JP2715308B2 - Flame retardant papermaking - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a flame-retardant papermaking, and more particularly, to a highly flame-retardant papermaking comprising aluminum hydroxide as a main component.

The flame-retardant papermaking of the present invention can be used in various difficulties, for example, as wallpaper, backing paper for wallpaper, as a material for honeycombs for fire prevention panels, as an exterior for glass wool insulation, and as a substitute for asbestos, which is concerned about health problems. It can be used for fuel applications.

(Prior art) Conventionally, flame-retardant papermaking involves applying or impregnating various flame-retardants to papermaking using ordinary pulp, or making part of the pulp non-flammable or flame-retardant organic or inorganic fibers or Instead of a powder, a flame retardancy was imparted as an inorganic material-containing material.

(Problems to be Solved by the Invention) However, pulp paper coated or impregnated with a flame retardant also burns out when exposed to a flame, and when non-flammable or flame-retardant fibers or powders are used, the paper-making properties are reduced. In order to maintain the pulp, it is necessary to use a considerably large amount of pulp, and if the pulp component is burned off, there is a drawback that the shape of paper cannot be maintained. In particular, when aluminum hydroxide is used as the non-combustible substance, a substance containing aluminum hydroxide at a high rate and capable of maintaining its shape even after the combustible components used in combination have been burned off cannot be obtained.

When such a paper is used as a backing paper for wallpaper, etc. and subjected to a flame retardancy test, there is no resistance enough to support the decorative layer on the surface.
Even a flame-retardant material having a remarkably excellent surface layer has the disadvantage that the surface layer peels off or falls off before or during combustion.

(Means for Solving the Problems) The present inventors can solve the above-mentioned drawbacks and give the wallpaper a positive fire protection performance, that is, retain the shape even after the organic matter is decomposed and exhibit the fire protection performance. As a result of intensive studies for the purpose of developing such flame-retardant papermaking, the present invention has been achieved. That is, in the present invention, the aluminum hydroxide component is reduced to 50 to 50
The present invention relates to a flame-retardant papermaking method characterized by being rich in various post-processing properties while being contained in a large amount such as 90% by weight, and capable of maintaining its shape even after a flame combustion test according to JIS A-1322, and a method for producing the same. . Examples of the production method include 5 to 30 parts by weight of cellulosic fiber, 1 to 10 parts by weight of inorganic fiber, 1 to 10 parts by weight of hydrated swellable mineral, and 50 to 95 parts of aluminum hydroxide.
A method in which a wet dispersion is prepared by mixing a dispersion containing 2 parts by weight of an organic binder and 2 to 10 parts by weight of an organic binder and, if desired, a coagulant and various other papermaking additives and dispersing the mixture in water. Can be

It should be noted that the wet papermaking method used for producing the flame-retardant papermaking of the present invention refers to, for example, a filtration network such as a band, a cylinder, or a square, a filtration cloth, or a filtration medium such as a filtration plate. This is a general term for a method in which an aqueous dispersion of each of the above components is flown, or after being sandwiched between these filtration media, and then filtered into a sheet form by, for example, natural filtration or vacuum filtration.

Examples of the cellulosic fibers used in the present invention include cotton linter pulp, bleached sulphite pulp (NBSP, LBSP), bleached kraft pulp (NBKP, LBK)
P), dissolved pulp (DP), rayon, hemp and the like.

Examples of the inorganic fiber used in the present invention include glass fiber, micro glass wool, rock wool, mineral wool, alumina silica fiber, alumina fiber, mullite fiber, boron fiber, quartz fiber, silicate glass fiber, and the like.
Fused silica fiber, potassium titanate fiber, zirconia fiber, calcium sulfate fiber, phosphate fiber,
Examples include, but are not limited to, fibrous substances such as borosilicate fiber, carbon fiber, and activated carbon fiber, and one or more of these inorganic fibers are appropriately selected and used. Among them, it is practical to use glass fiber because the fiber diameter and fiber length are relatively uniform and the price is low.

Aluminum hydroxide is a main component of the papermaking of the present invention. When the papermaking is exposed to a high temperature, it releases hydrated water, suppresses the temperature rise and combustion of the papermaking and the surroundings, and releases water. Aluminum oxide remains in the form of a heat-resistant substance and remains as a main component of papermaking. The hydrated swellable mineral is an inorganic compound having a crystal structure in which a crystal unit cell is repeated in the thickness direction. It has the property of being drawn in and swelling, and in the most developed stage of swelling, it is a general term for minerals that break down into ultrafine particles and form a stable sol in water.
Such hydrated and swellable minerals have the property of hardening when dried, function as a binding substance between inorganic fibers and an inorganic filler containing aluminum hydroxide as a main component, and give the papermaking flexibility.
Even after exposure to a high temperature, the paper retains its shape retention performance.

Things. Examples of such hydrated swellable minerals include bentonites (eg, colloidal bentonite, modified bentonite, colloidal sodium montmorillonite, etc.), natural products such as mountain skin, hydrated swellable mica groups (eg, sodium tetra There is, but is not limited to, synthetic products of silicic mica, sodium or lithium nitrite, sodium or lithium hectorite, and the like.

Further, the organic binder mainly contributes to the bonding between the cellulosic fibers, and gives the flexibility and strength of the papermaking. Examples of the organic binder used in the present invention include water-soluble urea resins, melamine resins, cationized starch, CMC, polyamide polyamine epichlorohydrin resins, polyimine resins, water-soluble acrylic resins, paper strength agents such as methylcellulose, ethylcellulose, and hydroxyethylcellulose. Maleic acid neutral sizing agents, rosin-based sizing agents, petroleum-based sizing agents, polymer resin emulsions, sizing agents such as rubber latex, and the like.

The flocculant is effective for aggregating aluminum hydroxide and other inorganic fine particles to a particle size suitable for papermaking and improving the yield during papermaking. Is particularly preferably a polyacrylamide-based flocculant.

In addition to the essential components as described above, various additives commonly used for papermaking can be used in combination within a range that does not impair the object of the present invention.

Examples of such additives include various synthetic fibers such as polyamide fibers, polyester fibers, and polyolefin fibers;
Anionic polymer (eg, sodium polyacrylate,
Polyacrylamide and salts of partially hydrolyzed products thereof, salts of maleic acid copolymer), cationic polymers (eg, partially hydrolyzed products of polyacrylamide), nonionic polymers (eg, polyacrylamide, polyvinyl alcohol, polyethylene oxide, etc.) ), Or spinnable polymer flocculants such as natural spinnable polymers such as egg white, trolley mallow and okra nut mucus;
Modified bentonite, fluorine-based oil-proofing agent, release agent, silane coupling agent, silicon-based repellent, bansulfate, sodium aluminate, polyphosphoric acid, ammonium polyphosphate and the like.

Further, an inorganic filler can be used in combination as long as the object of the present invention is not adversely affected. Examples of the inorganic filler include silica stone, silica sand, diatomaceous earth, kaolin, halloysite, montmorillonite, bentonite, zeolite, phosphorus ore, diaspore, gypsite, bauxite, acid clay, pottery stone, pyroxene, feldspar, limestone, limestone. Natural minerals such as stone, gypsum, dolomite, magnesite, and talc; water-insoluble metal hydroxides such as magnesium hydroxide and calcium hydroxide; calcium silicate hydrates such as tobermonite and zonotolite; calcium aluminate hydrate Hydrates of various oxides such as calcium sulfoaluminate hydrate, alumina, silica, hydrous silicic acid, spherical silica, magnesia, zinc oxide, spinel, synthetic cordierite, synthetic mullite, synthetic zeolite, synthetic calcium carbonate, Calcium phosphate, barium sulfate, magnesium carbonate Beam, titanium oxide, powders or length substantially less than 10μ fine fibrous material such as a synthetic inorganic, such as potassium titanate. Note that whiskers, scales, flakes, and the like are also included.

Examples of the method for producing the flame-retardant papermaking of the present invention using the various components described above include, for example, 5 to 30 parts by weight of cellulosic fibers, 1 to 10 parts by weight of inorganic fibers, and 1 to 10 parts of hydrated swellable minerals.
Parts by weight, 50 to 95 parts by weight of aluminum hydroxide and 2 to 10 parts by weight of an organic binder.
Other papermaking additives can be mixed and dispersed in water to obtain a papermaking by a wet papermaking method.

Among the components of the dispersion, the cellulosic fiber is 5%.
If the amount is less than 10 parts by weight, the strength and flexibility of the obtained paper are insufficient, and post-processing and other handling are difficult and impractical. The subsequent shape retention is insufficient and does not satisfy the object of the present invention.

On the other hand, if the amount of the inorganic fiber is less than 1 part by weight, the shape retention after the cellulose fiber is burned by exposure to high temperature is insufficient, and if the amount is more than 10 parts by weight, the surface smoothness of the paper is inferior. Practicality is insufficient.

On the other hand, if the hydrated swellable mineral is less than 1 part by weight, the papermaking paper is exposed to high temperature and the cellulosic fibers are burned off due to insufficient bonding between the inorganic fibers or with aluminum hydroxide or other inorganic fillers. Subsequent shape retention is insufficient and does not satisfy the object of the present invention. On the other hand, if it exceeds 10 parts by weight, the dewatering property is reduced and the papermaking is not performed smoothly.

Aluminum hydroxide is a main component of the papermaking of the present invention. When the papermaking is exposed to a high temperature, it releases hydrated water to suppress the temperature rise in the papermaking and the surroundings, and is also called aluminum oxide after releasing the water. It remains as a major constituent of papermaking in the form of a refractory material. If the content of aluminum hydroxide in the papermaking of the present invention is less than 50 parts by weight, the intended flame retardancy cannot be secured, and if it exceeds 95 parts by weight, the component of aluminum hydroxide in the obtained papermaking is not sufficient. It is not preferable because the strength becomes too large and the strength as papermaking is insufficient due to insufficient cellulose-based fibers, inorganic fibers and other constituent components.

In the papermaking method of the present invention, the organic binder mainly contributes to binding between cellulosic fibers or between cellulose fibers and other components, and it is preferable to use 2 to 10 parts by weight. If the amount is less than 2 parts by weight, the bonding effect is insufficient, so that the strength of the papermaking is weak and the paper is broken during post-processing or other treatments, resulting in bending or the like, which is not practical. On the other hand, when the amount exceeds 10 parts by weight, the flame retardancy is reduced, which is not suitable for the purpose of the present invention.

When a coagulant is used, it is preferable to use about 100 to 600 ppm. If it is less than 100 ppm, the coagulation effect is not sufficiently exhibited, and the yield is reduced, which is disadvantageous in terms of cost and productivity. On the other hand, if it exceeds 600 ppm, the cohesive force becomes excessive, and as a result, fine particles such as aluminum hydroxide become coarse and pinholes frequently occur in papermaking, which is not preferable.

(Function and effect) When the flame-retardant paper manufactured as described above is exposed to a high temperature or a flame, it releases hydrated water and suppresses the temperature rise in the paper and the surrounding area, and releases water. Aluminum oxide remains as a major component of papermaking in the form of a heat-resistant substance called aluminum oxide, and it is considered that this aluminum oxide, inorganic fibers, hydrated swellable minerals, and other inorganic additives contribute to shape retention. . Such shape retention is formed by fixing the hydrated swellable mineral at the network structure of inorganic substances, that is, at the contact points between inorganic fibers and inorganic fibers and at the contact points between inorganic fibers and secondary aggregated particles of aluminum hydroxide. This is thought to be due to the fact that a relatively small amount of inorganic fibers and hydrated swellable minerals exert shape retention performance.

Although the mechanism that exerts its performance is not always clear, a network structure made up of inorganic substances that three-dimensionally overlaps the network structure made up of paper organic substances is responsible for maintaining the shape after the organic substances are decomposed. It is speculated that it might be. It is also possible that shrinkage due to decomposition and dehydration due to heat may affect the strength of the network structure due to inorganic substances.

(Examples) Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto.

Example 1 5 parts by weight of wood pulp (NBKP) was dispersed in 1000 parts by weight of water, beaten to about 25 SR, and then 5 parts by weight of glass fiber (3 mm × 6 μφ, manufactured by Nitto Boseki Co., Ltd.) Hydrated swellable mineral (Bentonite) 3 parts by weight Aluminum hydroxide 95 parts by weight Acrylic resin (Primal HA-16, manufactured by Nippon Acrylic Co., Ltd.) 2 parts by weight Coagulant (Himoloc-S, manufactured by Kyoritsu Organic Co., Ltd.) 400 ppm The dispersion was subjected to paper making using a fourdrinier paper machine to obtain a paper having a basis weight of 100 g / m ² . The content of aluminum hydroxide in the flame-retardant paper was measured by an atomic absorption method and found to be 86% by weight.

This paper was heated for 3 minutes with a Meckel burner using liquefied petroleum gas No. 5 as a fuel in accordance with JIS-A-1322 (flame retardancy test method for thin building materials). There was no flame strike-through during heating, and the sample after heating remained sheet-like without holes.

Separately, a vinyl chloride sol (13
5-J, manufactured by Zeon Corporation) was applied at 140 g / m ^{2 in} terms of solid content to prepare a decorative sheet. This sheet is attached to a non-combustible base material (10 mm thick pearlite plate) and JIS A-1321
A surface test was performed according to (flame retardancy test method for building interior materials and construction method). During the test, the decorative surface of the PVC did not fall off the surface until carbonized. The papermaking part remained without being peeled off and kept the papermaking shape.

Further, the same paper as the backing paper, basis weight 200 g / m ² woven vinyl acetate-based adhesive composed of 100% polychlal fibers thereon (Konishibondo CH-18, manufactured by Konishi Co., Ltd.) 20 g / m ²
And subjected to a surface burning test by the above-mentioned method. As in the case of the vinyl chloride decorative layer, no peeling or falling-off occurred from the backing paper until the woven fabric was carbonized.

Example 2 In Example 1, the dispersion liquid composition was changed to 7 parts by weight of wood pulp (NBKP) 5 parts by weight of glass fiber (3 mm × 6 μφ, manufactured by Nitto Boseki Co., Ltd.) 3 parts by weight of hydrated swellable mineral (bentonite) Aluminum hydroxide 80 Parts by weight Titanium oxide 10 parts by weight Acrylic resin (Primal HA-16) 3 parts by weight Coagulant (Himoloc-S) Except that the amount was changed to 400 ppm, the basis weight was 100 g / m ^{2 in the same} manner as in Example 1 completely. Was manufactured. The content of aluminum hydroxide in this flame-retardant papermaking was 73% by weight.

When a flame burning test was performed on this papermaking in the same manner as in Example 1, no flame strike-through occurred during heating, and the heated sample remained sheet-like without holes.

Also, in the same manner as in Example 1, vinyl chloride sol (135-
J) was applied at 140 g / m ² to prepare a decorative sheet. This sheet was subjected to a surface test according to JIS A-1321 (flame retardancy test method for building interior materials and construction methods). During the test, the decorative surface of the PVC did not fall off the surface until carbonized. The papermaking part remained without being peeled off and kept the papermaking shape.

Example 3 Wood pulp (NBKP) 15 parts by weight Glass fiber (3 mm × 6 μφ, manufactured by Nitto Boseki Co., Ltd.) 5 parts by weight Mountain skin 3 parts by weight Aluminum hydroxide 60 parts by weight Titanium oxide 10 parts by weight in Example 2 as dispersion composition Part SBR (SNX-3484, manufactured by Sumitomo Nogatack Co., Ltd.) 10 parts by weight Coagulant (Himolock-12MLH) Except for using 400 ppm, a flame-retardant papermaking paper of 100 g / m ² was produced in exactly the same manner as in Example 1.

The content of aluminum hydroxide in the obtained paper was low in yield and was 56% by weight. This paper was subjected to a flame heating test in the same manner as in Example 1. However, as in Example 1, no flame strike-through occurred during heating, and the heated sample remained sheet-like without holes. I was

Further, this papermaking was used as a backing paper, and vinyl chloride sol (135-J) was applied as a decorative layer on the surface at 140 g / m ^{2 in} terms of solid content to prepare a decorative sheet. The sheet was subjected to a surface combustion test according to JIS A-1321 in the same manner as in Example 1. During the test, the decorative vinyl chloride layer did not fall off the surface until carbonized. The papermaking portion was not peeled off and the rest retained the papermaking shape.

Comparative Example 1 In Example 1, without using a hydrated swellable mineral as a dispersion liquid composition Wood pulp (NBKP) 7 parts by weight Glass fiber (3 mm × 6 μφ, manufactured by Nitto Boseki Co., Ltd.) 5 parts by weight Aluminum hydroxide 80 parts by weight Titanium oxide fine powder 10 parts by weight Acrylic resin (Primal HA-16) 2 parts by weight Coagulant (Himoloc-S) Except for using 400 ppm, a flame-retardant papermaking of 100 g / m ² was produced in exactly the same manner as in the example. .

The content of aluminum hydroxide in the obtained paper was 73% by weight.

When a flame burning test was performed on this papermaking in the same manner as in Example 1, the flame passed through during heating, and the heated sample was not able to maintain a sheet-like shape due to perforations.

In the same manner as in Example 1, chloride fine (135-J) was added at 140 g /
to prepare a decorative sheet by applying a m ^2. This sheet was attached to a non-combustible base material, and a surface test was performed in the same manner as in Example 1. During the test, the backing paper peeled off, and the PVC decorative layer and a part of the papermaking dropped off, exposing the substrate.

Comparative Example 2 In Example 1, the dispersion composition was such that the amount of the inorganic fiber and the hydrated swellable mineral used was less than the range of the production method of the present invention. 7 parts by weight of wood pulp (NBKP) 0.5 part by weight of glass fiber (3 mm × 6 μφ) Hydrated swellable mineral (bentonite) 0.5 parts by weight Aluminum hydroxide 80 parts by weight Titanium oxide 10 parts by weight Acrylic resin (Primal HA-16) 2 parts by weight Coagulant (Himoloc-S) Similarly, a flame-retardant papermaking paper of 100 g / m ² was produced.

The content of aluminum hydroxide in the obtained paper was 72% by weight. The paper was subjected to a heating test using a flame in the same manner as in Example 1. However, unlike in the case of Example 1, the flame penetrated during heating, and the sample after heating was not able to maintain a sheet shape due to holes. Was. Separately, vinyl chloride sol (135-J) was applied as a decorative layer to this paper making in the same manner as in Example 1 to 150 g / m ^2.
It was applied to make a decorative wallpaper.

This wallpaper was stuck to a non-combustible substrate and subjected to a surface test in the same manner as in Example 1. As in Comparative Example 1, part of the PVC decorative layer and papermaking dropped off during the test, exposing the substrate.

Comparative Example 3 In Example 1, a dispersion liquid composition containing no inorganic fiber was used. Wood pulp (NBKP) 7 parts by weight Hydrated swellable mineral (bentonite) 3 parts by weight Aluminum hydroxide 80 parts by weight Polyester fiber (EP-202X5 Kuraray stock) Company) 10 parts by weight Acrylic resin (Primal HA-16) 2 parts by weight Coagulant (Himoloc-S) A flame-retardant papermaking paper of 100 g / m ² was prepared in exactly the same manner as in the example except that 400 ppm was used.

The content of aluminum hydroxide in the obtained paper was 74% by weight. The paper was subjected to a heating test using a flame in the same manner as in Example 1. However, the sample after the heat application was not perforated due to holes. Separately, a vinyl chloride sol (135-J) was applied as a decorative layer to the paper at 150 g / m ² to prepare a decorative sheet.

This sheet was attached to a non-combustible substrate, and a surface test was conducted in the same manner as in Example 1. In the course of the test, a part of the PVC decorative layer and the papermaking paper fell off and the substrate was exposed.

Claims (3)

(57) [Claims] The main component is composed of cellulose fiber, inorganic fiber, hydrated swellable mineral, aluminum hydroxide and organic binder, containing 50 to 90% by weight of aluminum hydroxide component,
Flame-retardant papermaking that can maintain its shape after a JIS A-1322 flame heating test. 2. Cellulose fiber 5-30 parts by weight, inorganic fiber 1-10 parts by weight, hydrated swellable mineral 1-10 parts by weight, aluminum hydroxide 50-95 parts by weight, organic binder 2-10 parts by weight The flame-retardant papermaking according to claim 1, wherein a dispersion obtained by dispersing a mixture as an essential component in water is formed by a wet papermaking method. 3. A composition comprising 5 to 30 parts by weight of cellulose fibers, 1 to 10 parts by weight of inorganic fibers, 1 to 10 parts by weight of a hydrated swellable mineral, 50 to 95 parts by weight of aluminum hydroxide, and 2 to 10 parts by weight of an organic binder. A method for producing flame-retardant papermaking, characterized by forming a dispersion obtained by dispersing a mixture as an essential component in water by a wet papermaking method.