JPH05117054A - Inorganic light-weight foamed material - Google Patents

Abstract

PURPOSE:To provide an inorganic light-weight foamed material excellent in incombustibility. CONSTITUTION:In a foamed material composed of a composition containing an inorganic substance and a vinyl chloride resin in a mixture ratio of (95:5)-(5:95), an inorganic fiber whisker having <=5mum fiber diameter and >=1000 deg.C melting point is added to the vinyl chloride resin in an amount within a range of 0.1wt.%-150wt.%. Thereby, the objective light-weight foamed material excellent in incombustibility can be obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inorganic lightweight foam having high incombustibility.

[0002]

2. Description of the Related Art Techniques for foaming a composition of an inorganic substance and a vinyl chloride resin have already been published. JP-A-56-129236
JP-A-59-8860 (Japanese Patent Publication No. 61-52115), JP-A-61-151073, JP-A-63-85071, JP-A 1-215773, etc. Organic peroxide,
By retaining the foaming gas in the foaming system by crosslinking vinyl chloride resin with carbon radicals or sulfur radicals generated from azo, sulfur, nitrile compounds, etc. or activating the vinyl chloride resin and inorganic substances by radicals. hand,
It is intended to produce a high-magnification foam.

However, there is no mention of measures for improving incombustibility, which are strongly demanded by the market for products manufactured by these techniques. The vinyl chloride resin that participates in the formation of a bubble film has a nonflammable temperature of 75, which is the object of the present invention.
Pyrolysis starts at around 200 ° C, which is much lower than 0 ° C, and then the zipper reaction (zi
It is considered that there is a background with a chain reaction called pper reaction).

[0004]

DISCLOSURE OF THE INVENTION The present invention has an improved incombustibility in order to address the essence of thermal decomposition of a vinyl chloride resin as a foaming medium in response to the problem of improving incombustibility which is strongly demanded by the market. It is intended to provide a foam.

The standard of "nonflammability" for the purpose of the present invention is
After heating for 20 minutes at the furnace temperature of the heating furnace of 740 to 760 ° C. in the Ministry of Construction Notification No. 1828 “Specifying non-combustible materials”, a surface test is conducted on the test body to find no harmful deformation or cracks for fire protection. It is based.

[0006]

The present invention provides a foam using a composition in which the compounding ratio of an inorganic substance and a vinyl chloride resin is within the range of 95: 5 to 5:95, and the fiber diameter is 5 μm or less, It proposes a lightweight non-combustible foam in which inorganic fiber whiskers having a melting point of 1000 ° C. or higher are added within a range of 0.1% to 150% to vinyl chloride resin.

Inorganic fiber whiskers referred to in the present invention
r) means potassium titanate (K ₂ O.nTiO ₂ );
Aluminum borate _{(9Al 2 O 3 · 2B 2} O 3); silicon carbide (SiC), silicon nitride _{(Si 3 N 4); Al} 2 O
₃ ; CaSO ₄ ; MgO whiskers. INDUSTRIAL APPLICABILITY The present invention is applied to a foam using a composition in which the compounding ratio of the inorganic substance and the vinyl chloride resin is in the range of 95: 5 to 5:95 (weight ratio). First, the improvement of nonflammability, which is the object of the present invention, will be described.

In the case of foaming a composition of an inorganic substance and a vinyl chloride resin, it is a conventional means to increase the melt viscosity of the foaming system with an organic carbon radical or the like, but a radical such as an organic peroxide. Since the generator itself becomes a strong spark during high temperature combustion, it is not preferable for improving the nonflammability in the present invention. Therefore, the present invention is intended to obtain a nonflammable foam by using whiskers of an inorganic substance without using such an organic peroxide.

The heat of combustion of vinyl chloride resin is 17,960 jo
ule / g, which is flammable at high temperature. However, the presence of the coexisting inorganic substance and the high-melting-point whiskers in the process of combustion from the thermal decomposition of the vinyl chloride resin through vaporization makes it possible to remarkably slow down the burning rate of the foam and also reduce the combustion heat itself generated.

When a whisker having a high melting point of 1000 ° C. or more is uniformly dispersed in a foam according to the present invention to form a network structure, the network of the whisker is 750 ° C. of vinyl chloride resin. It adsorbs decomposition products of chain reaction pyrolysis at high temperature to form a carbon layer. Due to this formed carbon layer,
Despite heating at 750 ° C. for 20 minutes, the shape of the foam is retained and no cracks are generated on the surface. For example, the heat resistance of the potassium titanate fiber, which is a typical whisker of the present invention, is fully explained by the fact that there is no abnormality even when heated at a temperature of up to 1200 ° C. for 1 year. Typical examples of the inorganic fiber whiskers used in the present invention are listed below. Type Fiber diameter (μm) Melting point (℃) Heat resistance (℃) Potassium titanate (K ₂ 0 ・ nTiO ₂ ) ~ 0.1 1370 1200 Aluminum borate 0.5 ~ 1.0 1440 1200 (9Al ₂ O ₃ .2B ₂ O ₃ ) Silicon carbide (SiC) 0.05 to 1.5 2690 Silicon nitride (Si ₃ N ₄ ) 0.1 to 1.6> 2000 Alumina (Al ₂ O ₃ ) 1.0 2040 1600 Calcium sulfate (CaSO ₄ ) 2.0 1450 1000 Magnesium oxide (MgO) 3.0 to 5.0 2825 1600

All of these whiskers can be used in the foam of the present invention. In the foam of the present invention,
Inorganic fiber whiskers with a fiber diameter of 5 microns or less and a melting point of 1000 ° C or more are added within the range of 0.1% to 150% (wt%) to vinyl chloride resin to improve the desired nonflammability. The effect of can be obtained.

In the present invention, by using whiskers having a fiber diameter of 5 μm or less, uniform foaming can be achieved by increasing the apparent viscosity of the foaming system. In this case, it is an essential condition that the whiskers have a fiber diameter of 5 μm or less. The reason is as follows.

Although the cell thickness of the foam of the present invention depends on the production conditions, it is about 100 μm. In the process of producing the foam having such a thin cell structure, the fiber diameter is 10 μm or more. When there are many inorganic fibers of the same thickness, the phenomenon in which the foam film of the foam is partially destroyed occurs, so that the foam gas escapes from the manufactured foam and the product shrinks. The underlying problem arises. This fact can be explained by the following relational expression. that is,
It is the relationship between the fiber rigidity and the fiber diameter. G = E · I G: rigidity (stiffness) E: elastic modulus I = (πD ³ ) / 64 I: Second moment of area D: Fiber diameter

That is, the rigidity of the inorganic fiber is proportional to the modulus of elasticity of the inorganic fiber, but is proportional to the cube of the fiber diameter. The fiber diameter has an overwhelming influence on the rigidity. The flexibility of an inorganic fiber is governed by the shape factor of the fiber diameter, not the modulus.

In the present invention, if an inorganic fiber having a fiber diameter of 5 μm or more is used, the high rigidity (high stiffness) of the fiber is obtained.
ness) and low flexibility, the thin foam film during the process is easily broken, and as a result, foam gas is leaked and the product shrinks. become.

Typical examples of the inorganic substances used in the present invention are as follows.
Non-toxic non halogen halogen
Ip's water-releasing flame retardant.
Decomposition above a temperature, dehydration reaction starts, and heat energy
It absorbs. Type and composition Toxicity Decomposition start temperature Thermal decomposition product Endotherm Aluminium hydroxide Non-toxic 200 ℃ Al₂O₃, H₂O 470 Cal / g Al (OH)₃  Calcium hydroxide non-toxic 380 ℃ CaO, H₂O 222 Cal / g Ca (OH)₂  Magnesium hydroxide Nontoxic 340 ℃ MgO, H₂O 320 Cal / g Mg (OH)₂  Calcium aluminate Non-toxic 250 ℃ CaO, Al₂O₃340 Cal / g Ca₃Al₂(OH)₁₂ H₂O Basic magnesium carbonate Non-toxic 200 ℃ MgO, CO₂295 Cal / g Mg_Four(CO₃)₃(OH)₂・ 4H₂OH₂O Hydrotalcites Non-toxic 180 ℃ Mg_1-x・ Al_xO, Mg_FourAl (OH)₁₂ CO₃・ 3H₂O CO₂, H₂O

All of the inorganic substances listed in this representative example contribute to the improvement of nonflammability, which is the object of the present invention, but calcium, magnesium, aluminum, titanium, iron, zinc, other than these inorganic substances, Metal carbonates, sulfates, silicates, phosphates, borates, oxides, etc.
Hydroxides, or hydrates thereof, silica, bentonite, clay and the like can be used for the production of the foam of the present invention, although they have a point that they are not sufficiently nonflammable.

When foaming a composition of an inorganic substance and a vinyl chloride resin, a known foaming agent can be used. For example, dinitrosopentamethylenetetramine, azodicarbonamide and the like can be used.

As the vinyl chloride resin used in the present invention, any of a paste resin by an emulsion polymerization method, a suspension resin by a suspension polymerization method, and a mass polymerization resin by a bulk polymerization method can be used. A typical manufacturing process of the foam of the present invention is as follows. Part 1 When using paste resin by emulsion polymerization

Vinyl chloride resin, inorganic substances, whiskers,
A kneader is charged with all raw materials of an organic solvent such as benzene, toluene, and acetone as a foaming agent, a stabilizer for vinyl chloride, and a lubricant for vinyl chloride, and they are kneaded for a predetermined time. In this step, the whisker fibers are well adapted to the organic solvent, so that the fibers are sufficiently stretched and uniformly dispersed in the vinyl chloride resin as the main component and the inorganic substance.

Next, a foaming reaction is carried out using a pressure press machine at a predetermined temperature for a predetermined time under a predetermined pressure. After releasing the pressure of the pressurizer, the organic solvent is removed by leaving it in the oven or the dryer for a predetermined time. Part 2 When using suspension polymerization resin or bulk polymerization resin

All the same raw materials as in 1 are uniformly mixed with a blender. In this case, it is necessary to knead this mixture with an extruder and gel it. Therefore, the extruder is kneaded twice at each predetermined temperature. In the second extrusion step, a honeycomb die is attached to the tip of the extruder to form spherical pellets having a small diameter. Next, kneading is performed for a predetermined time with a heating kneader. The rest is the same as that of the first.

[0023]

【Example】

Example (1) Compounding parts by weight Inorganic substance: Aluminum hydroxide 500 Vinyl chloride resin: Emulsion polymer paste resin 100 Nippon Zeon Co. 121 (p = 1650) Whiskers: Potassium octatitanate fiber-80 (K ₂ O.Ti ₈₎ O ₁₆ ) Otsuka Chemical TISMO-D Foaming agent: Dinitrosopentamethylenetetramine 10 and foaming aid (Sankyo Kasei Cermic AN) Baking soda 5 Stabilizer for vinyl chloride resin: Cadmium stearate 5 Organic solvent: Benzene 500

After kneading all of these raw materials in a kneader for 60 minutes, press them at 160 ° C. for 40 minutes at 150 kg / cm.
² The foaming reaction was carried out under pressure, and then the pressure was released after cooling. After releasing the pressure, 4 in a hot air circulation oven at 120 ° C
It was left for one day to remove benzene. Physical properties of the obtained foam: Apparent specific gravity 100 kg / m ³ , Compressive strength 8.2kg / m ² ,
Thermal conductivity 0.030 kcal / m ・ h ・ ℃,

Nonflammability test (according to Ministry of Construction notification No. 1828) Heated in a heating furnace at 750 ° C. for 20 minutes. No deformation or cracking was observed in the test body after heating.
It can be seen that the nonflammability is clearly improved. Example (2) Compounding parts by weight Inorganic substance: Magnesium hydroxide 600 Vinyl chloride resin: Suspension polymerization resin 100 Nippon Zeon 101 EP (p = 1450) 90 Whiskers: Potassium hexatitanate fiber (K ₂ O.Ti ₆ O ₁₂ ) River Iron Mining TIBREX Foaming agent: Azodicarbonamide and foaming aid 8 Baking soda 4 Stabilizer for vinyl chloride resin: Tribasic lead sulfate 7 Dibasic lead stearate 4 Organic solvent: Xylene 500

All the raw materials except the organic solvent were uniformly mixed in a blender and then kneaded at 170 ° C. in a twin-screw extruder. continue,
Only 100 parts of 500 parts of the organic solvent xylene were mixed therein, and then the mixture was heated at low temperature using a single-screw extruder to 150 parts.
Extrusion was carried out at 0 ° C., and a spherical die having a fine particle diameter was made with a honeycomb die at the tip.

Next, the pellets and the remaining xylene 40
0 part was kneaded with a kneader at a temperature of 70 ° C. for 2 hours, and then pressure-foamed with a pressure press. The conditions after the pressure press were the same as in Example (1). Physical properties of the obtained foam: Apparent specific gravity 120 kg / m ³ , Compressive strength 9.5kg / m ² ,
Thermal conductivity 0.030 kcal / m ・ h ・ ℃,

Nonflammability test (according to Ministry of Construction Notification No. 1828) The furnace temperature of 750 ° C. was applied for 20 minutes. No deformation or cracking was observed in the test body after heating. It can be seen that the nonflammability is clearly improved. Example (3) Compounding parts by weight Inorganic material: Calcium aluminate 700 Vinyl chloride resin: Emulsion polymerization paste resin Taiwan plastic 1069 (p = 1750) 100 Whiskers: Aluminum borate 75 (Shikoku Kasei Alvorex G) Foaming agent: Azodicarbonamide and foaming aid 12 Sodium bicarbonate 6 Stabilizer for vinyl chloride resin: Cadmium stearate 3 Barium stearate lead 2 Organic solvent: Toluene 600

After kneading all of these raw materials in a kneader for 70 minutes, press them at 170 ° C. for 50 minutes at 160 kg / cm.
² The foaming reaction was carried out under pressure, and then the pressure was released after cooling. After releasing the pressure, the same procedure as in Example (1) was performed. Physical properties of the obtained foam: Apparent specific gravity 80 kg / m ³ , Compressive strength 7.0 kg / m ² , Thermal conductivity 0.030 kcal / m ・ h ・ ℃,

Incombustibility test (according to Ministry of Construction notification No. 1828) Heating was carried out at a furnace temperature of 750 ° C. for 20 minutes. No deformation or cracking was observed in the test body after heating.
It can be seen that the nonflammability is clearly improved. Comparative example (without using whiskers) Compounding parts by weight Inorganic substance: Aluminum hydroxide 500 Vinyl chloride resin: Emulsion polymerization paste resin Nippon Zeon Co. 121 (p = 1650) 100 Blowing agent: Dinitrosopentamethylenetetramine 6 and blowing aid (Sankyo Kasei Cermic AN) Stabilizer for sodium bicarbonate 3 vinyl chloride resin: Tribasic lead sulfate 2 Dibasic lead stearate 1 Organic solvent: Toluene 200

In this comparative example, the above formulation was used without using potassium titanate whiskers, and the foaming operation and the like were carried out in exactly the same manner as in Example (1). Gas escaped and contracted, and no foam was obtained.

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[Procedure amendment]

[Submission date] November 11, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

According to the present invention, whiskers having a high melting point of 1000 ° C. or higher are uniformly dispersed in a foam to form a net work structure. The whiskers have a net structure of vinyl chloride resin 7.
A decomposition product of chain reaction thermal decomposition at a high temperature of 50 ° C. is adsorbed to form a carbon layer. Due to the carbon layer thus formed, the shape of the foam is retained and cracks do not occur on the surface despite heating at 750 ° C. for 20 minutes. For example, the heat resistance of the potassium titanate fiber, which is a typical whisker of the present invention, is fully explained by the fact that there is no abnormality even when heated at a temperature of up to 1200 ° C. for 1 year. Typical examples of the inorganic fiber whiskers used in the present invention are listed below. ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] November 12, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction content]

Vinyl chloride resin, inorganic substances, whiskers,
Blowing agents, stabilizers and vinyl chloride resin for a vinyl chloride resin
As a swelling agent , all raw materials of organic solvents such as benzene, toluene and acetone are charged into a kneader and kneading is performed for a predetermined time. In this step, the whisker fibers are well adapted to the organic solvent, so that the fibers are sufficiently stretched and uniformly dispersed in the vinyl chloride resin as the main component and the inorganic substance.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[Correction method] Change

[Correction content]

All the same raw materials as in 1 are uniformly mixed with a blender. In this case, it is necessary to knead this mixture with an extruder and gel it. Therefore, the extruder is kneaded twice at each predetermined temperature. In the second extrusion step, a honeycomb die is attached to the tip of the extruder to form spherical pellets having a small diameter. Next, kneading is performed for a predetermined time with a heating kneader. After following is similar to the 1.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0024

[Correction method] Change

[Correction content]

After kneading all of these raw materials in a kneader for 60 minutes, a pressure press machine was operated at 160 ° C. for 40 minutes at 150 kg /
The foaming reaction was performed under a pressure of cm ² , and then the pressure was released after cooling. After releasing the pressure, the mixture was left in a hot air circulation oven at 120 ° C. for 4 days to remove benzene. Physical properties of the obtained foam: apparent specific gravity 100 kg / m ³ , compressive strength 8.2 kg
/ Cm ² , thermal conductivity 0.030 kcal / m · h ·
℃,

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

Next, the pellets and the remaining xylene 40
0 part was kneaded with a kneader at a temperature of 70 ° C. for 2 hours, and then pressure-foamed with a pressure press. The conditions after the pressure press were the same as in Example (1). Physical properties of the obtained foam: apparent specific gravity 120 kg / m ³ , compressive strength 9.5 kg
/ Cm ² , thermal conductivity 0.030 kcal / m · h ·
℃,

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] 0029

[Correction method] Change

[Correction content]

After kneading all of these raw materials in a kneader for 70 minutes, a pressure press machine was used at 170 ° C. for 50 minutes at 160 kg /
The foaming reaction was carried out under a pressure of cm ² , and after cooling, the pressure was released. After releasing the pressure, the same procedure as in Example (1) was performed. Physical properties of the obtained foam: apparent specific gravity 80 kg / m ³ , compressive strength 7.0 kg / c
m ² , thermal conductivity 0.030 kcal / m · h · ° C, nonflammability test (according to Ministry of Construction notification No. 1828) 75
It heated at the furnace temperature of 0 degreeC for 20 minutes. No deformation or cracking was observed in the test body after heating. It can be seen that the nonflammability is clearly improved. Comparative Example (without use of whiskers) Compounding parts by weight Inorganic substance; Aluminum hydroxide 500 Vinyl chloride resin: Emulsion polymerization paste resin Nippon Zeon Co. 121 (p = 1650) 100 Foaming agent; Dinitrosopentamethylene tetramine 6 and foaming aid (Sankyo Kasei Celmic AN) Baking soda 3 Stabilizer for vinyl chloride resin; Tribasic lead sulfate 2 Dibasic lead stearate 1 Organic solvent: Toluene 200

Claims (1)

[Claims] 1. A foam using a composition in which the mixing ratio of an inorganic substance and a vinyl chloride resin is within the range of 95: 5 to 5:95, the fiber diameter is 5 μm or less, and the melting point is 1000 ° C.
The above inorganic fiber whiskers were added to vinyl chloride resin in an amount of 0.
Highly non-combustible lightweight foam added within the range of 1% to 150%.