JPH0247396A - Flame retardant formed paper - Google Patents

Abstract

PURPOSE:To obtain the subject highly flame retardant formed paper capable of retaining the shape even after decomposing organic substances by dispersing a mixture of aluminum hydroxide with cellulosic fibers, inorganic fibers, hydration swellable mineral and organic binder in specific amounts in water and forming sheets of paper. CONSTITUTION:The objective formed paper containing 50-90wt.% aluminum hydroxide and capable of retaining the shape even after heating tests by a flame of JIS A-1322 is obtained by dispersing a mixture containing (A) 5-30 pts.wt. cellulosic fibers, such as cotton linter or rayon, (B) 1-10 pts.wt. inorganic fibers, such as glass fiber or rock wool, (C) 1-10 pts.wt. hydration swellable mineral, such as colloidal bentonite, (D) 50-95 pts.wt. aluminum hydroxide which is a principal component and (E) 2-10 pts.wt. organic binder, such as melamine or water-soluble urea resin, as essential components in water and forming the resultant dispersion into sheets of paper by a wet sheet-forming method or a method according thereto.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to flame-retardant papermaking, and more particularly to highly flame-retardant papermaking containing aluminum hydroxide as a main component.

The flame-retardant paper of the present invention can be used, for example, as wallpaper, backing paper for wallpaper, and as a material for honeycombs for fireproof panels.

It can be used for various flame retardant purposes, such as as an exterior covering for glass wool insulation materials, and as an alternative material to asbestos, which is a concern for health problems.

(Prior art) Conventionally, flame-retardant paper has been made by coating or impregnating paper using ordinary valves with various flame retardants, or by replacing part of the valve with non-flammable or flame-retardant organic or inorganic fibers or Instead of powder, flame retardancy was imparted as a material containing an inorganic material.

(Problems to be Solved by the Invention) However, bulb paper coated with or impregnated with flame retardant burns out when it comes into contact with flame, and when non-flammable or flame-retardant fibers or powders are used, paper-making properties are reduced. In order to maintain the paper, it was necessary to use a considerable amount of bulbs, and once the bulb components were burned off, there were disadvantages such as the inability to maintain the paper shape. In particular, when aluminum hydroxide is used as the nonflammable substance, it has not been possible to obtain a product that contains a high proportion of aluminum hydroxide and that can maintain its shape even after the combustible components used in combination have been burned off.

When such paper is used as a backing paper for wallpaper, etc., and a flame retardant test is performed, it is found that it does not have enough resistance to support the decorative layer on the surface. There were inconveniences such as peeling or falling off before or during combustion.

(Means for Solving the Problems) The present inventors solved the above-mentioned drawbacks and provided wallpaper with active fire-retardant performance, that is, it retains its shape even after the organic matter decomposes and exhibits fire-retardant performance. The present invention was achieved as a result of extensive research aimed at developing such flame-retardant paper. That is, 9 the present invention uses a combination of hydration-swellable minerals and inorganic fibers to reduce the aluminum hydroxide component to 50 to 50%.
A flame-retardant paper and a method for producing the same, characterized in that it contains a large amount such as 90% by weight, is rich in various post-processing properties, and can maintain its shape even after a flame combustion test according to JIS A-1322. Regarding. The manufacturing method includes, for example, 5 to 30 parts by weight of cellulose fibers, 1 part by weight of inorganic fibers,
-10 parts by weight, 1 to 10 parts by weight of a hydrated swelling mineral, 50 to 95 parts by weight of aluminum hydroxide, and 2 to 10 parts by weight of an organic binder, and optionally a flocculant and other various additions for paper making. For example, a method may be mentioned in which paper is made from a dispersion of a mixture of agents and dispersed in water using a wet paper making method or a method similar thereto.

9. The wet paper-making method or similar method used to produce the flame-retardant paper of the present invention refers to, for example, a belt-shaped, cylindrical, or square-shaped filter net, filter cloth, or filter plate. After pouring the aqueous dispersion of each of the above-mentioned components onto the filtration medium, or sandwiching the dispersion between these filtration media, it is filtered by, for example, natural filtration or vacuum filtration to form a sheet. It is a general term for methods of

The cellulose fibers used in the present invention include:
For example, Kotton linter valve, bleached sulfide valve (NBSP, LBSP), bleached craft valve (NBK)
P, LBKP), dissolving valve (DP), rayon, hemp, etc.

Examples of the fish fiber used in the present invention include glass fiber and micro glass wool.

Rock wool, mineral cotton, alumina silica fiber, alumina fiber, mullite fiber, boron fiber 2-quartz fiber, silicate glass fiber, fused silica fiber, potassium titanate fiber, zirconia fiber,! Fibrous materials include, but are not limited to, calcium acid fibers, phosphate fibers, borosilicate fibers, carbon fibers, and activated carbon fibers, and one or more of these inorganic fibers may be used as appropriate. Select and use. Among these, fiber diameter.

It is practical to use glass fiber because the fiber length is relatively uniform and the cost is low.

In addition, aluminum hydroxide is the main component of the papermaking process of the present invention, and when the papermaking process is exposed to high temperatures, it releases hydrated water to suppress the temperature rise and combustion of the papermaking and surrounding areas, and even after releasing the water. Hydration-swellable minerals, which remain as a main constituent of papermaking in the form of a heat-resistant substance called aluminum oxide, are inorganic compounds with a crystal structure in which crystal unit cells are repeated in the thickness direction.

It is a general term for minerals that have the property of drawing water molecules between crystal layers and swelling, and at the most developed stage of swelling, the crystals collapse into ultrafine particles and form a stable sol in water. These hydration-swellable minerals have the property of solidifying when dried, and function as a binding substance for inorganic fibers and inorganic filler, whose main component is aluminum hydroxide, giving papermaking flexibility.

It exhibits paper-making shape retention performance even after exposure to high temperatures.

It is something. Examples of such hydration-swellable minerals include the bentonite group (e.g., colloidal bentonite, modified bentonite, colloidal sodium montmorillonite, etc.)
, natural products such as mountain bark, and synthetic products such as hydration-swellable mica groups (e.g., sodium tetrasilisicumite, sodium or lithium taeniolite, sodium or lithium hectorite, etc.), but are limited to these. isn't it.

In addition, the organic binder mainly contributes to the bonding between cellulose ams and provides flexibility and strength to the paper. Organic binders 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, and paper strength agents such as methyl cellulose, ethyl cellulose, and hydroxyethyl cellulose. , maleic acid neutral sizing agent, rosin-based sizing agent, oil-based sizing agent.

Examples include polymer resin emulsions, sizing agents such as rubber latex, and the like.

In addition, the flocculant aggregates aluminum hydroxide and other inorganic fine particles into a particle size suitable for paper making.

Polyacrylamide-based flocculants are particularly suitable for the present invention, which is effective in improving the yield during papermaking, and whose main component is aluminum hydroxide.

In addition to the above-mentioned essential components, various additional components commonly used in paper making can be used in combination without impairing the purpose of the present invention.

Examples of such additives include various synthetic fibers such as polyamide fibers, polyester fibers, and polyolefin fibers, anionic polymers (e.g., sodium polyacrylate, salts of polyacrylamide and its partially hydrolyzed products, and maleic acid copolymers). salt).

Polymer flocculants such as cationic polymers (e.g., partial hydrolyzate of polyacrylamide), nonionic polymers (e.g., polyacrylamide, polyvinyl alcohol, polyethylene oxide), or egg white, yellow mallow, and octa fruit. Thready polymer flocculants such as natural stringy polymers such as mucus, modified bentonite, and fluorinated oil-resistant agents.

Examples include a mold release agent, a silane coupling agent, a silicone-based water return agent, sulfuric acid peroxide, sodium aluminate, polyphosphoric acid, and ammonium polyphosphate.

Furthermore, an inorganic filler may be used in combination as long as it does not contradict the purpose of the present invention. Examples of inorganic fillers include silica stone, silica sand, diatomaceous earth, kaolin, halloysite, montmorillonite, hentonite, zeolite, phosphate rock,
diasbore, gibbsite, bauxite, acid clay,
Natural inorganic substances such as pottery stone, waxite, feldspar, limestone, wollastonite, gypsum, F lomite, magnesite, talc, water-insoluble metal hydroxides such as magnesium hydroxide and calcium hydroxide, and silica such as tobermonite and sonodride. Hydrates of various oxides such as acid calcium hydrates, calcium aluminate hydrates, calcium sulfoaluminate hydrates,
Synthetic inorganic materials such as 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, titanium oxide, late potassium titanium, etc. Examples include powders such as, or fine fibrous materials having a length of approximately less than 10 μm. Note that whisker-like substances, scale-like substances, flake-like substances, etc. are also included.

A method for producing the flame-retardant paper of the present invention using the above-mentioned various components includes, for example, 5 to 30 parts by weight of cellulose fibers and 1 to 10 parts by weight of inorganic fibers.

1 to 10 parts by weight of hydrated swelling mineral, 5 parts by weight of aluminum hydroxide
0 to 95 parts by weight of an organic binder and 2 to 10 parts by weight of an organic binder are essential components, and if desired, a flocculant and other various additives for paper making are mixed and dispersed in water, and a dispersion is prepared by a wet paper making method or a method similar thereto. paper can be obtained by

The strength of the paper obtained when cellulose fibers are less than 5 parts by weight among the components of the dispersion.

The flexibility is insufficient, making post-processing and other handling difficult, making it impractical, and if the amount exceeds 30 parts by weight, the shape retention after the fiber is burned off by exposure to high temperatures is insufficient, so the present invention does not meet the purpose of

Furthermore, if the amount of inorganic fiber is less than 1 part by weight, the shape retention after the cellulose fibers are burned off by exposure to high temperatures will be insufficient, and if it exceeds 10 parts by weight, the surface smoothness of the paper will be poor, making it difficult to make paper. It is not practical enough.

In addition, if the amount of hydration-swellable minerals is less than 1 part by weight, the bond between inorganic fibers or with aluminum hydroxide and other inorganic fillers is insufficient, resulting in paper being exposed to high temperatures and cellulose fibers being burned off. The purpose of the present invention is not met because of insufficient shape retention. or.

If it exceeds 10 parts by weight, dewatering properties will be reduced and paper making will not proceed smoothly.

In addition, aluminum hydroxide is the main component of the papermaking process of the present invention, and when papermaking is exposed to high temperatures, it releases hydrated water and suppresses the rise in temperature of the papermaking and surrounding areas. It remains as a main constituent of papermaking in the form of a heat-resistant substance called . In the paper making of the present invention, if the aluminum hydroxide content is less than 50 parts by weight, the desired flame retardance cannot be achieved, and if it exceeds 95 parts by weight, the aluminum hydroxide component in the paper produced is undesirable because it becomes too large and lacks cellulose fibers, inorganic fibers, and other constituent components, resulting in insufficient strength for paper making.

In addition, in the paper making method of the present invention, the organic binder is mainly used between cellulose fibers or between cellulose fibers! l! It contributes to the bonding between iI and other components, and it is preferable to use 2 to 10 parts by weight. If it is less than 2 parts by weight, the binding effect will be insufficient and the strength of the paper will be weak, resulting in tearing and bending during post-processing and other treatments, making it impractical. Moreover, if it exceeds 10 parts by weight, the flame retardance will decrease, making it unsuitable for the purpose of the present invention.

When using a flocculant, it is preferable to use approximately 100 to 600 ppm. If the amount is less than loOppm, the aggregation effect will not be sufficiently exhibited and the yield will decrease, which is disadvantageous in terms of cost and productivity. or.

If it exceeds 600 ppm, the cohesive force becomes excessive, and as a result, fine particles such as aluminum hydroxide become coarse and pinholes occur frequently in paper making, which is not preferable.

(Function and Effect) The flame-retardant paper produced as described above is exposed to high temperature,
Alternatively, when exposed to flame, it releases hydrated water to suppress the rise in temperature of the papermaking and surrounding areas, and even after the water is released, it remains as a main component of papermaking in the form of a heat-resistant substance called aluminum oxide.

It is thought that the aluminum oxide, inorganic fibers, hydrated minerals, and other inorganic additives contribute to shape retention. Such shape retention is formed by a network structure formed by inorganic substances, that is, hydration-swellable minerals adhere to the contact points between inorganic fibers and the contact points between inorganic fibers and secondary agglomerated particles of aluminum hydroxide. . This is thought to be due to the presence of a relatively small amount of inorganic fibers and hydration-swellable minerals, which results in shape retention performance.

Although the mechanism by which this performance is demonstrated is not necessarily clear, an inorganic network structure is formed that three-dimensionally overlaps with the organic network structure in paper 9, and the inorganic network structure is responsible for maintaining the shape after the organic matter decomposes. It is speculated that this may be the case. It is also possible that shrinkage due to decomposition and dehydration due to heat may affect the strength of the inorganic network structure.

(Example) The present invention will be explained in more detail with reference to Examples below.9
The present invention is not limited to these.

Example 1 5 parts by weight of wood bulbs (NBKP) were dispersed in 1000 parts by weight of water, beaten to about 25°SR, and then glass fibers (3 ms x 6 μΦ) were added.

Nitto Boseki Co., Ltd. 5 parts by weight Hydration-swellable mineral (Hane) 3 parts by weight Aluminum hydroxide 95 parts by weight Acrylic resin (7'-IIA-IQ)

(manufactured by Nippon Acrylic Co., Ltd.) 21 Abe flocculant (Himoloku-8゜ manufactured by Kyoritsu Organic Co., Ltd.) 400 ppm was added and dispersed, and this dispersion was made into paper using a Fourdrinier paper machine to make 9 tsubo ff.
A paper of i 100 g/m' was obtained. The content of aluminum hydroxide in the flame-retardant paper was measured by atomic absorption spectrometry and was found to be 86 times over.

This paper was heated with a Metzkel burner for 3 minutes using liquefied petroleum gas No. 5 as fuel in accordance with J15-A-1322 (Testing method for flame retardancy of thin materials for construction). There was no flame bleed through during heating, and the sample after heating remained sheet-like without any holes.

In addition, vinyl chloride sol (1
35-J, manufactured by Nippon Zeon Co., Ltd.) in terms of solid content of 14
A decorative sheet was prepared by applying 0 g/Trf. This sheet was attached to a noncombustible base material (perlite board with a thickness of 10 mm), and a surface test was conducted according to JIS A-132'1 (Flame retardancy test method for building interior materials and construction methods). During the test, the PVC decorative surface did not fall off the surface until it was carbonized.

The part of the paper made from paper did not peel off and remained as it was, maintaining the shape of the paper.

Furthermore, the same paper was used as a backing paper, and on top of that, a sheet of 200 g / rrr (
The woven fabric D was coated with vinyl acetate adhesive (Konishi Bond CH-18).
, manufactured by Konishi Co., Ltd.) and subjected to a surface combustion test using the method described above, the woven fabric did not peel or fall off from the backing paper until it was carbonized, as in the case of the vinyl chloride decorative layer. Ta.

Example 2 The composition of the dispersion in Example 1 was changed to wood bulb (NBKP), 7 parts by weight of glass fiber (3 m x 6 μφ).

(manufactured by Nittobo Co., Ltd.) 5 parts by weight of hydration-swellable minerals (Hentite) 3 parts by weight of aluminum hydroxide 80 parts by weight of titanium oxide
10 parts by weight of acrylic resin (Blymarl HA-16) 3 parts by weight of coagulant (Himolok-5) Same as Example 1 except that the amount was changed to 400 ppm.Flame-retardant paper with tsubo fft of 100 g/l/ was prepared in the same manner as in Example 1. was manufactured.

The content of aluminum hydroxide in this flame-retardant paper is 73
% by weight.

When this paper was subjected to a flame combustion test in the same manner as in Example 1, there was no flame bleed through during heating, and the sample after heating remained sheet-like without holes.

Further, in the same manner as in Example 1, vinyl chloride sol (135-J
) was applied at 140 g/m' to prepare a decorative sheet.

This sheet was subjected to a surface test according to JIS A-1321 (Flame retardant test method for building interior materials and construction methods). During the test, the PVC decorative surface did not fall off the surface until it was carbonized.

The paper-making portion did not peel off and remained as it was, maintaining the paper-making shape.

Example 3 In Example 2, the dispersion composition was wood bulb (NBKP) 15 weights 1 part glass fiber (3×6 μφ).

Nittobo Co., Ltd.) 5 parts by weight 3 parts by weight 60 parts by weight 10 parts by weight Mountain bark aluminum hydroxide Titanium oxide SBR (SNX-3484° manufactured by Naugatuck Co., Ltd.) Sumitomo 10 parts by weight Flocculant (High [Rowku 12MLH)] 400p
A 100 g/I flame-retardant paper was produced in exactly the same manner as in Example 1, except that the pm was changed.

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

In addition, this paper was used as a backing paper, and vinyl chloride sol (135-J) was applied as a decorative layer on the surface of the paper at 140 g/solid content.
A decorative sheet was prepared by applying "Wi". When this sheet was subjected to a surface combustion test according to JISA-1321 in the same manner as in Example 1, the vinyl chloride decorative layer fell off from the surface during the test until it carbonized. The paper-making portion did not peel off and remained as it was, maintaining the paper-making shape.

Comparative Example 1 In Example 1, no hydration-swellable mineral was used in the dispersion composition, and wood bulbs (NBKP) were prepared using 7 parts by weight of glass fibers (3 m x 6 μΦ).

(manufactured by Nittobo Co., Ltd.) 5 parts by weight Aluminum hydroxide 80 parts by weight Titanium oxide fine powder 10 parts by weight Acrylic resin (00 Reimall HA-16) 2 parts by weight Coagulant (Himorok-5) Same as the example except that it was 400 ppm. A 100 g/yn' flame-retardant paper was produced in exactly the same manner.

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

When this paper was subjected to a flame combustion test in the same manner as in Example 1, the flame bleed through during heating, and the sample after heating had holes and could not maintain its sheet shape.

Also, in the same manner as in Example 1, vinyl chloride, ru(135-J)
A decorative sheet was prepared by applying 140 g/m' of the following. This sheet was attached to a noncombustible substrate in the same manner as in Example 1, and a surface test was conducted. During the test, the backing paper part peeled off, the PVC decorative layer and a part of the paper fell off, and the base material was exposed.

Comparative Example 2 Wood bulb (NBKP) 7 parts by weight Glass fiber & 1t (3+wX6μφ) 0.5 parts by weight Partly hydrated swelling mineral (Hent t()) 0.5 parts by weight Aluminum hydroxide 80 parts by weight Titanium oxide
10 parts by weight of acrylic resin (0L7-L HA-16) 2 parts by weight of flocculant (Himorock)
5) A 100 g/n/flammable paper was produced in the same manner as in the example except that the content was 400 ppm.

The content of aluminum hydroxide in the obtained paper was 72% by weight. This paper was subjected to a flame heating test in the same manner as in Example 1, but unlike in Example 1, the flame bleed through during heating, and the sample after heating had holes and could not maintain its sheet shape. Ta.

Separately, 150 g/tn' of vinyl chloride sol (135-J) was applied as a decorative layer to this paper in the same manner as in Example 1 to prepare a decorative wallpaper.

This wallpaper was attached to a noncombustible base material and a surface test was conducted in the same manner as in Example 1. As in Comparative Example 1, the PVC decorative layer and a portion of the paper fell off during the test, exposing the base material.

Comparative Example 3 The composition of the dispersion in Example 1 was changed to 7 parts by weight of a wood bulb (NBKP) that does not use any inorganic fibers, 7 parts by weight of a hydration-swellable mineral (Höhnnite), 3 parts by weight of aluminum hydroxide, 80 parts by weight of polyester fibers (
EP-202X5 Kuraray Co., Ltd.) 10 parts by weight acrylic resin (
) 0 Reimall HA-16) 2 parts by weight of flocculant (Himolok-5) A flame-retardant paper having loOg/m' was produced in exactly the same manner as in the example except that the amount was changed to 400 ppm.

The content of aluminum hydroxide in the obtained paper was 74% by weight. This paper was subjected to a flame heating test in the same manner as in Example 1, but the sample after heating had holes and could not maintain its sheet shape.

Separately, vinyl chloride sol (135-
J) was applied at 150 g/rrr to prepare a decorative sheet.

This sheet was attached to a noncombustible base material in the same manner as in Example 1, and a surface test was conducted. During the test, the PVC decorative layer and a portion of the paper fell off, exposing the base material.

Claims (3)

[Claims] (1) A flame-retardant paper containing 50 to 90% by weight of an aluminum hydroxide component and capable of retaining its shape even after a JISA-1322 flame heating test. (2) When producing flame-retardant paper containing aluminum hydroxide as a main component, 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 hydration-swellable minerals, and aluminum hydroxide. 50-95 parts by weight, organic binder 2
The flame-retardant paper according to claim 1, wherein the paper is made from a dispersion in water of a mixture containing up to 10 parts by weight of essential components by a wet paper-making method or a method similar thereto. (3) When producing flame-retardant paper containing aluminum hydroxide as a main component, 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 hydration-swellable minerals, and aluminum hydroxide. 50-95 parts by weight, organic binder 2
A method for producing flame-retardant paper, which comprises producing a dispersion in water of a mixture containing up to 10 parts by weight as an essential component, by a wet papermaking method or a method similar thereto.