JPS62253636A - Inorganic material-containing foam - Google Patents

Abstract

PURPOSE:The titled foam, obtained by containing a large amount of an inorganic material in which at least part thereof is inorganic fibers, having improved heat resistance, incombustibility, sound absorbing property, etc., as well as shape holding property after burning organic materials and suitable for interior incombustible interior finish, heat insulating materials, etc. CONSTITUTION:A foam obtained by expanding a blend prepared by blending (A) water with (B) a water-soluble urethane prepolymer, (C) 70-99wt%, preferably 85-99wt% inorganic material containing >=0.5wt% inorganic fibers, e.g. asbestos, etc., having 1-50mm fiber length and 0.03-10mum diameter and (D) a low-boiling liquid. The amounts of the components are 180-5,000pts.wt. component (A) based on 100pts.wt. component (B) and 1-40pts.wt. component (B) based on 100pts.wt. component (C).

Description

[Detailed Description of the Invention] Industrial Application Fields The present invention is directed to inorganic-containing foams that contain a large amount of inorganic materials, more specifically, noncombustible materials that retain their shape even after the organic materials are burned. The present invention relates to a suitable mineral-containing foam.

<Conventional technology> Conventionally, an inorganic-containing foam is produced by mixing a urethane prepolymer having a specific amount of free isocyanate groups, an inorganic powder, a low-boiling point liquid, and water as an inorganic-containing urethane resin foam. body is known (Tokuko Sho 53-3)
Publication No. 800).

<Problems to be Solved by the Invention> However, this inorganic-containing foam has a small content of inorganic powder of about 65% by weight or less and a high content of water-soluble urethane prepolymer, so it has poor flame retardancy. There was a drawback that the mold opening was caused especially after combustion, resulting in a lack of shape retention. In addition, because it is obtained by simultaneously mixing and foaming a urethane prepolymer with a specific amount of free isocyanate groups, inorganic powder, a low boiling point liquid, and water, the bubbles are uneven, and the opening of the bubbles causes problems such as sound absorption. Not sexual enough,
In addition to the drawback of large variations in quality, when the inorganic content increases, the properties of the urethane resin, which are rich in elasticity and stretchability, are significantly lost, resulting in a lack of elasticity. In addition, conventional inorganic-containing foams use a large amount of water-soluble urethane prepolymer, and when they come into contact with water, a curing reaction immediately proceeds and fluidity is lost.
A homogeneous mixture cannot be obtained, the mixture does not conform to the mold when poured into a mold, poor workability, and extremely non-uniform products are obtained. Moreover, since a large amount of carbon dioxide gas is generated during the curing reaction, a uniform foam cannot be obtained.

<Objective of the Invention> The object of the present invention is to improve the properties of urethane resin without impairing its properties, to have a high inorganic content, and to have good properties such as sound absorption, as well as nonflammability, especially shape retention after combustion of solid matter. An object of the present invention is to provide an inorganic silicon-containing foam that has excellent properties.

Means for Solving the Problems This invention provides an inorganic-containing foam obtained by foaming a mixture of water, a water-soluble urethane prepolymer, an inorganic substance, and a low-boiling point liquid, in which the inorganic-containing foam contains an inorganic substance. The above-mentioned conventional problems are solved by an inorganic material-containing foam containing 70 to 99% by weight and in which at least a part of the inorganic material is free of V3gli fibers.

The above water-soluble urethane prepolymer exhibits water solubility,
These are various urethane prepolymers having free isocyanate groups, and are obtained by reacting a hydrophilic polyether polyol with an excess of an isocyanate compound to generate free isocyanate groups.

Examples of the above-mentioned wood-philic polyether polyols include polyethylene glycol alone, polyols such as polypropylene glycol, 1,6-hexanediol, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol, or polyester polyols, and the above-mentioned polyethylene glycols. Examples include condensates with.

Examples of the isocyanate compound include compounds having two or more isocyanate groups, such as toluene diisocyanate, diphenylmethane diisocyanate, and hexamethylene diisocyanate.

In addition, the above-mentioned water-soluble urethane prepolymer may be stabilized by masking the isocyanate groups with a masking agent such as acidic sodium sulfite.

The above-mentioned water-soluble urethane prepolymer reacts with water to generate urea bonds and carbon dioxide gas that serves as a blowing agent, and further reacts with the urea bonds to generate Goulet bonds, forming a three-dimensional structure. Become.

In addition, the above-mentioned inorganic substances include 5 blue, kaolin, talc,
Examples include inorganic powder such as mica, calcium carbonate, crushed stone, aluminum hydroxide, alumina, cement, and ceramic powder.

Inorganic fibers constituting at least a part of the above-mentioned inorganic materials include asbestos, rock wool, glass fiber, ceramic fiber, carbon fiber, steel Pa such as stainless steel, etc.
Various ta-free fibers such as inorganic fibers such as N, multi-knotted fibers are exemplified.

There are various forms of the above-mentioned non-meter fibers, such as fiber length 1 to 50-1 diameter 0.03 to 10μ.For example, rock wool is a layered cotton with a rough length of 4Ii of about 50m and a diameter of about 3-10μ. This layered cotton is cut to the size of a handful to produce filled cotton with a fiber length of about 25 m and a diameter of about 3 to 10 microns, and this filled cotton is further refined to a fiber length of about 5 to 25 microns and a diameter of about 3 to 10 microns. Various forms such as granulated cotton are exemplified. Among the above-mentioned inorganic fibers, rock wool has the advantage that it is inexpensive, does not have carcinogenic properties like asbestos, and is amorphous so that its diameter does not become small when mixed.

The above-mentioned rock wool is made by melting rocks, slag, etc. in a blast furnace, etc., and turning it into flocculent LLI fibers using centrifugal force or the like.

The inorganic material-containing foam contains 70-99% by weight of inorganic material.
, preferably contains 85 to 99% by weight of inorganic matter. If the solid content is less than 7% by weight, heat resistance and flame retardance will not be sufficient, and if it exceeds 99% by weight, the elasticity will be poor due to the small amount of water-soluble urethane prepolymer as a binder. These characteristics are not sufficient and are not desirable.

In addition, an inorganic-containing foam with an inorganic content of 95% by weight or more passes the base material test of the flame retardancy test according to the JIS^1321 test method, and also has an inorganic content of 8% by weight.
A foam containing 5% or more of inorganic matter has the ability to pass the surface test among the above flame retardant tests.

At least a part of the inorganic substance is the inorganic 4I
It is made up of fibers. The ms-free fibers are used in an appropriate amount necessary to prevent the bond from opening and retain its shape after burning the organic matter contained in the inorganic-containing foam, but at least 0% of the above-mentioned inorganic matter is used. .5% by weight, preferably at least 10% by weight, more preferably at least 5G!
ffi% is preferable; if it is less than 0.5% by weight, the shape retention after combustion of the organic matter is insufficient.

The inorganic-containing foam of the present invention may contain bromine-based,
It may contain an appropriate amount of a phosphorus-based flame retardant or the like.

Below, one method for manufacturing the blank-containing foam of the present invention will be explained.

The inorganic material-containing foam of the present invention is produced by preparing a mixture consisting of water, the above-mentioned water-soluble urethane prepolymer, the above-mentioned inorganic material, and a low-boiling point liquid, by adding (1) a bond in which the water-soluble urethane prepolymer is dissolved, an inorganic material to water; (2) After dispersing the inorganic substance, adding and mixing a water-soluble urethane prepolymer and foaming. In addition. The low-boiling liquid can be added at any stage.

In this method, the amount of the water-soluble urethane prepolymer used can be determined at an appropriate ratio to water depending on the water dilution viscosity characteristics of the water-soluble urethane prepolymer. 180 to 5000 parts by weight of water, preferably 300 parts by weight
It is better to use a ~3000 heavy lifting section. If the amount of water is less than 180 parts by weight, it is difficult to obtain a homogeneous mixture when inorganic substances are added and mixed, and if it exceeds 5000 parts by weight, a large amount of heat is required to remove water from the hydrous foam described below. In addition, the water-soluble urethane prepolymer does not form a gel, making the resulting product brittle, which is undesirable.

The ratio of the inorganic material to the water-soluble urethane prepolymer is such that it corresponds to the inorganic content of the inorganic material-containing foam of the present invention described above. That is, the amount is 1 to 40 parts by weight of the water-soluble urethane prepolymer per 100 parts by weight of the inorganic material, preferably 2 to 2 parts by weight of the water-soluble urethane prepolymer per 1 part by weight of the inorganic material.

Further, in the above manufacturing method, a low boiling point liquid is used as a blowing agent in order to obtain a foam having a small amount of water-soluble urethane prepolymer and having high R foam and homogeneous fine cells. Examples of this low-boiling point liquid include methylene chloride and monofluorotrichloromethane (Daikin Eki Co., Ltd.).
Examples include fluorine-based low boiling point liquids such as fluorine-based liquids such as fluorine-based liquids such as fluorine-based liquids (product name), and are used in appropriate amounts depending on the foaming ratio and the like.

In addition to the above-mentioned materials, as additives, bubble control agents such as silicone, flame retardants such as bromine-based and phosphorus-based flame retardants, etc. can be used as appropriate. These additives are used in appropriate amounts depending on the use of the foam.

In addition, when using the above method, the inorganic content can be easily increased, but in order to ensure the dispersibility of the inorganic material, it is necessary to use the inorganic material in combination with a nonionic or cationic surfactant, especially a cationic surfactant. It is preferable to use an inorganic material that has been treated with a surfactant or treated with a surfactant in advance. Note that when the inorganic fibers are layered long fibers, they may be physically loosened using a drawing machine.

Next, a mixture obtained by uniformly mixing the above components is placed in a predetermined mold and foamed by a conventional method to obtain a water-containing foam. In addition, in order to obtain a foam with high foaming or fine cells, it is preferable to foam under heating conditions, and the heating conditions vary depending on the amount of water-soluble urethane prepolymer used, the degree of foaming of the final product, etc. Appropriate conditions can be adopted depending on the conditions; usually, 100° C. for 5 to 10 minutes is sufficient. At this time, in order to obtain a uniform and fine foam, heating and foaming may be performed while pressing the mold.

Since the obtained foam contains water, the water content of the foam can be reduced under appropriate conditions, for example, at a temperature of 100°C or less, by about 5%.
By heating and drying for ~10 hours to remove,
A mineral-containing foam is obtained.

(Function) The inorganic material-containing foam of the present invention not only contains a large amount of inexpensive and nonflammable inorganic material, but also has dense cells that contribute to elasticity, heat insulation, and sound absorption properties.
At least a portion of the inorganic material is made of PR-free fibers that have the function of holding the inorganic material-containing foam.

In addition, the high content of inorganic substances is bonded in a uniformly dispersed state by nine urethane resins, which are formed by curing a water-soluble urethane prepolymer to form a three-dimensional 41I structure, and this urethane resin has elasticity. , and has high elasticity.

<Example> Below is the fruit of this invention FII! An example i will be explained.

Example 1 Rock wool layered cotton (Nippon Steel Chemical Co., Ltd. type surface product name, Fiber length 5
After adding 0cm and diameter 5u > 40g and stirring to loosen,
Further, 860 fI of rock wool granular cotton (Shin Nippon@I Tetsu Seikagaku Co., Ltd. type surface product name, fiber length 10U1 diameter 5//ff1) was added, and the mixture was stirred and mixed to loosen it uniformly.

On the other hand, 90 g of OH grout 0H-4 (Toho Chemical Co., Ltd. type surface product name), which is a water-soluble urethane prepolymer, 1 g of PR607 (type surface product name, Toray Silicone Co., Ltd.) as a bubble regulator, and Freon 11 ( 60 g (trade name, manufactured by Daikin Industries, Ltd.) were uniformly mixed.

Next, the water suspension of rock wool was added to the water-soluble urethane prepolymer mixture, and the mixture was stirred and mixed until uniform.

Add this mixture to 4451'Iffix475imx25i
Injected into a mold of size n with a filling rate of 60%, and the pressure was 0.3.
After heating and foaming at 100°C for 10 minutes while applying pressure at 94° C., the foamed water-containing foam was taken out from the mold and heated at 90° C.
It was dried at ℃ for 5 hours.

The obtained inorganic material-containing foam is composed entirely of inorganic S fibers, has an expansion ratio of 14.7 times, and a density of 190 kg.
4. Thermal conductivity was 0.044 Kcal/+mh"C.

Moreover, even after being burned for 20 minutes with a gas burner, this foam retained its shape before burning and had excellent shape retention.

Table 1 below shows the physical properties of the above inorganic material-containing foam.
Table 2 shows the sound absorption properties at a measurement temperature of 24°C.

As is clear from these results, the above-mentioned foam containing solid materials had physical properties such as elasticity and heat insulation, and also had excellent sound absorption properties, despite having a large solid material content. .

(The following is a blank space) Table 1 Measurement results of physical properties, etc. Table 2 Normal incidence sound absorption coefficient measurement results Example 2
The average fiber length: 50M1, diameter: 5M) is loosened using a shinkai machine and crushed to an average fiber length of about 2 to 10cm, and the gypsum is mixed with the above-mentioned rock wool layered cotton/gypsum-674 in the weight ratio.
The inorganic substances were adjusted.

Next, the above MuIIJ! 2400 parts by weight to 1200 parts water
parts by weight and mixed until uniformly dispersed to prepare an inorganic substance suspension.

On the other hand, 100 parts by weight of OH grout 0H-1 (product name manufactured by Toho Chemical Co., Ltd.), which is a water-soluble urethane prepolymer,
100 parts by weight of Freon 11 (product name manufactured by Daikin Industries, Ltd.) and 30 parts by weight of CR-530 (product name manufactured by Daihe Kagaku Co., Ltd.), which is a flame retardant, were stirred and mixed to form a water-soluble urethane prepolymer mixture. It was adjusted.

Then, after adding the water-soluble urethane prepolymer mixture to the inorganic suspension and uniformly dispersing it, it is poured into a predetermined mold, and the mold is placed in a constant temperature bath at 100°C to foam and harden. It was left to dry for 5 hours.

The obtained mineral-containing foam has an inorganic content of 96%
, dense rf122ONy, &. Also, inorganic content R
As in Example 1, the m-body retained its original shape even after being burned in a gas burner for 20 minutes.

<Effects of the Invention> As described above, according to the inorganic material-containing foam of the present invention,
Because it contains a large amount of inorganic substances, it has great heat resistance, nonflammability, and is inexpensive. Also, because it has dense bubbles, it has excellent elasticity, heat insulation, and heat retention, and has good sound deadening and soundproofing properties. . In addition to the above-mentioned effects, the pyrotechnic fibers that constitute at least a portion of the inorganic material have a retention effect in the inorganic material-containing foam, so that even after the organic material in the inorganic material-containing foam is combusted due to a fire, etc. It has excellent shape retention and does not lose its shape. In addition, since a high content of inorganic substances is uniformly dispersed and bonded by a small amount of urethane resin with a three-dimensional structure, the properties of the urethane resin are not impaired and the resin has good elasticity, which is an effect unique to this invention. .

In order to achieve the above-mentioned effects, the inorganic-containing foam of the present invention can be used in a wide range of applications, such as nonflammable interior materials for buildings, insulation materials, sound-absorbing materials, cushioning materials for beds and chairs, and earth-retaining materials. Can be used.

Claims (1)

[Scope of Claims] 1. An inorganic-containing foam obtained by foaming a mixture of water, a water-soluble urethane prepolymer, an inorganic substance, and a low-boiling liquid, the inorganic foam containing 70 to 99% by weight of the inorganic substance. Also, an inorganic material-containing foam, wherein at least a part of the inorganic material is an inorganic fiber. 2. The inorganic material-containing foam according to claim 1, which contains 85 to 99% by weight of inorganic material. 3. The inorganic material-containing foam according to claim 1, wherein the inorganic fiber accounts for 0.5% by weight or more of the inorganic material.