KR101893282B1 - Non-curable refractory putty composition - Google Patents

Abstract

Curable fire retardant putty composition which is lightweight, excellent in workability, and excellent in fire resistance. Specifically disclosed is a noncurable refractory putty composition comprising a filler, a binder resin, a hollow inorganic filler, and a resin microballoons, wherein the filler is selected from the group consisting of aluminum hydroxide, magnesium hydroxide, talc and fly ash, Wherein the binder resin is selected from the group consisting of polybutene oil, liquid polybutadiene, liquid styrene butadiene rubber, liquid chloroprene rubber, and liquid isoprene rubber, wherein the resin microballoons are inorganic powders and at least a part of the surface is coated, Wherein the resin constituting the outer periphery of the resin microballoons is selected from the group consisting of acrylonitrile resin, phenol resin and vinylidene chloride.

Description

[0001] NON-CURABLE REFRACTORY PUTTY COMPOSITION [0002]

The present invention relates to a non-curable refractory putty composition used for filling an opening of a cable, a pipe or the like installed on a fire wall, a floor or the like in a building (such as a building or a ship).

In a building such as a building or a ship, a through hole is drilled in an arcing partition such as a wall or a floor separating each facility and each room, and piping of the air conditioning equipment and various electric cables are inserted into the through hole. However, when a fire occurs in a certain space, the resin pipe, the foam insulation of the piping of the air conditioner, the covering of the electric wire cable, etc. are burnt or melted and disappear with the heat or flame, so that the through- The combustion proceeds to nearby facility, room.

Putty having fire resistance or nonflammability has been used as a fire protection measure for these penetration portions. The putty is used to fill the opening or to combine with a nonflammable board such as a calcium silicate board to prevent the gap. The putty used herein includes a curing putty which is cured with the lapse of time after the application and a non-curable putty which is not dried and hardened even after the application.

The curing type putty has an advantage that the penetration part after the construction can be firmly maintained, but there is a disadvantage that it can not cope with the replacement of the wiring line due to the renovation of the building or the extension of facilities. In addition, when water glass was used for the composition, there was a problem in water resistance, and there was a weak problem when it was exposed to rain or dew in the open air.

As the non-curing putty, for example, a paste type filler containing an inorganic filler in an organic binder may be mentioned. The non-curing type putty is easy to pull out and re-work after putting, but a flame retardant having a high specific gravity such as aluminum hydroxide is used in order to maintain sufficient fire resistance, and a lot of putty itself has a high specific gravity. When used in penetrating parts such as high-rise buildings, it is necessary to transport the material to a higher layer, and a heavy putty requires less effort because it can be carried at a time.

As a technique for reducing the weight of products such as putty and clay, a method of using various lightweight fires has been examined. For example, hollow beads or organic microballoons have been used as lightweight fires (Patent Documents 1 and 2).

Patent Document 1: JP-A No. 2011-46821 Patent Document 2: JP-A-2000-212481

However, the putty described in Patent Documents 1 and 2 is a repairing putty having curability and is not a composition having a non-curable refractory property usable for fire protection measures.

When resin microballoons alone are used as lightweight fires in order to achieve a fire resistance putty less than a specific gravity of 1, resin microballoons occupy the majority of the volume percentage of the putty as a whole. Therefore, A portion is burnt and a gap is formed, so that it is impossible to provide a putty having a sufficient fire resistance performance.

In addition, when only a hollow inorganic filler such as fly ash balloons is used as a lightweight fire, its specific gravity is 0.6 to 1.0, and aluminum hydroxide, magnesium hydroxide, talc, etc. used as a refractory filler have a specific gravity of 2.5 or more. It becomes a putty having a specific gravity of 1.0 or more, so that it is difficult to achieve sufficient weight reduction and fire resistance. In addition, since the hollow inorganic filler tends to be broken by the force or pressure of the shearing in the kneading process in the production of the composition, when only the hollow inorganic filler is used as a lightweight fire, the specific gravity after the actual production is increased compared to the predetermined specific gravity It is also easy to lead to problems.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a non-curable refractory putty composition which is lightweight and excellent in workability and excellent in fire resistance.

The inventors of the present invention have conducted extensive studies in view of the above problems. As a result, it has been found that by using two resin microballoons and hollow inorganic fillers as lightweight fires, it is possible to provide a non-curable fire resistant putty having a specific gravity of less than 1 and having a fire resistance .

In order to achieve the above object, the following invention is provided.

(1) A non-curable refractory putty composition comprising a filler, a binder resin, a hollow inorganic filler, and a resin microballoons, wherein the filler is one or more selected from the group consisting of aluminum hydroxide, magnesium hydroxide, talc, Wherein the binder resin contains at least one kind selected from the group consisting of polybutene oil, liquid polybutadiene, liquid styrene butadiene rubber, liquid chloroprene rubber, and liquid isoprene rubber, and the resin Wherein the microballoons are inorganic powders and at least a part of the surface of the microballoons is coated, and the resin constituting the external angle of the resin microballoons is one or two selected from the group consisting of acrylonitrile resin, phenol resin and vinylidene chloride And the binder resin, the binder resin, The weight ratio of the hollow inorganic filler to the total weight of the resin microballoons coated with the inorganic powder is 25 to 65% by weight of the filler, 20 to 40% by weight of the binder resin, Of the filler, the binder resin, the hollow inorganic filler, and the resin micro-particles coated with the inorganic powder in the range of 5 to 40% by weight, the resin microballoons coated with the inorganic powder in the range of 1 to 13% Wherein the total amount of the balloons is 100% by weight.

(2) The non-curable fire retardant putty composition according to (1), wherein the hollow inorganic filler comprises at least one of fly ash balloons, shirasu balloons, and pearlite.

(3) The volume ratio (V _C / V _I ) of the volume (V _C ) of the resin microballoons coated with the inorganic powder to the volume (V _I ) of the hollow inorganic filler is 0.3 to 6.0 times, When the total volume of the filler, the binder resin, the hollow inorganic filler, and the resin microballoons coated with the inorganic powder is 100 volume%, the total amount of the inorganic filler and the resin microballoons coated with the inorganic powder is 100% (1) or (2), wherein the non-curable fire retardant putty composition is contained in an amount of 45 to 72% by volume based on the total volume.

(4) In the non-curable fire retardant putty composition, the weight ratio of the filler, the binder resin, the hollow inorganic filler, and the resin microballoons coated with the inorganic powder to the total weight of the filler, Wherein the inorganic filler is in the range of 50 to 65 wt%, the resin binder is 20 to 30 wt%, the hollow inorganic filler is 8 to 15 wt%, the resin microballoons coated with the inorganic powder are 4 to 7 wt% and as the binder resin and the hollow inorganic filler, is to the total of the resin microballoons coated with the inorganic powder containing them such that 100% by weight, yet the inorganic powder to the volume (V _I) of the hollow inorganic filler (V _C / V _I ) of the volume (V _C ) of the resin microballoons coated with the inorganic filler is in the range of 2.0 to 5.0 times, and the resin micro- The total amount of the balloons is 45 to 60% by volume based on the total volume when the total volume of the filler, the binder resin, the hollow inorganic filler, and the resin microballoons coated with the inorganic powder is 100% by volume Curable refractory putty composition according to (3).

(5) In the non-curable fire retardant putty composition, resin microballoons in which the surface of the resin microballoons are not coated with an inorganic powder are used in place of resin microballoons coated with the inorganic powder, and the resin microballoons coated with the inorganic powder that is a resin composition ratio of 0.3 to 3% by weight of the microballoons, a volume ratio of a volume (V _P) of the hollow inorganic filler, the volume (V _I) of claim microballoons resin that is not coated with the inorganic powder on the (V _P / V _I ) is in the range of 2.0 to 5.0 times, and further, the total amount of the hollow inorganic filler and the resin microballoons not coated with the inorganic powder satisfies the relationship of the filler, the binder resin and the hollow inorganic filler, (1), wherein the total volume of the resin microballoons not coated with the inorganic powder is set to 100 vol.%, Based fire retardant putty composition.

(6) The non-curable refractory putty composition according to any one of (1) to (5), wherein the specific gravity of the non-curable refractory putty composition is less than 1.0.

(7) The positive-type fire retardant putty composition according to any one of the above items (1) to (3), further comprising one or more kinds selected from the group consisting of ammonium polyphosphate, phosphoric acid ester, borax, boric acid, sodium polybasic acid, The non-curable fire retardant putty composition according to any one of (1) to (6), wherein the mixture is added in an amount of 3 to 10 parts by mass as a flame retardant.

(8) The thermosetting resin composition according to any one of the above items (1) to (3), wherein the thermosetting fire retardant putty composition is a thermosetting plasticizer composition comprising: Curable refractory putty composition according to any one of (1) to (7), wherein the plasticizer is added in an amount of 3 to 9 parts by mass as a plasticizer.

According to the present invention, it is possible to provide a non-curable fire retardant putty composition that is lightweight, excellent in workability, and excellent in fire resistance.

1 is a photograph of a sample before the electric furnace test and a sample after the test (Comparative Example 5 and Example 9), wherein A is a sample before the test (about 1.5 square centimeters), B is Comparative Example 5 , And C is Example 9 (shape retention after 10 minutes at 600 ° C).
Fig. 2 is a cross-sectional view showing an example of construction in the case of using a non-curable refractory putty composition to prevent through holes that have passed through a cable. Fig. 2A shows a section A, and B shows a section B. Fig.
Figure 3 is a standard heating curve in accordance with ISO 834.

<Non-curable fire resistant putty composition>

A non-curable refractory putty composition according to an embodiment of the present invention includes a filler, a binder resin, a hollow inorganic filler, and a resin microballoons coated with an inorganic powder. Resin microballoons coated with hollow inorganic filler and inorganic powder are included for light weight. The non-curable fire retardant putty composition according to the embodiment of the present invention is mainly used for applications requiring fire resistance at the time of fire, such as measures for penetrating the fire partition. The ratio of the filler, the binder resin, the hollow inorganic filler, and the resin microballoons coated with the inorganic powder to the total amount may be referred to as a ratio to the main composition.

A non-curable refractory putty composition according to an embodiment of the present invention is a non-curable refractory putty composition comprising a filler, a binder resin, a hollow inorganic filler, and a resin microballoons coated with an inorganic powder, wherein the filler, The weight ratio of the filler to the resin microballoons coated with the inorganic powder is 25 to 65 wt%, the binder resin is 20 to 40 wt%, the hollow inorganic filler is 5 to 40 wt% And a resin microballoons coated with the inorganic powder in an amount ranging from 1 to 13% by weight based on the total weight of the filler, the binder resin, the hollow inorganic filler, and the resin microballoons coated with the inorganic powder Curable refractory putty composition containing the total amount of 100 wt%. The noncurable refractory putty composition of the present invention contains at least the filler, the binder resin, the hollow inorganic filler, and the resin microballoons coated with the inorganic powder in an amount of 100 wt% The binder resin, the hollow inorganic filler, and the resin microballoons coated with the inorganic powder are contained in an amount of 100% by weight of the main composition composed of the binder resin, the inorganic filler and the resin microballoons coated with the inorganic powder. In addition, Quot; means to allow the non-curable fire retardant putty composition to include other materials such as impurities and additives.

The volume ratio (V _C / V _I ) of the volume (V _I ) of the hollow inorganic filler to the volume (V _C ) of the resin microballoons coated with the inorganic powder is 0.3 to 6.0 times, When the total amount of the resin microballoons coated with the inorganic powder is considered to be a volume of the noncurable fire retardant putty composition, the resin microballoons coated with the hollow inorganic filler and the inorganic powder in the putty composition are 45 to 72 parts by volume % Based on the total weight of the composition.

The non-curable fire retardant putty composition is prepared by blending 50 to 65% by weight of the filler, 20 to 30% by weight of the resin binder, 8 to 15% by weight of the hollow inorganic filler, 4 to 20% by weight of resin microballoons coated with the inorganic powder, And the resin microballoons in the range of 2.0 to 5.0 times the volume of the resin microballoons with respect to the hollow inorganic filler and further comprising a resin microballoons coated with the hollow inorganic filler and the inorganic powder As the non-curable fire retardant putty composition, it is preferable that the resin microballoons coated with the hollow inorganic filler and the inorganic powder in the putty composition in terms of volume are included in a total amount of 45 to 60% by volume in the main composition. The noncurable refractory putty composition preferably has a specific gravity of less than 1.0. The volume ratio of the resin microballoons coated with the inorganic powder to the hollow inorganic filler is preferably in a large ratio in terms of the volume ratio, but the resin microballoons coated with the inorganic powder at the time of production may exhibit a non- , It is preferable to set the upper limit to the volume ratio in consideration of the fire resistance of the product. In this case, the volume ratio is preferably 2.0 to 5.0 times, more preferably 2.5 to 4.5 times. In terms of weight reduction, the amount of resin microballoons to be added is large, and in terms of non-acidity, the amount of resin microballoons to be added is small.

The filler preferably includes one or more selected from the group consisting of aluminum hydroxide, magnesium hydroxide, talc, and fly ash, and the binder resin may be selected from the group consisting of polybutene oil, liquid polybutadiene, liquid styrene- A chloroprene rubber, and a liquid isoprene rubber. Wherein the hollow inorganic filler comprises at least one of fly ash balloons, pearlites, and shirasu balloons, and the resin constituting the shell of the resin microballoons is selected from the group consisting of acrylonitrile resin, phenol resin , Vinylidene chloride, and vinylidene chloride.

Further, it is preferable that one or two or more kinds of mixtures selected from the group consisting of ammonium polyphosphate, phosphoric acid ester, borax, boric acid, sodium polybromate, phosphazene and zinc tartrate are added to 100 parts by mass of the noncurable refractory putty composition May be added in an amount of 3 to 10 parts by mass as a flame retardant. By doing so, the flame retardancy of the non-curable fire retardant putty composition can be improved. One or two selected from the group consisting of a benzoic acid ester plasticizer, an epoxy plasticizer, a phosphate ester plasticizer, a chlorinated paraffin plasticizer, an adipic acid plasticizer and a phthalic acid ester plasticizer is added to 100 parts by mass of the non- Or more may be added in an amount of 3 to 9 parts by mass as a plasticizer. By doing so, the kneadability of the putty and the workability of the putty can be improved. The noncurable refractory putty composition of the present invention is characterized in that, with respect to 100 parts by mass of a noncurable refractory putty composition comprising a filler, a binder resin, a hollow inorganic filler, and a resin microballoons coated with an inorganic powder, Additives such as a flame retardant and a plasticizer and other materials such as impurities can be contained in a total amount of 25 parts by mass, but it is preferable that they are contained in a range of 20 parts by mass. In the case of this range, there is no problem in terms of properties as a non-curable fire resistant putty composition even if it contains other materials.

[Filler]

As the filler to be used in the putty composition according to the present embodiment, one kind or two or more kinds of aluminum hydroxide, magnesium hydroxide, talc and fly ash are included. The filler preferably accounts for 25 to 65% by weight of the main composition, more preferably 50 to 65% by weight. The fly ash having a specific gravity of 2 or more is preferably used. If the amount of the filler is too large, the specific gravity of the obtained putty composition becomes too heavy. In addition, if the amount of the filler is too small, it is difficult for the obtained putty composition to maintain its shape at the time of fire.

[Resin binder]

Examples of the binder used in the putty composition according to the present embodiment include one or more of polybutene oil, liquid polybutadiene, liquid styrene butadiene rubber, liquid chloroprene rubber, and liquid isoprene rubber, And the resin binder is not particularly limited to these. The resin binder preferably accounts for 20 to 40% by weight in the main composition, more preferably 20 to 30% by weight. If the amount of the resin binder is too large, the obtained putty composition does not harden and becomes a liquid phase. In addition, if the amount of the resin binder is too small, the proportion of the powder is too large, so that the putty composition can not be obtained and the putty composition can not be obtained.

[Hollow inorganic filler]

The hollow inorganic filler used in the putty composition according to the present embodiment is a hollow, lightweight product having an inorganic shell. These products include fly ash balloons, which are hollow coal ash obtained by floating coal ash (fly ash) obtained from thermal power plants and the like, shirasu balloons fired with microscopic volcanic clusters of glassy matter, and pearlite fired with volcanic rocks . These hollow inorganic fillers are mainly composed of SiO ₂ and Al ₂ O ₃ , and have heat resistance around 1000 ° C., so they remain when the composition is burned and are effective in improving the fire resistance. In fly ash balloon as the ratio of the major component SiO ₂ is _{60 ~ 65%, Al 2 O} 3 is 27 ~ 33%, SiO ₂ of 65 ~ 73% of the shirasu balloons, Al ₂ O ₃ from 12 to 18%, in the pearlite About 73% of SiO ₂ , and about 17% of Al ₂ O ₃ . The proportions of the above components may differ depending on the place of production, the manufacturing method, and the like. The particle diameters can be selected in different ranges depending on the grade of each product such as fly ash balloons of 5 to 300 mu m, shirasu balloons of 5 to 200 mu m and pearlite of 30 to 700 mu m, It is also possible to select an appropriate range. The true specific gravity is in the range of 0.6 to 1.0. Among them, spherical products and high-pressure-resistant grades are preferable because they can reduce the destruction due to pressure or mechanical stress during production. However, when the filler is mixed with the hollow inorganic filler or hollow inorganic filler during kneading at the time of putty production, A part thereof is destroyed by shear stress or the like. These hollow inorganic fillers may be used singly, but a plurality of different types of hollow inorganic fillers may be mixed and used. The hollow inorganic filler preferably accounts for 5 to 40% by weight of the main composition, more preferably 8 to 15% by weight. If the amount of the hollow inorganic filler is too large, the weight of the putty composition obtained becomes difficult to be reduced. If the amount of the hollow inorganic filler is too small, it is necessary to increase the amount of the resin microballoons in order to reduce the weight of the putty composition, so that the obtained putty composition can be reduced in weight, but on the contrary, the fire resistance is lowered. The hollow inorganic filler is also called a low specific gravity hollow inorganic filler or an inorganic balloon.

[Resin micro-balloon]

The resin microballoons used in the putty composition according to the present embodiment are hollow and lightweight products having a spherical resin shell. Generally, it is produced in a state containing a liquid gas, and expanded to a product particle diameter by several tens of times by the heat treatment to become hollow spherical particles. Examples of the resin for the exterior include acrylonitrile resin, phenol resin, vinylidene chloride and modified resins thereof. The particle diameter is 10 to 150 mu m and the true specific gravity is about 0.02 to 0.07, which is preferable for lightening the putty composition. Since resin microballoons are low density and smooth, they are coated with an inorganic powder on the outside of the outer wall made of resin so as to be easy to handle and have a specific gravity of 0.1-0.3. Here, the inorganic powder to be used for coating may be coated on at least a part of the surface of the resin microballoons, and from the viewpoint of light weight, coating on a part of the surface as described above, rather than coating the entire surface of the resin microballoons desirable. In addition, when resin microballoons are used which do not coat the surfaces of the resin microballoons in order to save lightweight, the resin microballoons are slightly scattered in the process of kneading the putty, May be used as it is without coating the surface.

As the inorganic powder to be used herein, calcium carbonate, talc, and aluminum hydroxide are generally used, but not particularly limited thereto. As a specific example, when the resin microballoons having a true specific gravity of about 0.03 are coated with calcium carbonate having a true specific gravity of about 2.6 and the resin microballoons: calcium carbonate = 22.5: 77.5 in a weight ratio in a coating process, calcium carbonate The true specific gravity of the resultant resin microballoons coated with calcium carbonate is about 0.13, and the resin microballoons: calcium carbonate = 96.2: 3.8 in volume ratio. As described above, the resin microballoons coated with the inorganic powder are powders which are several times the weight of the resin microballoons not coated with the inorganic powders but differ only in the volume by several%.

The resin microballoons preferably occupy 1 to 13% by weight, more preferably 4 to 7% by weight, of the main composition in a state in which the inorganic microparticles are coated. If the amount of the resin microballoons coated with the inorganic powder is too large, the fire resistance of the obtained putty composition deteriorates. In addition, if the amount of the resin microballoons coated with the inorganic powder is too small, it is difficult to reduce the weight of the putty composition obtained. The resin microballoons coated with the inorganic powder have high elasticity due to their outer material and structure and are less likely to be destroyed by pressure or mechanical stress. Do. When the resin microballoons coated with the inorganic powder and the hollow inorganic filler are used together, the destruction of the hollow inorganic filler in the preparation of the putty composition can be reduced.

[Mixing ratio of hollow inorganic filler and resin microballoons]

The non-curable refractory putty composition according to the present embodiment contains the hollow inorganic filler in an amount of 5 to 40 wt% of the main composition, and the volume (V) of the resin microballoons and the hollow inorganic filler The volume ratio (V / V _I ) of the volume (V _I ) of the particles is 0.3 to 6.0 times, preferably 2.0 to 5.0. The resin microballoons are used in an amount of 1 to 13% by weight of the main composition in the form of an inorganic powder coated, and 0.3 to 3% by weight of the main composition in the absence of the inorganic powder. By volume, these hollow inorganic fillers and resin microballoons in the putty composition together comprise 45 to 72% by volume of the main composition. The binder resin in the composition balance contains 20 to 40 wt% of the main composition, and the filler is contained in 25 to 65 wt% of the main composition.

[Flame Retardant]

Flame retardants may be used to improve the flame retardancy of the putty composition as well as the flame retardancy of the putty composition itself. As typical flame retardants, ammonium polyphosphate, phosphoric acid ester, borax, boric acid, sodium polybasic acid, phosphazene, zinc stannate and the like are preferable. It is preferable to add 3 to 10 parts by mass of a flame retardant to 100 parts by mass of the putty composition.

The term "flame retardancy" as used herein refers to a property that the putty composition itself has a characteristic of being unlikely to be burned, and refers to properties that do not ignite even when exposed to fire or turn off by the influence of the flame retardant contained in the composition even if the putty composition is ignited . On the other hand, the fire resistance refers to the property that the putty composition maintains its shape even when exposed to fire for a long time and does not apply heat to the opposite side of the putty composition.

[Plasticizer]

A plasticizer can be used to improve the softness, adhesiveness, texture, etc. of the composition. Also, when the putty is contacted with a PVC sheath or the like to which a plasticizer is added, it is possible to inhibit the plasticizer from migrating between the plasticizer and the plasticizer, thereby suppressing the influence of the plasticizer migration. As the plasticizer, a benzoic acid ester plasticizer, an epoxy plasticizer, a phosphoric acid ester plasticizer, a chlorinated paraffin plasticizer, an adipic acid plasticizer, a phthalate ester plasticizer and the like are preferable. It is preferable to add 3 to 9 parts by mass of a plasticizer to 100 parts by mass of the putty composition.

[fiber]

Organic fibers such as PET fibers, rayon, and cellulose may be added to the putty composition in order to improve the shape collapse property of the putty composition.

[Processing aid]

In order to easily carry out the preparation of the putty composition, a processing aid (auxiliary material) such as a surfactant or a lubricant may be added.

[Production method of putty composition]

The putty composition according to the present embodiment can be obtained by kneading each raw material by using a known kneader mixer, Banbury mixer or the like.

[Method of Using Non-Curable Fireproof Putty]

As an example of the construction of the non-curable refractory putty according to the present embodiment, as shown in Fig. 2, a cable 1 or a pipe is passed through a through-hole of a concrete 9 such as a wall or a floor separating the compartment A and the compartment B. , The non-curable refractory putty composition (7) is filled or filled in the through-holes to prevent the combustion at the time of fire. Blocks A and B are, for example, the first and second floors of a building, and some rooms and adjoining rooms. In the construction, the support bracket 3 and the backup material 5 may be used to fill only the putty composition 7 in the opening or improve the workability. By using the backup material 5, a pedestal of the putty composition 7 is formed, which facilitates the construction, and prevents the putty composition 7 from falling to the opposite side and reduces the amount of use of the putty. Mineral fibers such as rock wool, glass wool, and alkaline earth silicate wool can be used for the backup material (5). Alternatively, they may be wrapped with a nonwoven fabric and used in a block form. The backup material 5 is held in the opening by using the support metal fitting 3 as shown in Fig.

[Features of the present invention]

The non-curable fire resistant putty according to the present embodiment uses a resin microballoons and hollow inorganic fillers as a lightweight fire to provide a lightweight non-curing type putty having a specific gravity of less than 1, Curable refractory putty which is excellent in transparency and excellent in refractivity when cured.

Example

Hereinafter, the present invention will be described in more detail on the basis of Examples and Comparative Examples. However, the present invention is not limited to these examples. In the table, resin microballoons are abbreviated as &quot; resin balloons &quot;.

&Lt; Comparative Examples 1 and 2 &

Comparative Examples 1 and 2 are compositions obtained by adding only resin microballoons or hollow inorganic fillers without adding a filler to the binder resin.

&Lt; Comparative Examples 3 to 11 &

In Comparative Examples 3 to 11, a filler was added to the binder resin, and resin microballoons were added as a lightweight fire so that the specific gravity was less than 1.0.

&Lt; Comparative Examples 12 to 15 &

In Comparative Examples 12 to 15, a filler was added to the binder resin, and a hollow inorganic filler was added as a lightweight fire so that the specific gravity was less than 1.0.

&Lt; Examples 1 to 14 &gt;

Examples 1 to 14 are compositions obtained by adding a filler to a binder resin and further adding resin microballoons as lightweight fires and fly ash balloons as hollow inorganic fillers so that the specific gravity is less than 1.0.

&Lt; Examples 15 to 20 &gt;

Examples 15 to 20 are compositions using a hollow inorganic filler other than fly ash balloons or a plurality of hollow inorganic fillers.

&Lt; Example 21 &gt;

Example 21 is a composition using a fly ash balloon as a hollow inorganic filler and a resin microballoons not coated with an inorganic powder as resin microballoons.

The putty compositions according to each of the examples and comparative examples were obtained by kneading the raw materials with the kneader mixer in the ratios shown in Tables 1 to 8.

The raw materials used are described below.

· Polybutadiene: Liquid polybutadiene rubber

Polybutene oil A: polybutene oil (number average molecular weight 2400, kinematic viscosity at 40 DEG C of 206000 mm ² / s, kinematic viscosity at 100 DEG C of 4700 mm ² / s)

Polybutene oil B: Polybutene oil (number average molecular weight 2900, kinematic viscosity at 40 占 폚 160000 mm ² / s, kinematic viscosity at 100 占 폚 3710 mm ² / s)

Polybutene oil C: Polybutene oil (number average molecular weight 430, kinematic viscosity at 40 캜 110 mm ² / s, kinematic viscosity at 100 캜 9.5 mm ² / s)

· Plasticizer: adipic acid-based plasticizer

Resin balloons A: resin microballoons having an outer shell of acrylonitrile resin and coated with an inorganic powder of calcium carbonate. Average particle diameter of 50 to 70 占 퐉, true specific gravity of 0.12 占 .02 (including coating)

Resin Balloon B: Resin microballoons having an outer shell of acrylonitrile resin and not coated with an inorganic powder. Average particle diameter is 40 to 60 占 퐉, true specific gravity is 0.030 占 0.005

· Talc: talc powder

Aluminum hydroxide: Powder of aluminum hydroxide having an average particle diameter of 25 mu m

Hollow inorganic filler A: fly ash balloon (particle diameter: 5 to 300 탆, true specific gravity: 0.65 to 0.85 g / cm ³ , volume specific gravity: 0.3 to 0.5 g / cm ³ )

, The hollow inorganic filler B: perlite (particle size 30 ~ 700㎛, true specific gravity: 0.80 ~ 1.00g / cm ^3, bulk density 0.4g ~ 0.3 / cm ³⁾

Hollow particle filler C: Shirasu balloon (particle diameter: 5 to 200 탆, true specific gravity: 0.80 to 1.00 g / cm ³ , bulk specific gravity: 0.12 to 0.18 g / cm ³ )

Organic fiber A: Rayon fiber

· Organic fiber B: PET fiber (fiber made of polyethylene terephthalate resin)

· Flame retardant A:

Flame retardant B: Ammonium polyphosphate

[Properties]

The specific gravity of the putty composition obtained in each of the Examples and Comparative Examples was measured. It was also compared with the specific gravity calculated from the raw material composition to be mixed. Further, the properties and the state of the obtained putty composition were observed.

[Fire resistance evaluation by electric furnace test]

The fire resistance was evaluated by an electric furnace test. The evaluation method is as follows.

(1) The obtained composition is weighed so as to be about 3 cubic centimeters, and a cubic body having a side of about 1.5 cm is formed.

(2) The cube is put into a plate made of a non-combustible material in an electric furnace previously heated to 600 ° C, and left for 10 minutes.

(3) After 10 minutes, take out the plate made of non-combustible material and observe it.

The evaluation was made by visually checking the shape of the ash when the cube sample was taken out of the electric furnace after combustion and the ease of collapse of the ash when touched.

Here, as can be seen from the external photographs of the materials of Comparative Example 5 and Example 9 after the combustion test by the electric furnace of FIG. 1, the state of collapse after the combustion test can easily be determined visually.

In this evaluation, the sample whose ash is collapsed at the time of taking out from the electric furnace or the composition which is simply collapsed when touched does not have the fire resistance even when the combustion test is carried out in the construction state. On the other hand, in this test, when the ash is not collapsed and the shape is maintained and shrinkage or the like does not occur, the fire resistance tends to increase even in the combustion test in the construction state.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[Table 8]

[Discussion of Examples and Comparative Examples]

As shown in Comparative Example 1, in the case of using only the composition of the hollow inorganic filler for lightweight fire and the resin binder, the hollow inorganic filler remains unburned at the time of burning, but is disintegrated into a crushed sandy form, It is impossible to obtain fire resistance, and another filler is necessary to maintain the shape after combustion.

As shown in Comparative Example 2, when only the resin microballoons of a lightweight fire and the resin binder are used, there is no fire resistance because the composition is completely burned when the composition is burned at least 75% by weight and is hardly left.

As shown in Comparative Examples 3 to 11, in the case where the filler and the binder resin are composed only of resin microballoons as a lightweight fire, they are likely to collapse after combustion and fail to obtain sufficient fire resistance. For example, a composition having a specific gravity of less than 1 may be prepared by mixing a resin binder in an amount of about 36.8 wt% of the main composition, about 58.3 wt% of talc as a filler, about 4.9 wt% of a resin microballoons in a main composition About 38.1% by volume of the main composition) was considered, but this composition was liable to collapse after combustion, and sufficient fire resistance could not be obtained.

As shown in Comparative Examples 12 to 15, when a composition obtained by adding only a hollow inorganic filler as a lightweight fire to the filler and the binder resin was used, sufficient fire resistance could not be obtained. For example, as a composition having a specific gravity of less than 1, 30% by weight of a resin binder, 38% by weight of talc as a filler, and 32% by weight of a hollow inorganic filler, Fire resistance can not be obtained. Further, the putty compositions according to Comparative Examples 14 and 15 were prone to collapse when a force was applied after the electric furnace test because the feel and hardness were not good for use as a putty.

Examples 1 to 21 have a specific gravity of 0.6 to 1.0, all of which are excellent in fire resistance, so that no problem can be found in a combustion test in a state of construction. However, the smaller the specific gravity of the composition, the more the blending amount of resin microballoons is, and the lower the fire resistance is likely to be. When the resin microballoons and fillers corresponding to the same specific gravity are replaced by hollow inorganic fillers in order to reduce the resin microballoons while maintaining specific gravity, the amount of the hollow inorganic fillers to be blended increases, , Which makes stable production difficult.

Therefore, as in Examples 7 to 14, the hollow inorganic filler A as a non-curable fire retardant putty composition was contained in an amount of 8.4 to 12.8% by weight of the main composition, and the range of 2.0 to 5.0 times the volume of the hollow inorganic filler A was satisfied By weight, resin microballoons of 5.0 to 6.5% by weight. By volume, these hollow inorganic fillers A and resin microballoons in the putty composition together account for 50.4 to 56.2% by volume of the main composition. The resin binder in the composition balance is 20.5 to 29. 7% by weight, and the filler is included in the main composition in an amount of 53.4 to 63.2% by weight.

Examples 15 to 20 show the composition when the hollow inorganic filler is changed from the hollow inorganic filler A to the hollow inorganic filler B and the hollow inorganic filler C and when various kinds of them are used. Examples 15 to 19 are compositions corresponding to Example 13, the weight% is the same as in Example 13, and the volume% varies depending on the true specific gravity of each hollow inorganic filler. Example 20 is a composition when three types of hollow inorganic fillers A, B and C are used.

As shown in Examples 15 to 16, the hollow inorganic filler A and the hollow inorganic filler B do not have a problem of substituting and mixing.

The hollow inorganic filler C has a feature that its surface area is increased as compared with the hollow inorganic filler A and the hollow inorganic filler B due to the small difference in particle diameter, and the filling density becomes high to make it harder when putty becomes. It can be handled to the same extent as the inorganic filler A or the hollow inorganic filler B, and the refractory performance is sufficient as in Examples 17 to 19 using the hollow inorganic filler C (Shirasu balloon). Example 17 is a composition corresponding to Example 13 and a composition including hollow inorganic filler A and hollow inorganic filler C in a ratio of 1: 1 by weight, and is evaluated as a comprehensive evaluation (comprehensive evaluation ⊚). For this reason, Example 18 is a composition of the hollow inorganic filler C monolith corresponding to Example 13, so that the putty is hard and has poor continuity, and as a comprehensive evaluation, it is equivalent to those of Examples 1 to 6 (comprehensive evaluation). Similarly, for the above reasons, Example 19 has a composition corresponding to that of Example 13 and a composition including the hollow inorganic filler B and the hollow inorganic filler C in a ratio of 1: 1 by weight, The evaluation is the same as in Examples 1 to 6 (comprehensive evaluation ∘). Example 20 was a composition including the hollow inorganic fillers A, B and C together in a predetermined ratio, and there was no problem in the comprehensive evaluation as?.

Also, even when only the hollow inorganic filler C was used as the hollow inorganic filler, the composition of the evaluation (comprehensive evaluation?) Almost equal to those of Examples 10 and 11 was obtained by adjusting each composition.

Example 21 was prepared in the same manner as in Example 13 except that the volume corresponding to the resin balloon portion of the resin balloon A coated with the inorganic powder was replaced with the uncoated resin balloon B and the volume corresponding to the inorganic powder coating portion And a hollow inorganic filler (A). Here, replacing the portion corresponding to the inorganic powder coating with the hollow inorganic filler A is for lightening the weight. Since the substitution is weighted so as to replace the volume as described above, it is 6.4% by weight of the resin balloons A in Example 13 and 1.4% by weight in the resin balloons B in Example 21. As a result, the specific gravity of the putty composition is lighter than that of Example 13, but the physical properties thereof are substantially the same as those of Example 13.

[Fire resistance test]

Assuming a situation actually used, a lightweight foamed concrete panel having a thickness of 75 mm was provided with an opening having a diameter of 160 mm, and a fire resistance putty was applied to a test body passing through a cable and a pipe as shown in FIG. 2, and a fire resistance test was conducted for 60 minutes. The heating was carried out according to the standard heating curve according to ISO 834 in Fig. 3 and heated to a maximum of 945 캜 for 60 minutes. A non-curable fire resistant putty according to Example 7 was used as the fire resistant putty.

The backup material was prepared by cutting a plate-shaped rock face into a shape of an opening and filling a block of a biodegradable alkaline earth silicate wool blank with a non-woven fabric into each of the openings with a thickness of 25 mm.

As a result of the test, it was confirmed that all of the conditions were satisfied as shown in Table 9, and that the non-curable fire retardant putty according to Example 7 had sufficient fire resistance. Likewise, the same fire resistance test was carried out on the putties of Examples 1 to 6 and Examples 8 to 21 as a result, all of the materials and fire resistance were good and the specific gravity was less than 1, so that both the fire resistance and the light weight .

[Table 9]

While the preferred embodiments of the present invention have been described with reference to the accompanying drawings, the present invention is not limited to these examples. It will be apparent to those skilled in the art that various changes or modifications can be made within the scope of the technical idea disclosed herein and that they are obviously also within the technical scope of the present invention.

1: Cable
3: Support bracket
5: Backup material
7: Non-curable fire resistant putty composition
9: Concrete
11: Compartment A
13: Compartment B

Claims (8)

A non-curable refractory putty composition comprising a filler, a binder resin, a hollow inorganic filler, and a resin microballoons,
Wherein the filler comprises one or more selected from the group consisting of aluminum hydroxide, magnesium hydroxide, talc, and fly ash,
Wherein the binder resin contains one kind or two or more kinds selected from the group consisting of polybutene oil, liquid polybutadiene, liquid styrene butadiene rubber, liquid chloroprene rubber, and liquid isoprene rubber,
Wherein the resin microballoons are coated with at least a part of the surface of an inorganic powder, and the resin constituting the outer periphery of the resin microballoons is one kind selected from the group consisting of acrylonitrile resin, phenol resin and vinylidene chloride Or two or more kinds thereof,
The weight ratio of the filler to the total weight of the binder resin, the hollow inorganic filler and the resin microballoons coated with the inorganic powder is in the range of 25 to 65% by weight of the filler, And the resin microballoons coated with the inorganic powder are contained in an amount of 1 to 13% by weight, and at least the filler, the binder resin, the hollow inorganic filler, Wherein the total amount of resin microballoons coated with the inorganic powder is 100% by weight. The method according to claim 1,
Wherein the hollow inorganic filler comprises at least one of fly ash balloons, shirasu balloons, and pearlite. 3. The method according to claim 1 or 2,
The volume ratio (V _C / V _I ) of the volume (V _C ) of the resin microballoons coated with the inorganic powder to the volume (V _I ) of the hollow inorganic filler is 0.3 to 6.0 times,
Wherein the total amount of the hollow inorganic filler and the resin microballoons coated with the inorganic powder is 100 volume% of the total volume of the filler, the binder resin, the hollow inorganic filler, and the resin microballoons coated with the inorganic powder By volume based on the total volume of the non-curable refractory putty composition. The method of claim 3,
In the non-curable fire retardant putty composition, the weight ratio of each of the filler, the binder resin, the hollow inorganic filler, and the resin microballoons coated with the inorganic powder to the total weight is 50 to 65 Wherein the resin binder is 20 to 30% by weight, the hollow inorganic filler is 8 to 15% by weight, the resin microballoons coated with the inorganic powder is 4 to 7% by weight,
Wherein the total amount of the filler, the binder resin, the hollow inorganic filler and the resin microballoons coated with the inorganic powder is 100% by weight,
(V _C / V _I ) of the volume (V _C ) of the resin microballoons coated with the inorganic powder to the volume (V _I ) of the hollow inorganic filler is in the range of 2.0 to 5.0 times,
Wherein the total amount of the hollow inorganic filler and the resin microballoons coated with the inorganic powder is 100 volume% of the total volume of the filler, the binder resin, the hollow inorganic filler, and the resin microballoons coated with the inorganic powder By volume based on the total volume of the non-curable refractory putty composition. The method according to claim 1,
In the non-curable fire retardant putty composition, resin microballoons in which the surface of the resin microballoons are not coated with an inorganic powder are used in place of resin microballoons coated with the inorganic powder,
The mixing ratio of the resin microballoons not coated with the inorganic powder is 0.3 to 3% by weight,
The volume ratio (V _P / V _I ) of the volume (V _P ) of the resin microballoons not coated with the inorganic powder to the volume (V _I ) of the hollow inorganic filler satisfies the range of 2.0 to 5.0 times,
The total amount of the filler, the binder resin, the hollow inorganic filler, and the resin microballoons not coated with the inorganic powder is 100 By volume, and 45 to 60% by volume based on the total volume of the total amount of the non-curable fire retardant putty composition. The method according to any one of claims 1, 2, and 5,
And the specific gravity of the non-curable refractory putty composition is less than 1.0. The method according to any one of claims 1, 2, and 5,
A mixture of at least one member selected from the group consisting of ammonium polyphosphate, phosphoric acid ester, borax, boric acid, sodium polybasic acid, phosphazene, zinc stannate, and the like is added to 100 parts by mass of the non- And 3 to 10 parts by mass as a flame retardant. The method according to any one of claims 1, 2, and 5,
One or two selected from the group consisting of a benzoic acid ester plasticizer, an epoxy plasticizer, a phosphate ester plasticizer, a chlorinated paraffin plasticizer, an adipic acid plasticizer and a phthalic acid ester plasticizer is added to 100 parts by mass of the non- By weight, more preferably 3 to 9 parts by mass as a plasticizer.

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