JPS6047100B2 - Nonflammable lightweight composite material and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a noncombustible lightweight composite material that is easy to form deep groove embossing, and a method for producing the same.

In recent years, as buildings have become increasingly high-rise, there has been a significant increase in demand for lightweight building members that have mechanical strength that does not pose any practical problems.

Another demand is that there is a deep-rooted preference for high-quality building materials. Furthermore, in order to minimize the damage caused by fire accidents in densely populated areas, one of the important performance requirements is to make building materials incombustible. However, looking at the current situation, there is still no known building material that has all of the above-mentioned desirable characteristics, and in most cases, if weight reduction is attempted, mechanical strength sufficient for practical use cannot be achieved.

In addition, in order to increase the product value, it is possible to emphasize the beauty of the color tone, apply a beautiful uneven pattern that is not uniform like a sculptural mural, or a combination of these. It is known that the color tones are excellent due to advances in printing technology, but the concave and convex patterns have a depth of up to 50% of the total thickness, and are not uniform and cannot be mass-produced. Moreover, an excellent molding material that can be adapted to any design pattern has not yet been known. i In view of these circumstances, we have completed the present invention as a result of intensive research. In other words, the present inventor has developed an amorphous sphere, a phyllite, a senolite, (
By focusing on the characteristics of fly ash balloons made from lime, which has trade names such as (produced from coal mines in the UK), we have developed lightweight and structurally strong balloons by using fly ash balloons as a component of building materials. It was discovered that large building components could be obtained.

The most notable characteristic of fly ash balloons is that they are different from other microscopic hollow spheres such as white glass balloons.
Because it is nearly perfectly spherical and has a thick spherical shell, it has high strength and low oil absorption. Due to these characteristics, it is possible to manufacture a noncombustible composite material that is lightweight but has high strength. The present invention is based on such findings and has led to the invention of the following nonflammable lightweight composite material and method for manufacturing the same.

First, the manufacturing method of the present invention will be explained.

It has trade names such as Armosphere, Phyllite, and Zenolite, which are manufactured using lime as a raw material, and is listed in Table 1 below.
Using a fly ash balloon having the physical properties and chemical composition shown in Table 2, a micro hollow sphere mixture is formed by mixing the fly ash balloon and aluminum hydroxide at a volume ratio of 20:80 to 60:4, and the mixture is thermally cured. Resin 3-1
Adding 97 to 85 parts by weight of the micro hollow sphere mixture to 5 parts by weight, and further adding fibrous reinforcing material, coupling agent, inorganic filler, etc. to 100 parts by weight of thermosetting resin and 5% iron oxide (Fe2O3). Below, alkali (Na2O, K2O) 0.5-4% Others (C
It consists of a trace amount of chemical composition (aO, MgO, MnO...Etc), and is shaped like a microscopic hollow sphere.
Gray-white bulk specific gravity (g
/al) 0.3-0.4 apparent specific gravity (g
/Cfl) 0.6-0.7 particle size (μ)
20-250 Spherical shell thickness (μ)
2-20 melting point (℃)
1200 thermal conductivity (KcaI/Mh℃)
0.0750% breaking hydrostatic pressure (K9/Clt)
100-120 Moisture absorption (%) 0.
Using a fly ash balloon with a physical property of 0.05 or less hardness (Mohs hardness), the fly ash balloon and aluminum hydroxide were mixed in a ratio of 20:80 to 60.
：Constitute a mixture of micro hollow spheres mixed at a ratio of 4 to 4, and add 97 to 85 parts by weight of the micro hollow sphere mixture to 3 to 15 parts by weight of thermosetting resin, and further add a fibrous reinforcing material and a coupling agent. A base material layer is formed by compression molding a kneaded material containing 0.5 to 8 parts by weight per 100 parts by weight of a thermosetting resin, including an inorganic filler, and a metal on the surface of the base material layer. Powders, pigments, dyes, etc. - thermosetting resin mixed in advance with 5
A thin nonwoven fabric with a thickness of 0 to 300μ is laminated with an impregnated and dried surface layer, and a thermosetting resin is laminated on the back side with a thin nonwoven fabric impregnated and dried with approximately the same thickness as the surface layer. A non-combustible lightweight composite material.

4. The noncombustible lightweight composite material according to claim 3, which has an uneven pattern having deep embossed recesses from the surface layer to the back layer.

Detailed description of the invention. The present invention relates to a noncombustible lightweight composite material that is easy to form deep groove embossing, and a method for producing the same.

In recent years, as buildings have become increasingly high-rise, there has been a significant increase in demand for lightweight building members that have mechanical strength that does not pose any practical problems.

Another demand is that there is a deep-rooted preference for high-quality building materials. Furthermore, in order to minimize the damage caused by fire accidents in densely populated areas, one of the important performance requirements is to make building materials incombustible. However, looking at the current situation, there is still no known building material that has all of the above-mentioned desirable characteristics, and in most cases, when trying to reduce the weight, it is not possible to develop enough mechanical strength to withstand practical use.

In addition, in order to increase the product value, it is possible to emphasize the beauty of the color tone, to apply a beautiful uneven pattern that is not uniform like a sculptural mural, or to use a combination thereof. It is known that the color tones are excellent due to advances in printing technology, but the concave and convex patterns are as deep as 50% of the total thickness, and are not uniform and cannot be mass-produced. An excellent molding material that can accommodate any design pattern has not yet been known. i In view of these circumstances, we have completed the present invention as a result of intensive research. In other words, the present inventor has developed an amorphous sphere, a phyllite, a senolite, (
By focusing on the characteristics of fly ash balloons made from lime, which has trade names such as those produced from coal mines in the UK, and by using fly ash balloons as a component of building materials, we have created lightweight and structurally strong balloons. It was discovered that large building components could be obtained.

The most notable characteristic of fly ash balloons is that they are different from other microscopic hollow spheres such as white glass balloons.
Because it is nearly perfectly spherical and has a thick shell, it has high strength and low oil absorption. Due to these characteristics, it is possible to manufacture a noncombustible composite material that is lightweight but has high strength. The present invention is based on such findings and has led to the invention of the following nonflammable lightweight composite material and method for manufacturing the same.

First, the manufacturing method of the present invention will be explained.

It has trade names such as Armosphere, Phyllite, and Zenolite, which are manufactured using lime as a raw material, and is listed in Table 1 below.
Using fly ash balloons having the physical properties and chemical composition shown in Table 2, a micro hollow sphere mixture is formed by mixing the fly ash balloons and aluminum hydroxide at a sludge ratio of 20:80 to 60:4, and is then thermally cured. Resin 3-1
Adding 97 to 85 parts by weight of the micro hollow sphere mixture to 5 parts by weight, and further adding fibrous reinforcing material, coupling agent, inorganic filler, etc. to 0.5 to 80 parts by weight per 100 parts by weight of thermosetting resin. After adding parts by weight, the mixture is sufficiently kneaded, and the kneaded product is preformed into a plate-like material having a predetermined size to form a base material layer.

On the surface of the base layer, a thin non-woven fabric with a thickness of 50 to 300 μm is impregnated with a thermosetting resin containing metal powder, pigments, dyes, etc., and a dried surface layer is placed on it, and the thermosetting resin is applied on the back side. The impregnated and dried back layer is laid on a thin nonwoven fabric having approximately the same thickness as the front layer.

The front layer and the back layer are preformed to predetermined dimensions before being laminated onto the base material layer. Lamination of the surface layer, base material layer, and back layer is performed by integral molding using a saw stage.

In this way, the desired non-combustible lightweight composite material is obtained.

The surface layer, base material layer, and back layer are preformed before main molding, and the surface layer, base material layer, and back layer thus preformed are main molded as follows.

(a) After the preformed surface layer, base layer, and back layer are adhered together, they are put into a mold and main molding is performed. (b
) The preformed surface layer, base layer, and back layer are placed in a mold and overlapped.

Preformed surface layer, base material layer, put into the metal mold,
The back layer is made using a top mold with an uneven pattern of your choice.
~170℃, 5~50kgIc! By performing 5 to 1 powder hot press molding with e, a beautiful lightweight composite material is obtained which is not uniform in the saw stage and has an uneven pattern in which the depth of the concave portion can reach 50% of the total thickness. I was able to do that.

The reason why it was possible to create extremely deep embossing at such a low pressure is because the kneaded material using the fly ash balloon according to the present invention has a large volume, so the volume of the preform becomes large, which makes it difficult to compress. This is because it does not require By adopting this type of process, efficiency is achieved without causing major problems such as increased costs due to the complicated number of steps when painting processes are used, problems such as paint loss, and environmental pollution due to volatilization of solvents, etc. We were able to create a beautiful lightweight composite material. The mixing ratio of the fly ash balloon according to the present invention and aluminum hydroxide is preferably in the range of 20/80 to 60/40 (weight ratio), and the content of the fly ash balloon according to the present invention is 2 parts by weight. Below that, the benefits as a lightweight composite material are lost. Moreover, if the content of the fly ash balloon according to the present invention exceeds 6 parts by weight, the effect of aluminum hydroxide is reduced and a noncombustible material cannot be obtained. The mixing ratio of these mixtures with the thermosetting resin is 97/3 to 8.
V15 (weight ratio) is necessary, and if the resin content is less than 3 parts by weight, sufficient bonding strength will not be obtained, while if the content is more than 15 parts by weight, it will not be possible to obtain a noncombustible material. It is possible.

The amount of fibrous reinforcing material, coupling agent, inorganic filler, etc. added is 0.5 to 8 parts by weight per 100 parts by weight of thermosetting resin.
The amount should be kept within the range of the lumen. If it is more than this, the binding force of the resin will be insufficient, and if it is less than this range, sufficient efficiency cannot be obtained.

As the thermosetting resin used in the present invention, phenolic resin,
At least one of urea resin, melamine resin, xylene resin, resorcinol resin, and co-condensed resins thereof is used.

The micro hollow spheres used in the present invention are fly ash balloons manufactured using coal as a raw material, such as the trademark Armosphere, phyllite, and senolite, and have the characteristic chemical composition shown in Tables 1 and 2. . Table 1
Physical properties of fly ash balloon according to the present invention
Micro hollow sphere color
Gray-white bulk specific gravity (g/Crl)
0.3-0.4 apparent specific gravity (g/CTl)
0.6-0.7 grain size (p)
20-250 Spherical shell thickness (μ)
2-20 melting point (℃)
1200 Thermal conductivity (Kcal/Mh'C)
0.0750% breaking hydrostatic pressure (K9/Clt)
100-120 moisture absorption (%)
Hardness less than 0.05 (Mohs hardness)
5 Table 2 Chemical composition of fly ash balloon according to the present invention Silica (SlO2) 55-60
% Alumina (Al2O3) 25-30
% Iron oxide (Fe2O3) 5% or less Alkali (Na2O, K2O) 0.5-4% Others (CaO, MgO, MnO...etc) Trace amounts These fly ash balloons according to the present invention are Unlike micro hollow spheres, it has a true spherical shape (see Figures 1 and 2) and has a thicker shell than other spheres, making it extremely strong.These characteristics give it high strength despite being lightweight. It is possible to manufacture a composite material having the following properties.

Furthermore, as seen when resin and micro hollow spheres are mixed at the same weight ratio, the fly ash balloon according to the present invention can be kneaded with a very small amount of resin compared to other types of micro hollow spheres. (Oil absorption is small) Therefore, the noncombustible material of the present invention can be easily achieved. Examples of fibrous reinforcing materials include glass fiber, carbon fiber, gypsum fiber, asbestos, phenol fiber, etc., and inorganic fillers include silica, diatomaceous earth, calcium carbonate, gypsum, etc.
Mica, crane, talc, graphite carbon black, cement, antimony oxide, metal powder, etc. can be used.

Coupling agents include methacrylate chromic chloride, β-3,4-epoxycyclohexylethyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-chloropropyl Trimethoxysilane, vinyltrichlorosilane, vinyl-tris(β-methoxyethoxy)silane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltomethoxysilane, γ-amino Propyltriethoxysilane, γ-
Ureidopropyltriethoxysilane and the like are preferably used.

On the other hand, as a core material for impregnation, 50~! A thickness in the range of 300μ is preferably used.

If it is thinner than 50p, it will often break because it cannot follow the deep uneven pattern, and if it is more than 300μ, it will not be able to stretch freely, and the sharp pattern will become rounded, making full use of the good design. Beautiful Z.

Examples of the present invention will be given below.

[Example 1] To 8.5 parts by weight of a phenolic resin, 5 parts by weight of fly ash balloons (trade name: Armosphere) and 5 parts by weight of aluminum hydroxide were added, and further silane coupling and glass chop were added. After adding 6 parts by weight to the resin and thoroughly kneading, the kneaded material was pulverized to form granules, which was then filled into a formwork of a predetermined size.
A portable preform was obtained by temporary pressing for several seconds to several minutes at a temperature in the range of 0.degree. C. at which the resin does not completely cure.

On the surface of this preform, glass vapor is impregnated with a melamine urea cocondensation resin containing copper powder, colored titanium oxide (yellow), and phthalocyanine green, and then dried. Impregnated with condensation resin only, spread the dried material and shrink from 80 to 100
It was temporarily pressed at ℃ for 9 seconds to integrate the surface layer, base 7 material layer, and back layer into a portable state. This integrated laminate is inserted into a mold that has an upper mold with a concave-convex pattern with a beautiful, non-uniform design pattern and heated to 150 to 170°C.
Heat-press molded for 8 minutes at 35-45 k9 nod to give a bulk specific gravity of 0.9.
We have created a lightweight composite material with a bending strength of 135.2k9 JClt, an extremely beautiful calm color, and a three-dimensional effect. [Example 2] To 1 part of xylene resin, 6 parts of fly ash balloon (trade name: Armosphere) and 4 parts of aluminum hydroxide were added, and further glass chop, silane coupling agent, and mica were added in total. After adding 8 parts by weight to the resin and thoroughly kneading, the kneaded product was filled into a mold of a predetermined size and leveled, and the resin was completely cured in the range of 80°C to 100°C. A portable preform was obtained by temporary pressing for 1 minute at a low temperature.

Impregnating glass vapor with melamine resin to which copper powder, red iron oxide and carbon black have been added on the surface of the preform;
The dried material was placed on top, and the back side was covered with glass vapor impregnated with xylene resin and dried, and this was inserted into a mold with an upper mold that had a concave-convex pattern with a beautiful, non-uniform design pattern. ~170°C135~45
The bulk specific gravity was 0.85 by hot pressing for 10 minutes at k91d.
We have created a lightweight composite material with a bending strength of 114.2k91 cft, an extremely beautiful calm color, and a three-dimensional effect. [Example 3] 25 parts by weight of fly ash balloons under the trade name Armosphere and 75 parts by weight of aluminum hydroxide were added to 1 part by weight of phenolic resin, and further gypsum fiber and kaolin, a silane coupling agent, were added to form a resin. After adding 5 parts by weight and thoroughly kneading, the kneaded product is filled into a mold of a predetermined size and temporarily pressed for 3 [phases] at 800 to 100°C to form a portable preform. I got something.

A melamine urea cocondensation resin to which copper powder, chromium oxide, and phthalocyanine green have been added is impregnated into glass vapor and dried on the surface of the preform, and a phenolic resin impregnated into glass vapor and dried is placed on the back side. 1t, insert this into a mold that has an upper mold with a pattern of unevenness in a beautiful, non-uniform design pattern.
0~170'Cl35~45kgIcIt was hot pressed for 8 minutes to give a bulk density of 1.1 and a bending strength of 125.4k9 knots.
A lightweight composite material with an extremely beautiful surface pattern was obtained.
1! [Example 4] 6.5 parts by weight of phenolic resin and fly ash balloon 4 called AMOSPHERE (trade name)
A total of 2 parts of glass chop and a silane coupling agent were added to the resin, and 5 parts of aluminum hydroxide were added to the resin, followed by thorough kneading. Molding was carried out in the same manner as above, and the bulk specific gravity was 0.
．． 98, a lightweight composite material with a beautiful surface and a bending strength of 99.3k91d was obtained.

2JISA for the lightweight composite materials obtained in Examples 1 to 4
-1321, a nonflammability test was conducted and both the surface test and the base material test were passed.

[Comparative Example 1] In Example 1, Shirasubaru was used instead of the fly ash balloon called Armosphere! An experiment was carried out using a mold, but kneading was not possible due to insufficient wetting with the resin.

Also, a large amount of whitebait balloons were destroyed during kneading.

[Comparative Example 2] In Example 4, glass micro balloons (trade name: Armosphere) were used instead of the fly ash balloons.
(manufactured by Emerson Cuming Co.), but due to insufficient wetting with the resin, a kneaded material could not be obtained, and a considerable amount of glass microballoons were destroyed.

[Comparative Example 3] In Example 2, an experiment was conducted using a silica balloon instead of the fly ash balloon (trade name: Armosphere), but it was impossible to knead (due to insufficient resin).

Furthermore, destruction of a considerable amount of silica balene was observed.
The present invention has the above configuration, and the warping effects and advantages are summarized as follows. - Effects as a composite material: 1) Since the mixture of the fly ash balloon and aluminum hydroxide according to the present invention is the main component of the base layer, a lightweight and strong noncombustible material can be obtained.

That is, fly ash balloons are lightweight, strong, and heat-resistant aggregates due to their characteristics, and aluminum hydroxide is a noncombustible material.

b) Since the fly ash balloon according to the present invention has a small oil absorption amount, it can be kneaded with a resin using a small amount of resin.

Therefore, the amount of thermoplastic resin forming the base material layer can be reduced, and the amount of aluminum hydroxide and the fly ash balloon according to the present invention can be increased accordingly, resulting in increased nonflammability and light weight. (c) Since the coupling agent is used to strengthen the bond between the resin, aluminum hydroxide, and the fly ash balloon according to the present invention, the base layer can be completely integrated.

If only the resin is used, the bond between the aluminum hydroxide and the fly ash balloon according to the present invention is not necessarily sufficient, and the bending strength is also not sufficient.

(d) Since the front and back surfaces of the base layer are covered with a thin impregnated nonwoven fabric, the base layer can be protected and a decorative surface can be formed.

Advantages of manufacturing method B: (a) Main molding is performed after preliminary molding of the surface layer, base layer, and back layer, so gas generation during main molding can be suppressed and surface roughness can be prevented.

In addition, the main molding is reliably and easily performed, and there is no misalignment of each layer.

(b) Since the preformed surface layer, base layer, and back layer are integrally molded and embossed at the same time, deep recesses can be formed with low pressure. The reason for this is that since the kneaded material of the base material layer has a large bulk during preforming, recesses are formed at the same time as compression.

Further, the fly ash balloon according to the present invention has high strength against embossing pressure, so it will not be destroyed.

[Brief explanation of the drawing]

Figure 1 is a reproduction of a 33x magnification microscopic photograph of a fly ash balloon aggregate called Armosphere, and Figure 2 is a 33x magnification reproduction of a volcanic ash microscopic hollow sphere aggregate. .

Claims (1)

[Claims] 1 Silica (SiO_2) 55-60% alumina (Al_2O_3) 25-30% iron oxide (Fe
_2O_3) 5% or less Alkali (Na_2O, K_2O) 0.5-4% Other (CaO, MgO, MnO...etc) Trace chemical composition, shape, micro hollow sphere color, grayish white bulk specific gravity (g/cm ^3) 0.3-0.4 Apparent specific gravity (g/cm^3) 0.6-0.7 Particle size (μ) 2
0~250 Spherical shell thickness (μ) 2~20 Melting point (℃) 1200 Thermal conductivity (Kcal/mh℃) 0.07 50% breaking hydrostatic pressure (kg/cm^2) 100~120 Moisture absorption (%) 0 Using a fly ash balloon with a physical property of .05 or less hardness (Mohs hardness), the fly ash balloon and aluminum hydroxide were mixed in a ratio of 20:80 to
A mixture of micro hollow spheres was prepared by mixing in a weight ratio of 60:40, and 97 to 85 parts by weight of the micro hollow sphere mixture was added to 3 to 15 parts by weight of the thermosetting resin, and a fibrous reinforcing material and a coupling were added. A total of 0.5-80 parts by weight of additives, inorganic fillers, etc. are added to 100 parts by weight of the thermosetting resin, and then sufficiently kneaded to obtain the kneaded product. A thin non-woven fabric with a thickness of 50 to 300μ is coated with a thermosetting resin pre-blended with metal powder, pigments, dyes, etc. on the surface of the base layer. The surface layer is impregnated and dried, and the back layer is impregnated and dried with a thermosetting resin on a thin nonwoven fabric with approximately the same thickness as the surface layer, and the surface layer, base layer, and back layer are laminated. A method for manufacturing a non-combustible lightweight composite material, characterized in that it is carried out in one step by integral molding. 2. Manufacture of a non-flammable lightweight composite material according to claim 1, which uses a mold with an uneven pattern during main molding of the surface layer, base layer, and back layer, and forms an embossed uneven pattern at the same time as the main molding. Method. 3 Silica (SiO_2) manufactured using lime as raw material 55-60% Alumina (Al_2O_3) 25-30% Iron oxide (Fe
_2O_3) 5% or less Alkali (Na_2O, K_2O) 0.5-4% Others (CaO, MgO, MnO...etc) Trace chemical composition, shape, micro hollow sphere color, grayish white bulk specific gravity (g/cm^ 3) 0.3-0.4 Apparent specific gravity (g/cm^3) 0.6-0.7 Particle size (μ) 2
0~250 Spherical shell thickness (μ) 2~20 Melting point (℃) 1200 Thermal conductivity (Kcal/mh℃) 0.07 50% breaking hydrostatic pressure (kg/cm^2) 100~120 Moisture absorption (%) 0 Using a fly ash balloon with a physical property of .05 or less hardness (Mohs hardness), the fly ash balloon and aluminum hydroxide were mixed in a ratio of 20:80 to
A mixture of hollow micro spheres is prepared in a 60:40 weight ratio, and 97 to 85 parts by weight of the hollow micro sphere mixture is added to 3 to 15 parts by weight of the thermosetting resin, and a fibrous reinforcing material and a coupling agent are added. A base material layer is formed by compression molding a kneaded material containing 0.5 to 80 parts by weight of an inorganic filler and the like per 100 parts by weight of a thermosetting resin, and a metal powder is applied to the surface of the base material layer. A thin non-woven fabric with a thickness of 50 to 300 μm is impregnated with a thermosetting resin pre-blended with pigments, dyes, etc., and a dried surface layer is laminated, and a thermosetting resin is applied on the back side to form a thin non-woven fabric with approximately the same thickness as the surface layer. A non-flammable lightweight composite material characterized by laminating a backing layer that has been impregnated and dried on a non-woven fabric. 4. The nonflammable lightweight composite material according to claim 3, which has an uneven pattern having deep embossed recesses from the surface layer to the back layer.