JP2520336B2 - Flame retardant paper or flame retardant board - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant paper or a flame-retardant board, and more specifically, it contains cellulose fibers, a specific hydrous inorganic compound and calcium carbonate in a predetermined ratio range and has a low smoke emission property. The present invention relates to a flame-retardant paper or a flame-retardant boat having excellent flame retardancy.

[0002]

2. Description of the Related Art In recent years, fire prevention measures such as flame retardation and smoke reduction of buildings have been emphasized with the increase in the number of buildings, the increase in scale, and the concentration of buildings. Traditionally, for fire protection measures in buildings,
As a flame-retardant paper or flame-retardant board that imparts flame retardancy to various building materials, those containing asbestos fibers as the main component, those treated with a flame-retardant chemical, or a large amount of aluminum hydroxide powder. Items such as tatami are used.

[0003]

However, while those having asbestos fiber as a main component have excellent flame retardancy and less smoke emission, asbestos fiber has recently been a causative agent of lung cancer. Since then, it has been designated as a specific substance from the viewpoints of pollution prevention and work environment hygiene, and its use is severely restricted, and its use is prohibited in some countries. The paper or board produced by subjecting a flame retardant agent agent treatment, organic phosphorus compounds, phosphorus-containing nitrogen-containing compounds, sulfamate, inorganic phosphate, halogen-containing compounds, and the flame retardants such as antimony compounds Since it is contained, toxic gas is generated at the time of ignition and a large amount of smoke is generated, which poses a serious problem in safety measures. In this respect, paper or board produced by containing a large amount of aluminum hydroxide powder is 200
Since the flame retardation is achieved by the dehydration endothermic reaction at ˜300 ° C., the generation of toxic gas at the time of ignition and smoke generation are less likely to occur as much as those treated with the above flame retardant chemical treatment. However, even with paper or boards containing a large amount of this aluminum hydroxide powder, it is technically impossible at present to manufacture paper or boards with aluminum hydroxide powder alone, and cellulose fibers are It is a general method to fix or bond the aluminum hydroxide powder with various organic binders. Therefore, even when the paper or board containing a large amount of the above-mentioned aluminum hydroxide powder is combusted,
Smoke generation due to combustion of the contained cellulose fibers and organic binders is unavoidable, which is insufficient in terms of measures to reduce smoke generation. Therefore, development of a flame-retardant paper or a flame-retardant board having further low smoke emission and excellent flame retardancy has been urgently needed.
The present invention has been made to solve the above problems,
An object of the present invention is to provide a flame-retardant paper or a flame-retardant board having low smoke generation and excellent flame retardancy.

[0004]

The flame-retardant paper or flame-retardant board according to the present invention comprises 5 to 60% by weight of cellulose fiber as a solid content, aluminum hydroxide, magnesium hydroxide, and hydroxide.
Selected from calcium and calcium aluminate
15 to 94% by weight of a hydrous inorganic compound consisting of at least one kind , and calcium carbonate of 0.06 in a solid content.
To 52 containing wt%, and, in which the hydrated inorganic compound / calcium carbonate to the weight ratio of the solid content 99.6 / 0.4 to 45/55. Any water an inorganic compound described above
Also has water of crystallization in the molecule and has a chemically similar structure. The hydrous inorganic compounds have some differences in decomposition temperature and endothermic amount depending on their types, but they are quite common in that they decompose when heated at high temperature and exhibit a flame retardant effect by an endothermic action. Therefore, basically, any of the above-mentioned hydrated inorganic compounds may be used, but aluminum hydroxide is most suitable in consideration of economical efficiency such as manual cost. The content range of calcium carbonate in the flame-retardant paper or flame-retardant board according to the present invention is 0.06 to 52% by weight, preferably 0.4 to 45% by weight in terms of solid content.
Is. If the content of calcium carbonate is less than 0.06% by weight, the smoke reduction effect cannot be sufficiently obtained. On the contrary,
If the content exceeds 52% by weight, the flame-retardant paper or flame-retardant board having sufficient strength cannot be obtained due to the insufficient amount of cellulose fibers, or the appropriate ratio of the above-mentioned hydrous inorganic compound / calcium carbonate can be secured. It is not possible to obtain a sufficient smoke reduction effect.

[0005] The content range of the water-containing inorganic compound, 15 to 94% by weight solids, preferably 40 to 90 wt%. The content of the water-containing inorganic compound is less than 15 wt%,
Sufficient flame retardancy and smoke reduction effect cannot be obtained. On the contrary 94
When the content exceeds the weight%, flame-retardant paper or flame-retardant board having sufficient strength cannot be obtained due to the excess amount of the water-containing inorganic compound. The content range of the cellulose fiber is 5 to 60% by weight, preferably 10 to 40% by weight in terms of solid content. When the content of cellulose fibers is less than 5% by weight, sufficient strength cannot be obtained, and when it exceeds 60% by weight, the flame-retardant paper has sufficient flame retardancy and low smoke generation effect due to excess organic substances. Or you can't get a flame retardant board. The <br/> hydrous inorganic content ratio range of compounds / calcium carbonate, a solid content 99.6 / 0.4 to 45/55, preferably 99 /
It is a weight ratio of 1 to 60/40. The content ratio range is 9
Sufficient smoke reduction effect cannot be obtained on the above-mentioned water-containing inorganic compound excess side than 9.6 / 0.4 or on the calcium carbonate excess side than 45/55. Flame燃紙or flame retardant board of the present invention is composed of the hydrated inorganic compound and calcium carbonate with the cellulose fibers, and various organic retention aid or SBR to improve the yield of the water-containing inorganic compound or calcium carbonate , NBR, acrylic latex, etc. may be contained. If necessary, glass fiber,
Inorganic fibers such as carbon fiber and rock wool fiber, nylon,
It may contain various synthetic fibers such as polyester and polypropylene, synthetic resins or synthetic dyes for coloring. Furthermore, depending on the application, it should be said that a dry or wet paper strengthening agent, a sizing agent, a water resistant agent, etc. should be contained in order to improve the mechanical strength and post-processing suitability of the flame-retardant paper or flame-retardant boat. There is no end.

[0006] As method in which containing the free <br/> Mizunashi machine compounds or calcium carbonate flame燃紙or flame retardant board of the present invention, the coating of paper or board the surface of which contains the hydrated inorganic compound or calcium carbonate It is also conceivable to apply it to the above to contain it. However, to ensure the content of a given said containing <br/> Mizunashi machine compounds or calcium carbonate,
Alternatively, in order to achieve uniform quality in the thickness direction,
Wherein in the raw material slurry hydrous inorganic compound or calcium carbonate internally added in the form of powder or slurry, method in which content is most preferred. In this case, cellulose fibers, method of addition and order of addition or the like of the water-containing inorganic compound, and calcium carbonate is optional, may be subjected to beating treatment, etc. as needed. In order to produce the flame-retardant paper or flame-retardant board according to the present invention using the raw material slurry thus obtained, a usual papermaking method may be used. That is, the raw material slurry may be supplied onto a papermaking net such as an ordinary Fourdrinier, a round net, or a slanted net, filtered, dewatered, squeezed and dried. If necessary, two or more paper layers may be superposed by using various combination nets, multi-tank round nets, various laminators, and the like. Further, depending on the application, the obtained flame-retardant paper or flame-retardant board may be sprayed with various paints, or subjected to surface treatment such as coating or printing, or laminated with a decorative plate, leather, synthetic resin film, or the like. Needless to say, the added value of the flame-retardant paper or the flame-retardant boat can be further increased.

The flame-retardant paper or flame-retardant board of the present invention exhibits excellent flame retardancy only by containing the above-mentioned hydrous inorganic compound and calcium carbonate, but it prevents the use of conventional flame retardants. is not. As the flame retardant that can be used in combination, organic phosphorus compounds, phosphorus-containing nitrogen-containing organic compounds, sulfamate,
Known flame retardants such as inorganic phosphates, halogen-containing compounds and antimony compounds can be mentioned. The flame retardant may be used by internally adding it to the raw material slurry or by impregnating or applying it in the paper or board during or after the papermaking process. However, in this case, it is natural to define the content of the flame retardant in consideration of the content of the water-containing inorganic compound, and calcium carbonate.

[0008]

Although For more information about the low smoke emission properties of the expression mechanism is still unknown in the present invention, when the inorganic compound and the calcium carbonate is within a predetermined content ratio range, organic substances or combustion products thereof, such as cellulose fibers this caused some sort of specific physical, chemical interaction between the moisture inorganic compound and calcium carbonate, or their thermal decomposition products and
It is thought to be due to. That is, as will be described later, a very remarkable smoke-reducing effect is recognized only by adding a very small amount of calcium carbonate. A ratio of the hydrated inorganic compound and calcium carbonate deviates from a predetermined range, such a low smoke effect is less pronounced. Further, specifically, FIGS. 1, 2, 3 and as shown in FIG. 4, the water-containing inorganic compound / smoke coefficients in response to changes in the content weight ratio of calcium carbonate (smoke amount) of the paper or board Changes sharply with a minimum value (the above-mentioned hydrous mineralization
The compound / calcium carbonate content weight ratio is specified in the present invention.
When the content ratio is within the range,
Smoke generation coefficient (smoke amount) is 1 / compared to the case outside the specified range
It has decreased to 2 to 1/5. ) Since, by phase over - interaction between the organic material or combustion products thereof carbon dioxide and the like cellulose fiber produced by the thermal decomposition of water vapor and calcium carbonate generated by thermal decomposition of the hydrated inorganic compound, combustion In addition to the effect on the ratio of carbon monoxide / carbon dioxide in the combustion atmosphere, which is known as one of the parameters that regulates the state, as a result, a very peculiar and significant smoke reduction effect is exhibited. Conceivable. The effect of the gradual endothermic decomposition reaction due to the difference in their thermal decomposition temperature of the combination of the water-containing inorganic compound and calcium carbonate also will occur.

[0009]

EXAMPLES Next, the present invention will be described more specifically based on the following examples. Each item in this example was measured by the following method. Yonetsubo: According to JIS P-8118. Thickness and density: According to JIS P-8118. Flame retardance: According to UL94 standard V-0 or V-1. Smoke emission (smoke coefficient): According to the surface combustion test of JIS A-1321. Example 1 A predetermined amount of a cellulose fiber dispersion obtained by disintegrating commercially available softwood unbleached sulfate pulp with a disintegrator was taken, and an aluminum hydroxide powder (having an average particle size of 5.7 μm. The same) is added and sufficiently dispersed and mixed by a stirrer, then calcium carbonate powder (average particle size is 1.5 μm. The same applies hereinafter) is added, sufficiently dispersed and mixed by a stirrer, and a square type By hand making with a test paper machine, a board A containing 26.6% by weight of cellulose fibers, 71.8% by weight of aluminum hydroxide and 1.6% by weight of calcium carbonate was obtained. The board A, the thickness, the density, the smoke emission coefficient, and the flame retardancy were measured, and the results are shown in Table 1 and FIG. Example 2 Example 1 was repeated except that the amount of the cellulose fiber dispersion and the amounts of the aluminum hydroxide powder and the calcium carbonate powder added were changed. Cellulose fiber 2
A board B containing 5.9% by weight, aluminum hydroxide 65.3% by weight, and calcium carbonate 8.8% by weight was obtained. Example 3 The procedure of Example 1 was repeated, except that the amount of cellulose fiber dispersion and the amounts of aluminum hydroxide powder and calcium carbonate powder added were changed. Cellulose fiber 2
A board C containing 7.3% by weight, 53.0% by weight of aluminum hydroxide and 19.7% by weight of calcium carbonate was obtained. Comparative Example 1 Example 1 was repeated except that the amount of cellulose fiber dispersion and the amounts of aluminum hydroxide powder and calcium carbonate powder added were changed. Cellulose fiber 2
A board D containing 8.1% by weight, 31.4% by weight of aluminum hydroxide and 40.5% by weight of calcium carbonate was obtained. The board B, board C and board D obtained in Examples 2 and 3 and Comparative Example 1 were measured for rice pylon, thickness, density, smoke emission coefficient and flame retardancy, respectively, and the results are shown in Table 1 and FIG. It was shown to.

Comparative Example 2 Cellulose fibers were prepared in the same manner as in Example 1 except that the amount of the cellulose fiber dispersion liquid and the amount of the aluminum hydroxide powder added were changed and the calcium carbonate powder was not added. 25.9% by weight, aluminum hydroxide 74.
A board E containing 1% by weight was obtained. With respect to the board E, the weight per square meter, the thickness, the density, the smoke emission coefficient, and the flame retardancy were measured, and the results are shown in Table 1 and FIG. Example 4 Example 1 was the same as Example 1 except that magnesium hydroxide powder was used instead of aluminum hydroxide powder, and the amount of cellulose fiber dispersion and the amount of calcium carbonate powder added were changed. I did the same. A board F containing 32.4% by weight of cellulose fibers, 65.4% by weight of magnesium hydroxide and 2.7% by weight of calcium carbonate was obtained. Example 5 Example 1 was the same as Example 1 except that magnesium hydroxide powder was used instead of aluminum hydroxide powder and the amount of cellulose fiber dispersion and the amount of calcium carbonate powder added were changed. I did the same. A board G containing 30.5% by weight of cellulose fibers, 59.3% by weight of magnesium hydroxide and 10.2% by weight of calcium carbonate was obtained. Example 6 Example 1 was the same as Example 1 except that magnesium hydroxide powder was used instead of aluminum hydroxide powder, and the amount of cellulose fiber dispersion and the amount of calcium carbonate powder added were changed. I did the same. A board H containing 31.1% by weight of cellulose fibers, 40.5% by weight of magnesium hydroxide and 28.4% by weight of calcium carbonate was obtained. Comparative Example 3 The same as Example 1 except that magnesium hydroxide powder was used instead of aluminum hydroxide powder, and the amount of cellulose fiber dispersion and the amount of calcium carbonate powder added were changed. I did the same. A board I containing 30.2% by weight of cellulose fibers, 19.9% by weight of magnesium hydroxide and 49.9% by weight of calcium carbonate was obtained. The board F, board G, board H and board I obtained in the above Examples 4 to 6 and Comparative Example 3 were each measured for the weight per square meter, the thickness, the density, the smoking coefficient and the flame retardancy, and the results are shown in Table 1. And shown in FIG.

Comparative Example 4 The procedure of Comparative Example 2 was repeated except that magnesium hydroxide powder was used instead of aluminum hydroxide powder and the amount of cellulose fiber dispersion was changed. A board J containing 32.8% by weight of cellulose fiber and 67.2% by weight of magnesium hydroxide was obtained. With respect to Board J, the weight per square meter, the thickness, the density, the smoke emission coefficient, and the flame retardancy were measured, and the results are shown in Table 1 and FIG. Example 7 Cellulose fibers were prepared in the same manner as in Example 1 except that the amount of cellulose fiber dispersion and the amounts of aluminum hydroxide powder and calcium carbonate powder added were changed.
A paper a containing 23.8% by weight, aluminum hydroxide 74.8% by weight and calcium carbonate 1.4% by weight was obtained. For the paper a, the tsubo, thickness, density and flame retardancy were measured,
The smoke emission coefficient was measured by stacking two sheets of the above and the results are shown in Table 1 and FIG. Example 8 Example 8 was performed in the same manner as in Example 7 except that the amount of cellulose fiber dispersion and the amounts of aluminum hydroxide powder and calcium carbonate powder added were changed. Cellulose fiber
A paper b containing 24.2% by weight, 67.2% by weight of aluminum hydroxide and 8.6% by weight of calcium carbonate was obtained. Example 9 The procedure of Example 7 was repeated, except that the amount of cellulose fiber dispersion and the amounts of aluminum hydroxide powder and calcium carbonate powder added were changed. Cellulose fiber
A paper c containing 24.5% by weight, 55.7% by weight of aluminum hydroxide and 19.8% by weight of calcium carbonate was obtained. Comparative Example 5 The procedure of Example 7 was repeated, except that the amount of cellulose fiber dispersion and the amounts of aluminum hydroxide powder and calcium carbonate powder added were changed. Cellulose fiber
A paper d containing 25.1% by weight, aluminum hydroxide 33.0% by weight and calcium carbonate 41.9% by weight was obtained. Example 8 above
And the paper b, the paper c, and the paper d obtained in Comparative Example 5,
In the same manner as in Example 7, the basis weight, the thickness, the density, the smoke emission coefficient, and the flame retardancy were measured, and the results are shown in Table 1 and FIG.

Comparative Example 6 Comparative Example 2 was carried out in the same manner as Comparative Example 2 except that the amount of cellulose fiber dispersion and the amount of aluminum hydroxide powder added were changed. A paper e containing 25.9% by weight of cellulose fiber and 74.1% by weight of aluminum hydroxide was obtained. With respect to the paper e, in the same manner as in Example 7, the tsubo, the thickness, the density, the smoke emission coefficient, and the flame retardancy were measured, and the results are shown in Table 1 and FIG. Example 10 Example 7 was repeated except that magnesium hydroxide powder was used in place of aluminum hydroxide powder, and the amount of cellulose fiber dispersion and the amount of calcium carbonate powder added were changed. Same as. Cesarrose fiber 26.8% by weight, magnesium hydroxide 71.1% by weight, calcium carbonate 2.
A paper f containing 1% by weight was obtained. Example 11 Example 7 was repeated except that magnesium hydroxide powder was used in place of aluminum hydroxide powder and the amount of cellulose fiber dispersion and the amount of calcium carbonate powder added were changed. Same as. Cellulose fiber 27.0% by weight,
Paper g containing 63.1% by weight of magnesium hydroxide and 9.9% by weight of calcium carbonate was obtained. Example 12 Example 7 was repeated except that magnesium hydroxide powder was used in place of aluminum hydroxide powder and the amount of cellulose fiber dispersion and the amount of calcium carbonate powder added were changed. Same as. 27.4% by weight of cellulose fiber,
A paper h containing 45.3% by weight of magnesium hydroxide and 27.3% by weight of calcium carbonate was obtained. Comparative Example 7 Example 7 was repeated except that magnesium hydroxide powder was used in place of aluminum hydroxide powder, and the amount of cellulose fiber dispersion and the amount of calcium carbonate powder added were changed. Same as. Cellulose fiber 28.1% by weight,
A paper i containing 24.3% by weight of magnesium hydroxide and 47.6% by weight of calcium carbonate was obtained. For the paper f, the paper g, the paper h and the paper i obtained in the above Examples 10 to 12 and Comparative Example 7, the tsubo, the heat, the density, the smoking coefficient and the flame retardancy were measured in the same manner as in Example 7, The results are shown in Table 1 and FIG.

Comparative Example 8 The procedure of Comparative Example 2 was repeated except that magnesium hydroxide powder was used in place of aluminum hydroxide powder and the amount of cellulose fiber dispersion was changed. Cellulose fiber 27.3% by weight, magnesium hydroxide 72.7% by weight
A paper j containing With respect to the paper j, the rice tsubo, the heat, the density, the smoke emission coefficient, and the flame retardancy were measured in the same manner as in Example 7, and the results are shown in Table 1 and FIG.

[0014]

[Table 1]

[0015] Table 1, Figure 1, Figure 2, for the additional inclusion of a predetermined amount of the hydrous inorganic compound and the calcium carbonate in the paper or board as apparent from FIGS. 3 and 4, and hydrous inorganic
The compound / calcium carbonate content weight ratio is within the predetermined range.
By be Rukoto, smoke coefficients, i.e. amount of smoke was reduced dramatically. That is, the hydrous inorganic compound / calcium carbonate
The content weight ratio of is within the range specified in the present invention.
When the content weight ratio is out of the range specified in the present invention,
The smoke coefficient (smoke amount) is reduced to 1/2 to 1/5 compared to
It was It was also found that excellent flame retardancy can be maintained.
In particular, it has been found that a remarkable smoke reduction effect can be obtained even if the content of calcium carbonate is extremely small.

[0016]

As can be seen from the above description, the present invention comprises a paper or board containing a predetermined amount of the above-mentioned hydrated inorganic compound and calcium carbonate, and the hydrated inorganic compound / carbonic acid.
Since the calcium content weight ratio was within the predetermined range, the amount of smoke generation could be dramatically reduced. Further, it is possible to obtain a flame-retardant paper or flame-retardant board having low smoke generation and excellent flame retardancy. In addition, calcium carbonate is aluminum hydroxide, magnesium hydroxide, calcium hydroxide and calcium hydroxide.
At least one selected from lumine calcium oxide
Since the price is one-tenth to one-tenth or less of the water-containing inorganic compounds of the same type, economically inexpensive flame-retardant paper or flame-retardant board can be obtained.

[Brief description of drawings]

FIG. 1 is a diagram showing the relationship between a smoke emission coefficient and a weight ratio of a hydrous inorganic compound / calcium carbonate content in a board, showing a case where the hydrous inorganic compound is aluminum hydroxide.

FIG. 2 is a diagram showing the relationship between the smoke emission coefficient and the weight ratio of the hydrated inorganic compound / calcium carbonate content in the board, showing the case where the hydrated inorganic compound is magnesium hydroxide.

FIG. 3 is a diagram showing the relationship between the smoke generation coefficient and the water-containing infinitesimal compound / calcium carbonate-containing weight ratio in paper, showing the case where the water-containing inorganic compound is aluminum hydroxide.

FIG. 4 is a diagram showing a relationship between a smoke emission coefficient and a water-containing infinitesimal compound / calcium carbonate-containing weight ratio in paper, showing a case where the water-containing inorganic compound is magnesium hydroxide.

[Explanation of symbols]

 A to J board a to j paper

Claims (1)

(57) [Claims] 1. Cellulose fiber is a solid content of 5 to 60% by weight, aluminum hydroxide, magnesium hydroxide, and hydroxide.
Selected from calcium and calcium aluminate
15 to 94% by weight of a hydrous inorganic compound consisting of at least one kind , and calcium carbonate of 0.06 in a solid content.
To 52 containing wt%, and hardly燃紙or flame retardant board, characterized in that said hydrated inorganic compound / calcium carbonate in a weight ratio of the solid content 99.6 / 0.4 to 45/55.