydroxide, basic magnesium carbonate or magnesium fatty acid referred to herein is a white powder, and the fatty acid magnesium is magnesium oleate, magnesium stearate, magnesium palmitate, magnesium myristate, magnesium laurate, octyl acid. It is a magnesium salt of a carboxylic acid such as magnesium, magnesium tartrate or magnesium citrate. Grain size is 2
It is a fine powder of 0 μ or less, preferably 10 μ or less.

The foaming agent composition of the present invention is prepared by adding magnesium hydroxide, basic magnesium carbonate or magnesium fatty acid to the azodicarbonamide as described above, and the composition ratio thereof is not necessarily limited. Usually, the total addition amount of one or more of magnesium hydroxide, basic magnesium carbonate or magnesium fatty acid is 0.1 parts by weight to 5 parts by weight, preferably 0.5 to 100 parts by weight with respect to 100 parts by weight of azodicarbonamide. 4 parts by weight, more preferably 1 to 3 parts by weight.

The use of the foaming agent composition of the present invention is determined by various properties such as the softening temperature and the deterioration temperature of the synthetic resin to be foamed, and the foaming agent composition of the present invention is processed at a predetermined temperature. When the product is used, the composition is decomposed at a predetermined temperature and can be easily used under the same conditions without changing the conventional conditions. When the addition amount of the rapid decomposition inhibitor consisting of magnesium hydroxide, basic magnesium carbonate or magnesium fatty acid is 0.1 parts by weight or less relative to 100 parts by weight of azodicarbonamide, the effect of suppressing the rapid decomposition of the foaming agent is low and 5 parts by weight. The effect of suppressing rapid decomposition can be sufficiently achieved with an addition amount of at least 1 part by weight, but further it is not preferable to use the same amount as in the conventional case when the resin is used for molding, because the expansion ratio decreases.

In these compositions, known organic foaming agents, dinitrosopentamethylenetetramine, oxybis (benzenesulfonylhydrazide), toluenesulfonylhydrazide, toluenesulfonylsemicarbazide, azobisisobutyronitrile, urea auxiliaries, etc. It is also possible to use a filler and the like in combination.

The method for preparing the foaming agent composition of the present invention is not particularly limited, and for example, a high speed mixer such as a Hensiel mixer or a super mixer, a ribbon blender,
Azodicarbonamide is put in a mixer such as a Banbury mixer or a ball mill, and magnesium hydroxide, basic magnesium carbonate or fatty acid magnesium is mixed and treated. It is also possible to mix them at the time of drying.

The foaming agent composition of the present invention can be used for molding foams of various synthetic resins. As such a synthetic resin, a thermoplastic resin such as vinyl chloride resin, vinyl chloride copolymer resin, polyethylene, polypropylene, polyolefin copolymer resin, ABS resin or polycarbonate can be used. The amount of the foaming agent composition of the present invention used for these synthetic resins depends on the molding method of the foamed product and the expansion ratio, and in the case of producing a vinyl chloride resin foam, 2 to 5 parts by weight relative to the resin, In the case of the crosslinked polyolefin foam, it is 3 to 20 parts by weight with respect to the resin, and in the case of the injection molding method or the extrusion molding method, it is about 0.1 to 5 parts by weight with respect to the resin or asphalt.

[0012]

The present invention will be described in more detail with reference to the following examples. As a comparison of the ability of the foaming agent composition to suppress the rapid thermal decomposition reaction, the pressure vessel test and the expansion ratio of the foam were measured as follows. (1) Measurement is performed using a pressure vessel test device (Kurachi Scientific Equipment Co., Ltd.). Pressure vessel (stainless steel) content 2
Orifice plate 00cm ² (thickness 2 mm · pore diameter 1.0
(mm) is attached to a device equipped with an aluminum (5 mm) sample, 5 g of the measurement sample is weighed and placed in an Al sample container, an aluminum rupture plate is set, heating and measurement are performed 10 times, and it is dangerous to rupture 5/10 times or more. It becomes a thing judgment.

[0013]

Example 1 100 parts by weight of azodicarbonamide and 4 parts by weight of magnesium hydroxide were put into a Hensiel mixer,
The mixture was mixed at room temperature for 5 minutes to obtain a foaming agent composition. A pressure vessel test was performed on this foaming agent composition according to the above-mentioned measurement method, and the results are shown in Table 1. The resulting foaming agent composition was used in Reference Example 1-1.

[0014]

Example 2 100 parts by weight of azodicarbonamide and 5 parts by weight of basic magnesium carbonate were put into a Henschel mixer and mixed at room temperature for 5 minutes to obtain a foaming agent composition. A pressure vessel test was performed on this foaming agent composition according to the above-mentioned measurement method, and the results are shown in Table 1. The resulting foaming agent composition is shown in Reference Example 1-
Used for 2.

[0015]

Example 3 100 parts by weight of azodicarbonamide and 5 parts by weight of magnesium stearate were charged into a Henschel mixer and mixed at room temperature for 5 minutes to obtain a foaming agent composition. A pressure vessel test was performed on this foaming agent composition according to the above-mentioned measurement method, and the results are shown in Table 1. The resulting foaming agent composition is shown in Reference Example 1
-3 was used.

[0016]

Comparative Example 1 A pressure vessel test of an untreated product of azodicarbonamide was measured, and the results are shown in Table 1. The untreated azodicarbonamide was used in Comparative Reference Example 1-1.

[0017]

Comparative Example 2 100 parts by weight of azodicarbonamide and 2 parts by weight of silicon dioxide were added to a Hensiel mixer, and the mixture was stirred at room temperature for 5 hours.
Mixing for minutes gave a foaming agent composition. A pressure vessel test was performed on this foaming agent composition according to the above-mentioned measurement method, and the results are shown in Table 1. The resulting foaming agent composition was used in Comparative Reference Example 1-2.

[0018]

Comparative Example 3 5 parts by weight of silicon dioxide was added to 100 parts by weight of azodicarbonamide in a Hensiel mixer, and the mixture was stirred at room temperature for 5 hours.
Mixing for minutes gave a foaming agent composition. A pressure vessel test was performed on this foaming agent composition according to the above-mentioned measurement method, and the results are shown in Table 1. The resulting foaming agent composition was used in Comparative Reference Examples 1-3.

[0019]

[Reference Example 1-1] An ethylene-vinyl acetate copolymer was kneaded under heating at a roll temperature of 90 to 100 ° C. while kneading the following composition, and a thickness of 15 mm in order to produce this into a foam.
200 x 200 x 15m after taking out the sheet
16 minutes at a vapor pressure 6.5Kg / cm ² in a mold of m, a pressure of gauge pressure 150 Kg / cm ^2, to obtain a foam with a decompression after heating. The obtained foam has a smooth surface,
The bubbles were uniform and fine. The density and hardness of the foam are shown in Table 1.
Shown in. The density was measured by slicing the skin layer, and the hardness was measured by C-type (for sponge) Kobunshi Keiki Co., Ltd. Blending ethylene-vinyl acetate copolymer (MI.1.5) 100. Parts by weight stearic acid 0.3 parts by weight zinc white 2 parts by weight dicumyl peroxide 0.9 parts by weight blowing agent composition of Example 1 5 parts by weight

[0020]

[Reference Example 1-2] A foam was produced using the foaming agent composition of Example 2 under the conditions of Reference Example 1, and the density and hardness of the obtained foam were measured and shown in Table 1.

[0021]

[Reference Example 1-3] A foam was produced using the foaming agent composition of Example 3 under the conditions of Reference Example 1, and the density and hardness of the obtained foam were measured and shown in Table 1.

[0022]

[Comparative Reference Example 1-1] A foam was produced using the azodicarbonamide of Comparative Example 1 under the conditions of Reference Example 1, and the density and hardness of the obtained foam were measured and shown in Table 1.

[0023]

[Comparative Reference Example 1-2] A foam was produced using the foaming agent composition of Comparative Example 2 under the conditions of Reference Example 1, and the density and hardness of the obtained foam were measured and shown in Table 1.

[0024]

[Comparative Reference Example 1-3] A foam was produced using the foaming agent composition of Comparative Example 3 under the conditions of Reference Example 1, and the density and hardness of the obtained foam were measured and shown in Table 1.

[0025]

[Table 1]

[0026]

Example 4 100 parts by weight of azodicarbonamide was dried by a fluid dryer, and then 4 parts by weight of magnesium stearate was put into the fluid dryer and mixed by fluidization to obtain a foaming agent composition.
A pressure vessel test was conducted on the foaming agent composition according to the above-mentioned measuring method, and the results are shown in Table 2. The resulting foaming agent composition was used in Reference Example 2.

[0027]

Comparative Example 4 A pressure vessel test of an untreated azodicarbonamide was measured, and the results are shown in Table 2. The untreated azodicarbonamide was used in Comparative Reference Example 2-1.

[0028]

COMPARATIVE EXAMPLE 5 4 parts by weight of silicon dioxide was added to 100 parts by weight of azodicarbonamide in a Hensiel mixer, and the mixture was stirred at room temperature for 5 hours.
Mixing for minutes gave a foaming agent composition. A pressure vessel test was conducted on the foaming agent composition according to the above-mentioned measuring method, and the results are shown in Table 2. The resulting foaming agent composition was used in Comparative Reference Example 2-2.

[0029]

Reference Example 2 After uniformly kneading the following composition, this composition was spread on a release paper to a thickness of 0.5 mm and heated in a Gar oven at 150 ° C. for 1 minute to prepare a cure sheet.
The obtained sheet was placed in a Gar oven kept at 200 ° C. to foam. The obtained foamed sheet has a smooth surface,
The bubbles were uniform and fine. The foaming ratio is measured by the thickness in Table 2
Shown in. Blend Polyvinyl chloride (Geon 131) 100 parts by weight DOP 70 parts by weight Stabilizer 3 parts by weight Foaming agent composition of Example 4 3 parts by weight

[0030]

[Comparative Reference Example 2-1] A foam was produced using the azodicarbonamide of Comparative Example 4 under the conditions of Reference Example 2, and the foaming ratio of the obtained foam was measured and shown in Table 2.

[0031]

[Comparative Reference Example 2-2] A foam was produced using the foaming agent composition of Comparative Example 5 under the conditions of Reference Example 2, and the expansion ratio of the obtained foam was measured and is shown in Table 2.

[0032]

[Table 2]

[0033]

As shown in Examples, Comparative Examples, Reference Examples and Comparative Reference Examples of Tables 1 and 2, azodicarbonamide may be supplemented with one or two types of magnesium hydroxide, basic magnesium carbonate or magnesium fatty acid. Combined addition,
By performing the mixing treatment, the thermal decomposition initiation temperature of azodicarbonamide is accelerated to a low temperature range, and rapid thermal decomposition is suppressed, and in the pressure vessel test, it becomes a non-dangerous substance composition and Uniform dispersibility was also improved, and it was not necessary to change the molding conditions during foam molding under the same molding conditions as before the treatment with the foaming agent, and the foam cells were uniformly fine.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ryoen Yamawaki 1-8 Nitto-cho, Handa-shi, Aichi Nagawa Chemical Industry Co., Ltd. Kinuura factory (72) Inventor Saburo Sakai 1-kichi, Ikedaminami-cho, Kichijoin, Minami-ku, Kyoto Nagakazu Kasei Kogyo Co., Ltd. (72) Inventor Kenji Ichikawa 1 Kichishoin Ikeda-Minami-cho, Minami-ku, Kyoto Nagawa Kasei Kogyo Co., Ltd. (72) Inventor Teruo Hayashi 1 Nitto-cho, Handa-shi, Aichi 8 Eiwa Co., Ltd. Kinuura Plant Co., Ltd. (72) Inventor Tomiya Tomiya 8, Nitto-cho, Handa City, Aichi Prefecture 8 Eiwa Chemical Industry Co., Ltd. Kinuura Plant

Claims (1)

Claim: What is claimed is: 1. 0.1 to 5 parts by weight of a rapid decomposition inhibitor comprising 100 parts by weight of azodicarbonamide and one or more of magnesium hydroxide, basic magnesium carbonate or magnesium fatty acid. A foaming agent composition characterized by being added as a non-dangerous substance in the pressure vessel test of Class 5 Dangerous Goods of the Fire Service Act.