JPH0137520B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to flame retardant paper with excellent heat setting properties. Conventionally, as a method for manufacturing general paper or mica-containing paper, a method of forming cellulose fibers or an aqueous slurry in which mica is mixed with cellulose fibers is known. However, the paper produced by this method does not have heat setting properties, so if heat setting is required, the paper may be soaked in a resin such as phenol resin, melamine resin, urea resin, etc. for 5 to 50 minutes. 30%
After being pre-dried, it is molded into the desired shape and heated in a heating furnace for heat setting. Furthermore, these papers have the disadvantage of being combustible because they use cellulose fibers. If flame retardancy is required, methods such as spraying or immersing paper in an aqueous solution of flame retardants such as ammonium phosphate, ammonium sulfamate, guanidine phosphate, guanidine sulfamate, borax, and boric acid are used. ing. However, paper treated with flame retardancy using this method has poor texture. Especially if it is placed in a humid atmosphere, the texture will deteriorate due to moisture absorption.
Disadvantages include decreased hardness and electrical resistance, and corrosion of metals in contact with the paper. If both heat setting properties and flame retardancy are required, general paper is immersed in a processing solution made by dissolving a halogenated phosphate ester in a methanol solution of phenolic resin, pre-dried, and shaped into the desired shape. After molding, heat setting is performed in a heating furnace. In this case, about 30% flame retardant and 10-30% flame retardant based on the weight of paper
% of phenolic resin needs to be deposited, the paper often loses its original properties. In order to eliminate these drawbacks, the inventors of the present invention conducted extensive research and found that it is possible to simultaneously impart heat setting properties and flame retardancy, which were considered impossible with conventional paper. The present invention uses 50 to 1000 parts by weight of mica and 4 to 4 parts by weight of aluminum hydroxide to 100 parts by weight of cellulose fiber.
It is a flame-retardant paper with excellent heat setting properties, characterized by containing 100 parts by weight of antimony trioxide, 2 to 40 parts by weight of antimony trioxide, and 4 to 60 parts by weight of chlorinated paraffin with a chlorine content of 65% or more. The flame-retardant paper of the present invention contains 50 to 1000 parts by weight of mica, 4 to 100 parts by weight of aluminum hydroxide, 2 to 40 parts by weight of antimony trioxide, and chlorinated paraffin with a chlorine content of 65% or more based on 100 parts by weight of cellulose. 4～
An aqueous slurry containing 60 parts by weight can be produced by papermaking. When producing the flame retardant paper of the present invention, there is no need for special equipment for applying heat setting agents or flame retardants, and conventional mica paper manufacturing equipment can be used as is. Further, the flame-retardant paper of the present invention can be processed into any shape, such as a sheet, a honeycomb, a pipe, or a ribbon. The cellulose fibers used to produce the flame-retardant paper of the present invention refer to cellulose fibers produced from pulp, and contain regenerated cellulose fibers such as rayon or inorganic fibers such as asbestos, rock wool, and glass fibers. It's okay. Mica used in the present invention includes:
Examples of muscovite-based mica include muscovite, red mica, soda mica, sericite, vanadium mica, and illite; biotite-based examples include biotite, phlogopite, iron mica, Chinwald mica, and the like; synthetic mica; and the like. The composition of these mica is shown below. Phlogopite _KMg3 ( _{AlSi3O10 )}
(OH) ₂ , muscovite KAl ₂ (AlSi ₃ O ₁₀ ) (OH) ₂ , soda mica NaAl ₂ (AlSi ₃ O ₁₀ ) (OH) ₂ , biotite (K ₂ MgFe〓Fe〓) ₆ (SiAl) ₈ O ₂₀ (O・OH) ₄ , lepidolite
KLi ₂ Al(Si ₄ O ₁₀ ) (OH) ₂ , synthetic fluorophlogopite KMg ₃
(AlSi ₃ O ₁₀ )F ₂ , synthetic fluorine tetrasilicon mica KMg _{2.5
( Si4O10} ) _F2 . Commercially available mica, aluminum hydroxide, and antimony trioxide can be used, but these particles preferably have a particle size of 50 mesh or less, particularly 100 mesh or less. If the particle size is larger than 50 mesh, the surface of the resulting flame-retardant paper may become rough. Furthermore, it is preferable to use chlorinated paraffin having a chlorine content of 65% or more with a particle size of 50 mesh or less, but there is no problem even if powder with a particle size larger than 50 mesh is mixed in. The chlorinated paraffin powder used in the present invention has a chlorine content of 65% or more. If chlorinated paraffin with a chlorine content of 65% or less is used, the flame retardant effect will be weakened, and since the chlorinated paraffin will soften at room temperature, it will not easily turn into powder, making papermaking at room temperature difficult. When producing the flame retardant paper of the present invention, first 50 to 1000 mica is added to 100 parts by weight of cellulose fibers.
parts by weight, aluminum hydroxide 4-100 parts by weight, antimony trioxide 2-40 parts by weight, and chlorine content 65%
An aqueous slurry containing 4 to 60 parts by weight of the above chlorinated paraffin is prepared. If the amount of mica, aluminum hydroxide, antimony trioxide or paraffin chloride is less than this, sufficient flame retardancy and heat setting properties cannot be obtained. If the amount of these components is greater than this, the strength and heat setting properties of the resulting flame-retardant paper will be reduced. Various additives used in general paper making may be added to this aqueous slurry. Examples of additives include paper strength enhancers, wet paper strength enhancers, retention improvers, water improvers, fixing aids,
Examples include sizing agents, coloring agents, erasing agents, light fastness improvers, and auxiliary agents. There are no restrictions on the order of addition, the method of addition, etc. Next, this aqueous slurry is made into paper using a conventional method to obtain flame-retardant paper with excellent heat setting properties. The flame retardant paper of the present invention is heated at 100°C or higher, preferably at 120°C.
Heat setting can be achieved by heating to a temperature above. Conventional mica-containing paper obtained by making paper from an aqueous slurry of cellulose fibers and mica does not exhibit heat setting properties. Also, when using only aluminum hydroxide, only antimony trioxide, or only chlorinated paraffin powder, no heat setting property is shown. The reason that heat setting properties can only be obtained by papermaking in the coexistence of these components is presumed to be due to some effect of the composite of the layered structure of mica, aluminum hydroxide, antimony trioxide, and chlorinated paraffin. be done. Comparing the flame retardant paper of the present invention with conventional mica-containing paper and kraft paper in terms of heat setting properties, in the case of conventional kraft paper and mica-containing paper, first the original paper is immersed in a methanol solution of phenolic resin,
Paper is used that has been impregnated with a processing solution that is apparently 100% applied to the original paper and pre-dried at 80 to 100°C. Heat set conditions require 25-30 minutes at 160°C. On the other hand, the flame retardant paper of the present invention can be used as is, and the heat setting conditions are 120 to 130°C and 25°C.
It is a minute. As described above, the flame-retardant paper of the present invention does not require any impregnation or addition of phenolic resin, and can be heat-set at a lower heating temperature than those to which phenolic resin is added. Furthermore, the flame retardant paper of the present invention has good heat setting properties and good shape. Example 1 A pulper equipped with a stirring device, a thermometer, etc. was charged with 1,000 ml of water, 0.3 kg of caustic soda was dissolved therein, and 9 kg of kraft pulp was added to prepare a slurry. Mica powder (muscovite,
Particle size 200 mesh or less, particle size approx. 10-150μ) 15Kg,
Antimony trioxide (particle size 2~3μ) 1.2Kg, aluminum hydroxide powder (particle size 50~60μ) 2.4Kg, chlorinated paraffin powder (chlorine content 70%, softening point 95~
105℃, particle size of 50 mesh or less) was added with stirring to make a uniform slurry. Next, 0.1 kg of a cationic paper strength enhancer was added, and then sulfuric acid band (8% aqueous solution) was added to adjust the pH to 6.5. Furthermore, paper strength enhancer (anionic acrylamide type)
By adding 0.1 kg and 0.007 kg of acrylamide-based cationic fixing agent, a slurry with a concentration of about 3% is obtained. This slurry is diluted to a concentration of approximately 0.2%, sent to a paper making machine, dried using a Yankee twin dryer at 100°C, and then wound up on a winding machine ^. Burnt paper was obtained. The obtained flame retardant paper was stretched into a honeycomb shape and heated to 120℃.
Heat set for 25 minutes. After immersing the heat-set honeycomb in water at room temperature for 48 hours, it was heated to 100°C.
After drying for 10 minutes, I visually observed the shape of the honeycomb and measured its diameter, but it remained unchanged from the original shape. Using the flame retardant paper obtained in this way as is,
When a flame retardant test was conducted according to the JISL-1091A-4 method, the carbonization length was 7 to 8 cm, and the afterflame and residual dust were both 0 seconds. In addition, the limiting oxygen index (LOI) was 30.0. In addition, after setting the honeycomb to heat, it was immersed in water for 48 hours, then the dried honeycomb was placed in water, and an alcohol lamp was lit for 5 seconds at the cut corner of the honeycomb shape, and the afterflame was measured, and the afterflame was 0. It was hot in seconds. Comparative Example 1 A slurry containing kraft pulp and mica was prepared in the same manner as in Example 1 except that antimony trioxide, aluminum hydroxide, and chlorinated paraffin were not used, and this slurry was made into paper containing mica. was manufactured. When a combustion test was conducted using this mica-containing paper, it completely burned down, and the limiting oxygen index was 25.5.
It was hot. Also, spread this paper into a honeycomb shape,
When heat setting was performed at 160°C for 30 minutes, no honeycomb could be produced. Comparative Example 2 Pulp,
A slurry containing mica and antimony trioxide was prepared, and this slurry was made into paper to produce mica paper. The combustion test results and heat setting properties of this mica-containing paper were similar to those of Comparative Example 1. Comparative Example 3 A slurry containing pulp, mica, and aluminum hydroxide was prepared in the same manner as in Example 1 except that antimony trioxide and chlorinated paraffin were not used, and this slurry was made into paper to produce mica-containing paper. did. The combustion test results and heat setting properties of this mica-containing paper were similar to those of Comparative Example 1. Comparative Example 4 Pulp,
A slurry containing mica and chlorinated paraffin was prepared, and this slurry was made into paper to produce mica-containing paper. The combustion test results and heat setting properties of this mica-containing paper were similar to those of Comparative Example 1. Comparative Example 5 A slurry containing pulp, mica, antimony trioxide, and aluminum hydroxide was prepared in the same manner as in Example 1 without using chlorinated paraffin, and this slurry was made into a paper containing mica. Manufactured. The combustion test results and heat setting properties of this mica-containing paper were similar to those of Comparative Example 1. Example 2 Flame-retardant paper was produced in the same manner as in Example 1 except that recycled kraft waste paper was used instead of the kraft pulp used in Example 1. The basis weight of the obtained flame-retardant paper was 175 g/m ² . Heat set and combustion tests were conducted in the same manner as in Example 1. Similar tests were also conducted on the mica-containing papers of Comparative Examples 6 to 10, which were manufactured in the same manner as Comparative Examples 1 to 5. The results are shown in Table 1.

[Table] Example 3 Using the same equipment as in Example 1, 1 kg of caustic soda was dissolved in 2500 kg of water, and 15 kg of kraft pulp and 15 kg of recycled kraft waste paper were added to prepare a pulp slurry. Next, 40 kg of mica powder (phlogopite, particle size of 200 mesh or less) and 20 kg of synthetic mica (fluorotetrasilicon mica, manufactured by Topy Industries, Ltd., 200 mesh or less) were added. Furthermore, 4 kg of antimony trioxide powder, 8 kg of aluminum hydroxide, and 9 kg of chlorinated paraffin (chlorine content 70%, softening point 95° C.) were added to prepare a uniform slurry. After adding 0.4Kg of a cationic paper strength enhancer to this slurry, sulfate band (8% aqueous solution) was added to adjust the pH to 6.5, and then 0.3Kg of a paper strength enhancer (anionic acrylamide type) and acrylamide type Added 0.02Kg of cationic fixer. This slurry was sent to a paper-making machine and paper-made under the same conditions as in Example 1 to produce flame-retardant paper. This flame retardant paper had a basis weight of 85 g/m ² . A honeycomb was produced according to the honeycomb work process. Heat set 25 at 120℃
It was hot in minutes. Heat set and combustion test is as in Example 1.
I went the same way. Similar tests were conducted on the mica-containing papers of Comparative Examples 11 to 14, which were produced in the same manner as Comparative Examples 1 to 4, and the mica-containing paper of Comparative Example 15, in which antimony trioxide was removed from this example. The results are shown in Table 2.

【table】

[Table] Example 4 Using the same equipment as in Example 1, 1,000 ml of water was charged into a pulper (disintegrator), and after dissolving 0.3°C of caustic soda, 3 kg of kraft waste paper was added to prepare a slurry. Add to this slurry 24 kg of mica powder (muscovite, particle size 200 mesh or less), 1 kg of antimony trioxide (particle size 2-3μ), 2 kg of aluminum hydroxide, and chlorinated paraffin powder (chlorine content 70
%, softening point 95-105℃, particle size 50 mesh or less) 1.5
Kg was added to make a uniform slurry. Next, 0.2 kg of cationic paper strength enhancer was added, and sulfate band (8%
Aqueous solution) was added to adjust the pH to 6.5. Additionally, paper strength enhancer (anionic acrylamide type) 0.2Kg
and an acrylamide-based cationic fixative.
Added 0.01. This slurry was diluted to a concentration of about 0.2%, sent to a paper making machine, and made into paper under the same conditions as in Example 1 to produce flame retardant paper. This flame retardant paper had a basis weight of 110 g/m ² . Heat set and combustion tests were conducted in the same manner as in Example 1. Similar tests were also conducted on the mica-containing papers of Comparative Examples 16 to 20, which were manufactured in the same manner as Comparative Examples 1 to 5. The result is the third
Shown in the table.

【table】

Claims (1)

[Claims] 1 50 mica per 100 parts by weight of cellulose fiber
~1000 parts by weight, 4 to 100 parts by weight of aluminum hydroxide, 2 to 40 parts by weight of antimony trioxide, and 4 to 60 parts by weight of chlorinated paraffin with a chlorine content of 65% or more. Excellent flame retardant paper.