JP3061886B2 - Flame retardant cone paper - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to cone paper used for a diaphragm of an electroacoustic transducer such as a speaker, and more particularly to a flame retardant cone paper having flame retardancy.

[0002]

2. Description of the Related Art In order to make highly flammable cellulose fiber paper flame-retardant, a flame-retardant solution of an inorganic phosphate, which is said to be effective in a small amount on cellulosic fibers after forming the paper, is used. The method of impregnation is most common. However, in this processing method, the impregnating liquid containing the flame retardant does not easily penetrate the size paper, the high-density paper, or the corn paper adopting the press-dry method for drying, and the self-extinguishing property cannot be maintained. extremely difficult.

[0003] Cone paper dried at a high temperature by the press-drying method is similar to a honeycomb structure, so that the density of the formed paper is much higher than that of the inside, and even if the paper is impregnated with a flame retardant solution. It only penetrates the surface and is not evenly impregnated into the interior. Therefore, the fire remains in the paper layer and does not become completely self-extinguishing. Further, if the size is given, the impregnating liquid containing the flame retardant does not easily penetrate. Paper impregnated with an inorganic phosphate compound, which is generally said to be optimal for flame retardancy of cellulose fiber paper, is brittle, has low strength, does not have a low elongation and does not have toughness. Vibration can lead to destruction. When the paper impregnated with inorganic phosphate is placed in a hot and humid environment, a part of it is hydrolyzed, releasing free phosphoric acid and causing mold in a short period of time. Corrosion of the fine wire also occurs, which may lead to a disconnection regarded as a fatal defect.

[0004] Cone paper used for a speaker is heavy (100 g / m ² or more) because of its stiffness stiffness, which is different from ordinary paper, newsprint and corrugated cardboard.
Low freeness (500 cc or more CSF = Tanada Standard Freeness) in density is low (0.5 g / m ³ or less), therefore rigid, surface is rough, not suitable for such printing, there specificity among paper It is. In particular, the cone part and the edge part are the same wood pulp,
Moreover, in the case of fixed corn paper, which is made of the same low beating degree material, the weight and density of the edge portion and the cone portion are greatly different. The weight of the edge part (basis weight: 20 to 50 g / m ² ) of a typical fixed corn paper (80 to 160 mm in diameter) is free corn (Free
Cone) The weight of the cone equivalent to paper (basis weight: 120 to 16)
0 g / m ² ), which is extremely light and has a low density, so that its strength is usually weak. If a solid material such as an inorganic phosphate flame retardant is impregnated into an edge portion having no such strength, the edge portion becomes more brittle, the strength is reduced, and the toughness (strength Kg / m
(m ² × elongation%), and easily breaks when stress is repeatedly applied, that is, when subjected to forced vibration.

As described above, the edge portion has the lowest resonance frequency F
Since the weight is light and the degree of beating is low in order to reduce 0, the dewatering pressure during papermaking is not applied, the water content is reduced, and the density is extremely reduced. Therefore, the contact area with air is larger than that of the cone part, and even if a large amount of the inorganic phosphate flame retardant is impregnated, the impregnation rate is low, and it is difficult to make the flame retardant. The fired corn paper flame-retarded for these reasons does not yet exist.

Even if flammable cellulose fiber paper is treated with a flame retardant so as to easily penetrate it, it is difficult to obtain a paper having uniform flammability because the cellulose fiber has a strong flocking property and thus has a large variation in density. It is very difficult, and it is impossible for quality assurance. It is more reliable to use a flame-retardant fiber to form a paper matrix. For these reasons, Nissan Chemical Industries (trade name: Go-cut), Sumitomo Chemical Industries (trade name: Sumisafe), etc., which have supplied phosphate compounds as flame retardants for papermaking, have all discontinued their products.

Further, even if the flame retardant cellulose fiber paper is required to have heat resistance, it does not fall out of the performance range of the cellulose fiber.
It has only a durability of around 180 ° C for a short time. Therefore,
Cone paper having both flame retardancy and heat resistance needs to have the properties from the beginning due to the fiber material used.
Highly elastic carbon fiber as a fiber with such properties,
There was also corn paper made by blending glass fibers and the like with wood pulp, but all were only partially added in consideration of the reduction in paper strength, and only had a blending rate of about 5 to 10%. It is difficult to maintain flame retardancy, and heat resistance is almost impossible at present. Also, it is difficult to obtain an internal loss which is important for speaker cone paper emanating from the frictional resistance between fibers.

[0008] Flame retardation by impregnating cellulose fiber paper with an inorganic phosphate compound has problems such as deterioration of mechanical strength, generation of mold, and corrosion to metal. On the other hand, when a fiber paper is formed using flame-retardant fibers, how to raise the strength is a major issue. The method for increasing the mechanical strength of the flame-retardant fiber paper is described below.

The mechanical strength of the paper-like matrix is determined by the sum of the strength of a single fiber of the fibers constituting the network and the contact area between fibers (bonding strength between fibers). Ideally, a fiber material having a high fiber strength and a high fiber-to-fiber adhesive strength would be ideal, but none of them satisfy both. Cellulose fibers have lower fiber strength than synthetic inorganic and organic fibers, but have higher inter-fiber adhesion strength. Therefore, if there is a fiber material having the same strength as that of carbon fiber as well as the adhesive strength of wood pulp, heat resistant paper having excellent mechanical strength can be obtained. If the single fiber strength is high and there is no cut surface, that is, if the length of the fiber is long, the contact area increases and the density increases, resulting in a strong paper-like matrix. Therefore, in order to obtain a strong paper-like matrix, the fiber length of the cut fiber is increased to the extent possible to form a paper, and the inter-fiber contact area is increased even when a fibrillated fiber substance having a large specific surface area or a short milled fiber is blended. It is to increase the density by increasing the surface tension of water, increase the strength of the web (composite of fiber and water), and increase the drying strength.

In fact, in the case of chemical fibers other than cellulose fibers, if the fiber length is long, the density of the paper-like matrix is reduced. Therefore, fibrillated fibers or fibers are finely pulverized mechanically in the spaces between these fibers. A method of increasing the density by filling the milled fiber is adopted. In addition, there is a method in which an adhesive substance such as a resin emulsion or a rubber latex is added for adhesion. The internal loss (Tanδ) of the paper matrix increases in proportion to the contact area between the fibers, and is affected by the chemical structure of the fibers used and the shear rate (frequency) between the crystals. 0.02 or more is required. Paper that forms a network of cellulosic wood pulp
It has strong polar hydroxyl groups (-OH) on the fiber surface and forms strong hydrogen bonds between the fibers upon contact, forming a stronger network. It is clear from the above theory that the efficient way of increasing the strength of the network is that fibrous binders that have both a fiber shape and an adhesive function are more advantageous than fibers with high strength or additives that have only adhesive performance. That is.

An aromatic polyamide, imide-based fiber, polybenzimidazole fiber, organic sulfur-containing fiber, phenol fiber, or other general-purpose flame-retardant fiber (flame-retardant fiber such as rayon, vinylon, polyethylene terephthalate, or polypyroprene) is used for the fiber length. Even if the paper is cut into 0.5 to 10.0 mm and dispersed in water to form a slurry, the paper is never obtained, and the paper alone is not practically used. This has a specific surface area of 0.2 compared to wood pulp.
This is because it is as small as 4 m ² / g or less, the surface does not have a strongly polar hydroxyl group, and no hydrogen bond is established.

[0012] Therefore, in order to form a paper, a binder is required to bind the fibers more strongly. Generally, paper-like substances (including non-woven fabrics) are made of such synthetic fibers having a small specific surface area.
When paper is made, a widely used fibrous binder is a hot-water-reactivated polyvinyl alcohol fiber containing a large amount of hydroxyl groups (in this case, poval fiber with a low degree of saponification).
Then, a cut fiber obtained by cutting this into 2-3 mm is added to a synthetic fiber to obtain a fibrous binder.

[0013]

In order to achieve the above object, the flame-retardant cone paper of the present invention comprises an aromatic polyamide, imide-based fiber, organic sulfur-containing fiber, polybenzimidazole having flame retardancy and heat resistance. Fiber, phenol fiber or other flame-retardant general-purpose staple fibers as the main fiber, and finely fibrillated aromatic polyamide fiber as a fibrous binder into pulp-like fibrous fibers, or mechanically pulverized Ultra-beaten milled fiber and wood pulp 10.
It is made by adding a binding fiber such as ultra-beaten wood pulp having a specific surface area of 0 m ² / g or more, has flame retardancy and heat resistance, has moisture resistance and water resistance, and has high strength and high strength. It is characterized by having elastic modulus and high internal loss.

The present invention has been made in view of the above points, and has as its object to have flame retardancy and heat resistance, have moisture resistance and water resistance, and have high strength and high strength. An object of the present invention is to provide a flame-retardant cone paper having an elastic modulus, a high internal loss, and excellent mass productivity.

[0015]

In order to achieve the above object, the flame-retardant cone paper of the present invention comprises an aromatic polyamide, imide-based fiber, organic sulfur-containing fiber, polybenzimidazole having flame retardancy and heat resistance. Fibers, phenol fibers or other flame-retardant general-purpose staple fibers as the main fibers, and pulp-like fibrous fibers obtained by finely fibrillating aromatic polyamide fibers as fibrous binders, or mechanically pulverized It is made by adding milled fiber and binding fiber such as ultra-beaten wood pulp obtained by ultra-beaten wood pulp, has flame retardancy and heat resistance, has moisture resistance and water resistance, and has high strength and high strength. It is characterized by having an elastic modulus and a high internal loss.

In order to achieve the above object, the flame-retardant corn paper of the present invention comprises an aromatic polyamide, an imide compound, an organometallic polymer compound having flame retardancy and heat resistance, Impregnated with a solution such as an inorganic compound or flame-retardant resin as an impregnating agent, and coated to further improve various properties such as high flame retardancy, heat resistance, water resistance, and humidity resistance, and have high strength and high elasticity. It is a flame-retardant cone paper with a high internal loss and a fiber with a heat-softening point.It is characterized by improving the strength and elastic modulus of the fiber paper by hot pressing at that temperature. Have.

[0017]

[Function] Aromatic polyamide, imide-based fiber, polybenzimidazole fiber, organic sulfur-containing fiber, phenol fiber, excellent in physicochemical properties such as high elastic modulus, high strength, heat resistance, and high flame retardancy with high limiting oxygen index Alternatively, a fiber length of 0.5 capable of forming a flame-retardant general-purpose fiber (a flame-retardant fiber such as rayon, vinylon, polyethylene terephthalate, or polypropylene).
~ 7.0mm, and to increase the fiber contact area and the filling rate between fibers, add fibrillated fibers and milled fibers to increase the density to increase the web strength,
By further adding 0.5 to 30% of ultra-beaten wood pulp, which is a fibrous binder, in order to further increase the inter-fiber adhesion strength,
Realizes strong web strength and dry strength, and achieves weight (basis weight g /
Even if m ² ) is light, fiber paper having strong strength can be obtained.

In particular, even among aromatic polyamide fibers, meta-based fibers have a lower elastic modulus and higher elongation than para-based fibers, so they are supple, have good web-forming properties (consolidation properties), and have good cut properties. When combined with fibrillated fibers (fibrit fibers), thin and strong fiber paper can be formed. Since the strength of the meta-based fiber is high and the elongation is large, even if it is made into a paper, its fiber properties are also reflected in the fiber paper, and the paper becomes supple and tough. As described above, fixed cone paper (Fixed Cone) having a thin edge can be formed, and the edge becomes a thin, strong, stretched edge, withstands repeated stress, and has an increased input resistance. In particular, the elongation is greater than 1% of wood pulp paper and about 4% or more. Such properties are difficult to obtain with cellulose fibers impregnated with a flame retardant.

[0019]

EXAMPLES In order to further improve the inter-fiber bond strength and elastic modulus of fiber paper, the following method is employed. 1. Impregnating or coating fiber paper with a solution of organic aromatic polyamide, imide compound, organometallic polymer compound, inorganic compound (silicate compound), flame retardant resin (flame retardant), etc., which has both flame retardancy and adhesiveness I do. Thereby, various properties such as heat resistance, flame retardancy, water resistance, and humidity resistance are simultaneously improved. 2. Some fibers have a softening point even with flame retardant fibers,
For example, a meta-aromatic polyamide fiber paper or a fiber paper partially containing the fiber has a softening point around 350 to 400 ° C., and therefore, when pressed at this temperature, the density is improved and the fiber paper strength is increased. Get higher. 220 ° C for polyethylene terephthalate fiber, 16 for polypropylene fiber
There is a softening point at 0 ° C or the like. 3. The meta-aromatic polyamide fiber paper itself swells and plasticizes with a strong polar organic solvent (dimethylformamide = DMF, tetrahydrofuran = THF, dimethylacetamide = DMAc). When hot pressing is performed, the contact area between fibers increases, and the strength is further improved.

Next, the fiber material and the impregnating agent used in the present invention will be described. The limit oxygen index (LOI = Linite)
d Oxygen Index) is the catalog value of the manufacturer. still,
The LOI of the cellulose fiber is 16 to 18, and the flame retardancy, that is, the value called self-extinguishing property (UL94 standard V = 0 or more) is 25.
That is all. Therefore, if fiber paper is made using fibers having an LOI of 25 or more, it can be a flame-retardant fiber paper.

Cut fiber The fiber bundle (yarn) of the long fiber is fixed with a sizing agent,
Cut to 7 mm. This is used as a basic fiber of synthetic paper.
In general, polyvinyl alcohol (PVA) is used as a sizing agent, so that a surfactant, an antifoaming agent, and the like are added at the time of papermaking to improve the wetting with water.

(Limit oxygen index / softening point ° C) Fiber name Manufacturer and trade name a. Aromatic polyamide fiber Para system: Dupont Toray Kevlar "Kevlar 29,49,149" (29): Sumitomo Chemical "Twaron" (29) Meta: Dupont Toray “Nomex” (31) Teijin “Cornex” (33/350) Unitika “Apier” (33/350) b. Aromatic polyetheramide fiber: Teijin “Technola” (25) c. Aromatic Polyetherimide fiber: Teijin "PEI" (47/340) d. Polybenzimidazole fiber: Teijin "Tenzan PBI" (42) e. Aromatic polyamideimide fiber: Rhone-Poulin "Kermer" (32) f. Holiparafe Nilenbenzbisthiazole fiber: USA Air Force () g. Polyethersulfon fiber: () h. Polyphenylenesulfon fiber: Teijin "PPS" (35/285) i. Phenyl fiber: Gunei Chemical "Kynol" ( 31) j. Polyetheretherke Fiber: Teijin “PEEK” (35/335) k. Aromatic polyimide fiber: Ube Industries “” () l. Flame retardant rayon fiber: Daiwabo “flame retardant rayon” (32) m. Flame retardant vinylon fiber : Kuraray “PBX” (35) n. Flame retardant polyethylene terephthalate fiber: Teijin “Fire retardant tetron” (32/220) o. Flame retardant polypropylene fiber: Chitso “Chitso polypro” (30/160) Nitrogen, sulfur, etc. Are heat-resistant and flame-retardant, but there are many fibers that have been made flame-retardant by mixing a conventional general-purpose fiber with a flame retardant. Neither is common for papermaking.

Milled Fibers and Fibrillated Fibers Milled fibers are obtained by mechanically pulverizing fiber offcuts such as long fibers, short fibers, cut fibers and the like, and woven offcuts into fine powder (milled). Cut fiber 1-7m when making fiber paper
When only m is used, the water content is low and the surface tension of water does not work between fibers, so that the web strength is low. Therefore, transfer cannot be performed from the paper net. Milled fibers and fibrillated fibers are added as fillers for cut fibers to increase the density and water content of the webs and to increase the strength of the webs by using the surface tension of water between the fibers. The ratio is 20 to 50% with respect to the cut fiber, and if it is more than this, the strength is reduced. Naturally, the web strength also affects and improves the dry strength.

The fibrillated fiber can be finely fibrillated by dissolving the fiber material in an organic solvent and jetting the fibrous material into a non-solvent at a high speed to increase the specific surface area. The specific surface area can be further increased depending on the type of the non-solvent. This method was developed by Dupont "Nomex" and is marketed under the trade name "Fibrit" and is hereinafter referred to as fibrit fiber. This can be used in a similar manner to the milled fibers to increase the density of the fiber paper. Since the specific surface area is larger than that of the milled fiber, it is effective in improving the strength of the fiber paper.

A. Aromatic polyamide milled fiber manufacturer Dupont Toray Kevlar "Kevlar pulp" Teijin "Technola pulp" b. Fibrillated fiber (fibrillated fiber) manufacturer Teijin "Cornex pulp" Unitika Pierre Pulp "Dupont" Fibrit 101,102 "

Ultra-beaten wood pulp Wood pulp in the wet state (Wet) is pressed with high pressure into the gap between two cylinders having different diameters, and is beaten by rotating each other. Ultra-beaten down to submicron along the axis and its specific surface area is 200
m ² / g. This large specific surface area (10.0 m ² /
g) is added to short fibers of synthetic fibers (cut fibers, milled fibers, fibrillated fibers) to act as a fibrous binder and form a high-strength web, The strength is improved. In addition, because of its large specific surface area, it also acts as a dispersant in water, which helps to prevent sedimentation of inorganic fibers with high density and fibers with low buoyancy.

As the heat-resistant and flame-retardant impregnating agent, a resin or a compound having the following flame-retardant and heat-resistant properties is dissolved in each solvent, and impregnated with corn paper and coated.
Various properties such as heat resistance, flame retardancy, water resistance, and humidity resistance can be improved to high performance.

A. Aromatic polyamide and imide compounds The corn paper after press drying is impregnated with the following resin solution, and the polyamic acid-type compound is cured at a high temperature. Representative product names and manufacturing companies are noted. Each of them has flame retardancy, and the heat resistance of polyimide is the highest, and the order of polyamide imide, polyamide and polyester imide is as follows.

Compound name Manufacturer and trade name 1. Aromatic polyamide compound Unitika “Apier Varnish” 2. Aromatic polyimide compound Toray “Trenez”, Dupont “Pile”, Mitsubishi Gas Chemical “BT resin” 3. Aromatic polyamide Imide compounds Hitachi Chemical "HI-400", Sumitomo Electric "Sumitherm", Amco "Amco AI-10" 4. Aromatic polyesterimide compounds Sumitomo Electric "Sumitherm F-555", Dainichi Seika "Telebec" 5.Aroma Aromatic polyester amide imide compound Westinghouse "Omega" 6. Aromatic polyhydatoin compound Sumitomo Bayer "Resiram PH-10" 7. Aromatic benzimidazole compound 8. Aromatic polybenzothiazole compound 9. Aromatic polypyromellitic imide compound 10. Silicone polyimide compound Shin-Etsu Chemical "JKR-651" 11. Polyparabanic acid compound Tonen Rack "

B. Organometallic polymer compound In the organometallic compound, silicon enters the main chain bond, and carbon,
A structure in which elements of nitrogen, titanium, and boron are combined. At high temperatures, organic substances disappear, metal components increase, and ceramics (metal oxide) is formed, giving heat resistance and flame retardancy.

Compound name Main chain structure Manufacturer and trade name 1. Organic silicon-containing compound a. Polysilane -Si-Si- Silicone oil, Silicone rubber, Silicone varnish b. Polycarbosilane -Si-C- Nippon Carbon "Nicarocoat""C. metal Arukokisshido compounds _{M (OR) n, M =} Ti, Si, Zr, Zn.R = -C n H 2n + 1 Si- (OC 2 H 5) 4, Ti- (OC 2 H 5) Compounds with a small amount of R and C, such as _4, are hydrolyzed in the air to become amorphous ceramics SiO ₂ and TiO ₂ , and have a heat resistance of 400 ° C. or more. Nippon Synthetic Rubber, Catalyst Chemicals, Nippon Soda 2. Organic Boron-Containing, Silicon Compound Borosiloxane -BO-Si- Showa Densen, "Borosiloxane" 3. Organic Titanium-Containing Silicon Compound Polytitanocarbosilane -Ti-Si- OC- Ube Industries "Titanocoat" 4. Organic nitrogen-containing, silicon compound polysilazane -N = Si (R) Tonen "Polysilazane" 5. Organic aluminum-containing, silicon compound polyaluminoxane -Al-O- Sumitomo Chemical 6. Organic fusophazene compound- N = P (OR) ₂ -Idemitsu Petrochemical, Dainichi Seika 7.Organosol a.Alumina sol b.Silica sol

C. Inorganic compound silicate compound Sodium, potassium, lithium salt, (Na, K, Li) ₂ Si
O ₃ primary reagent, especially lithium silicate (Li ₂ SiO ₃ , Li ₂
(O / SiO ₂ = 7.2-7.8 mol ratio), dried after impregnation, does not dissolve again in water, improves water resistance and humidity resistance, and has no loss on heating up to 1000 ° C.

D. Flame Retardant Resin (Flame Retardant) Although super-beaten wood pulp has been given flame retardancy and heat resistance, the aromatic polyamide, imide resin, organometallic polymer compound, inorganic compound (silicate) Compound), the heat resistance is slightly inferior.

1. Phenol resin and its modified resin Resol type Sumitomo Bakelite “PR-14170S”, Showa polymer “BRL-120” Novolac type Gunei Chemical Acrylic modified type Gunei Chemical cash register top “PL-4962” Urethane modified type Dainippon Ink and Chemicals Tung oil-modified Gunei Chemical register top "PL-4962" 2. Organic halogenated compounds Bromine compounds Decabromodiphenyl oxide (DBDO), Tetradiphenyl methane (TBA) Chlorine compounds Chlorinated polypro, chlorinated polyethylene , Chlorinated rubber Chlorinated phosphorus compound 3. Phosphorus compound Inorganic phosphorus compound Ammonium polyphosphate, Ammonium phosphate Organic phosphate ester compound Tricresyl phosphate, Tetrakis hydroxy phosphonium salts (cellulose reaction type) (Cellulose reaction type)

The corn paper of the present invention has flame retardancy (critical oxygen index).
25 or more), heat-resistant aromatic polyamide, imide-based fiber, polybenzimidazole fiber, organic sulfur-containing fiber,
Phenol fiber or other flame-retardant general-purpose fibers (rayon,
Vinylon, polyethylene terephthalate, flame-retardant fiber such as polypropylene fiber) and the like are cut into 0.5 to 10 mm short fibers, and as a fibrous binder, in order to increase the specific surface area of the aromatic polyamide fiber, it is once treated with an organic solvent. The fibrillated fiber produced by dissolving and jetting this at once into a non-solvent (ie, fibrit fiber, specific surface area)
4.0 m ² / g or more) and a fibrous binder such as ultra-beaten wood pulp (microfiber) whose wood pulp is mechanically super-beaten to increase the specific surface area to 10.0 m ² / g or more. Thus, the contact area between the fibers is increased to increase the strength of the network to obtain a tough fiber paper cone paper having high strength and high elongation. As a result, it has flame retardancy, heat resistance, excellent humidity resistance and water resistance, and a remarkable increase in frictional resistance between fibers due to the addition of a fibrous binder having a large specific surface area. It is a cone paper having a loss.

[0036] Fixed corn paper, which is impossible in the past, is also possible because of its high strength and toughness. If necessary, aromatic polyamides, imide compounds, organometallic polymer compounds, inorganic compounds (silicate compounds), and the like are used to improve various properties such as heat resistance, flame retardancy, water resistance, and humidity resistance. It can be impregnated with a solution of a flammable organic compound or the like.

The surface of the fibers has poor wettability with water,
Even if it is put into the water as it is, it does not blend with the water and floats on the water surface, and air bubbles easily adhere to the fiber surface, so that most of the fibers gather near the water surface as the stirring progresses. To prevent this, add a surfactant and an antifoaming agent to each
Add about 00 PPM to make a uniform slurry. This is made into a uniform fiber paper by papermaking. Moisture resistance and water resistance reduced by the addition of ultra-beaten wood pulp are improved by chemicals for papermaking.

1. Physical property measurement method Tensile strength: Calculated from the breaking strength of a tensile tester Tensile elasticity: Calculated from the 0.25% modulus of the stress-strain curve (SS-Curve) of the tensile tester Internal loss: Free torsion 1. Measured and calculated using a damping type viscoelasticity tester JIS K-7213 Heat resistance: Evaluated by weight loss after 400 ° C. + 2 hours Flame retardancy test method According to JIS D 1201 "Test method for flammability of organic materials for automobile interiors".

Example 1 A conex of a meta-aromatic polyamide fiber (Teijin fiber, fiber diameter: 1.5 De) was cut into 3 mm, and a fibril of the same meta-aromatic polyamide fiber was used as a fibrous binder. In addition, 0.5 to 50% was added, and ultra-beaten wood pulp (microfiber) obtained by ultra-beaten wood pulp was added.
Add 5-30% and dilute with water to 3% slurry,
Stir for 10 minutes with a disintegrator to completely disintegrate. A predetermined amount of a wet strength improver is added together with a papermaking agent to prevent the strength from dropping when wet, and the resulting paper is formed into a cone paper shape by an ordinary paper machine, and then dried by pressing to obtain a speaker cone paper. When the diaphragm obtained in the above experimental example was placed in a mold set at a mold temperature of 350 to 400 ° C. and molded under a pressure of 1 to 10 kg / mm ² , the meta-aromatic fiber was softened and the inter-fiber strength was increased. Improves to a strong fiber paper.

A. The following are used as the above fiber materials. Meta-aromatic polyamide fiber Short fiber 3mm × 1.5De 80 parts by weight (Teijin Cornex fiber 3mm × 1.5De, Unitika Apierre fiber 3mm × 1.5De) Meta-aromatic polyamide fiber Fibrillated fiber 20 parts (Teijin “Cornex” (Pulp) fibrillated fiber or Unitika "apier pulp" fibrillated fiber) 10 parts of ultra-beaten wood pulp (microfiber) b. The following chemicals are used for papermaking. Wet strength improver (epoxy polyamide resin) 1.5 parts Size (dimer acid ester) 0.5 parts Anionic surfactant 100 PPM Silicone defoamer 100 PPM Neutral PH: 6.5 c. It is as follows. The results are shown in Tables 1 and 2 of the attached sheets. d. Results of flame retardancy test Test method According to JIS D 1201 "Test method for flame retardancy of organic materials for automobile interiors". It does not reach the mark and is self-extinguishing.

Example 2 Para-aromatic polyamide fiber Kevlar 29, 49, 149 (Dupont
Toray Kevlar) short fibers (cut fiber length 0.5-10.0mm,
Ultra-beaten wood pulp (microfiber) obtained by ultra-beaten wood pulp as a fibrous binder to milled fiber Kevlar pulp having a fiber diameter of 1.5De) and mechanically crushed.
%, And if necessary, fibrillated fibers of meta-aromatic polyamide fibers are also added in an amount of 0.5 to 50%, and water is added thereto to make the pulp concentration 3%, and a uniform pulp slurry is obtained with a disintegrator. . To this is added a predetermined amount of a papermaking chemical, papermaking is carried out with a normal papermaking machine, and press drying is performed to obtain speaker cone paper. Compared with Example 1, since the single fiber strength and the elastic modulus are excellent, the elastic modulus and the rigidity are further improved, and the flame retardancy and the heat resistance are excellent.

A. The following are used as the above fiber materials. a-1 Para-based aromatic polyamide fiber Short fiber Kevlar 149 3mm × 1.5De 40 parts Para-based aromatic polyamide fiber Milled fiber Kevlar pulp 40 parts Meta-based aromatic polyamide fiber Fibrillated fiber 20 parts (Teijin “Cornex pulp” fibril Modified fiber or Unitika "Apier pulp" fibrillated fiber) Ultra-beaten wood pulp (microfiber) 10 parts a-2 Para-aromatic polyamide fiber Short fiber Kevlar 149 3 mm x 1.5 De 80 parts Meta-aromatic polyamide fiber Fibrillated Fiber 20 parts (Teijin “Cornex pulp” fibrillated fiber or Unitika “Apier pulp” fibrillated fiber) Super beaten wood pulp (microfiber) 10 parts a-3 Para-aromatic polyamide fiber Short fiber Kevlar 149 3mm × 1.5 De 50 parts para aromatic polyamide fiber milled Fiber Kevlar pulp 50 parts Super beaten wood pulp (microfiber) 10 parts

B. The following papermaking chemicals are used: The same as Example 1. c. The physical properties and performance obtained are as follows. Same as in Example 1. d. Results of flame retardancy test Test method According to JIS D 1201 "Test method for flame retardancy of organic materials for automobile interiors". It does not reach the mark and is self-extinguishing.

Example 3 Polybenzimidazole fiber (Teijin PBI fiber) was 3 mm
0.5 to 50% of fibrillated fiber of meta-aromatic fiber is added as a fibrous binder to the cut short fiber,
0.5 to 30% of ultra-beaten wood pulp (microfiber) obtained by ultra-beaten wood pulp is added thereto, and a predetermined chemical is added thereto to form a slurry. I do. Compared with Examples 1 and 2, the flame retardancy is higher and the heat resistance is superior to para- and meta-based aromatic polyamide fiber paper.

A. The following materials are used as the above fiber material. Polybenzimidazole fiber Short fiber PBI 3mm × 1.5De 80 parts Meta-based aromatic polyamide fiber Fibrillated fiber 20 parts (Teijin “Cornex pulp” fibrillated fiber or Unitika “Apier pulp” fibrillated fiber) Super beaten wood pulp ( Microfiber) 10 parts b. The following chemicals are used as papermaking chemicals. The same as Example 1. c. The physical properties and performance obtained are as follows. Same as in Example 1. d. Results of flame retardancy test Test method According to JIS D 1201 "Test method for flame retardancy of organic materials for automobile interiors". It does not reach the mark and is self-extinguishing.

Example 4 Para-aromatic polyetheramide fibers, short fibers (1.5 De) obtained by cutting Technora (Teijin) into 3 mm, and milled fibers mechanically pulverized (average fiber length: 0.5 to 0.7 mm) Ultra-beaten wood pulp (microfiber) is added as a fibrous binder to Technora pulp at 0.5 to 30%, and if necessary, 0.5 to 50% of fibrillated fiber of meta-aromatic polyamide fiber is added and stirred. A more uniform slurry, a predetermined amount of a papermaking chemical is added to the slurry, papermaking is performed with a normal paper machine, and press-dried, flame-retardant, heat-resistant, moisture-resistant, water-resistant, and high-strength. An excellent speaker paper having a high elastic modulus and a high internal loss can be obtained.

A. The following are used as the above fiber materials. a-1 Para aromatic polyetheramide fiber Short fiber Technora 3mm × 1.5De 40 parts Para aromatic polyetheramide fiber Milled fiber Technora pulp 40 parts Meta aromatic polyamide fiber Fibrillated fiber 20 parts (Teijin “Cornex Pulp "fibrillated fiber or Unitika" Apier pulp "fibrillated fiber) Ultra-beaten wood pulp (microfiber) 10 parts a-2 Para-aromatic polyetheramide fiber Short fiber Technora 3mm x 1.5De 80 parts Meta-aromatic Polyamide fiber Fibrillated fiber 20 parts (Teijin "Cornex pulp" fibrillated fiber or Unitika "Apier pulp" fibrillated fiber) Super beaten wood pulp (microfiber) 10 parts a-3 Para-aromatic polyetheramide fiber Short Textile Technora 3mm × 1.5De 50 parts Para system Aromatic polyether amide fibers milled fiber Technora pulp 50 parts super beaten wood pulp (microfiber) 10 parts

B. The following are used as papermaking chemicals. The same as Example 1. c. The physical properties and performance obtained are as follows. Same as in Example 1. d. Results of flame retardancy test Test method According to JIS D 1201 "Test method for flame retardancy of organic materials for automobile interiors". It does not reach the mark and is self-extinguishing.

Example 5 Aromatic polyetherimide fiber PEI (Teijin) was 3 mm
A fibrillated fiber of a meta-aromatic polyamide fiber is added to a short fiber (1.5De) cut into
To 50%, and further, 0.5 to 30% of ultra-beaten wood pulp (microfiber) is added to form a uniform slurry by stirring, and a predetermined amount of a papermaking chemical is added to the slurry. In addition, it is possible to obtain an excellent speaker cone paper which is press-dried, flame-retardant and heat-resistant, has moisture resistance and water resistance, and has high strength, high elastic modulus and high internal loss.

A. The following are used as the above fiber materials. Aromatic polyetherimide fiber Short fiber PEI 3mm × 1.5De 80 parts Meta-based aromatic polyamide fiber Fibrillated fiber 20 parts (Teijin “Cornex pulp” fibrillated fiber or Unitika “Apier pulp” fibrillated fiber) Super beaten wood Pulp (microfiber) 10 parts b. The following papermaking chemicals are used. The same as Example 1. c. The physical properties and performance obtained are as follows. Same as in Example 1. d. Results of flame retardancy test Test method According to JIS D 1201 "Test method for flame retardancy of organic materials for automobile interiors". It does not reach the mark and is self-extinguishing.

Example 6 A fibril-forming fiber of a meta-aromatic polyamide fiber was used as a fibrous binder for short fibers (1.5 De) obtained by cutting phenol fiber kainol (Gunei Chemical Co., Ltd.) into 3 mm.
In addition, 0.5 to 30% of ultra-beaten wood pulp (microfiber) is added, and a uniform slurry is obtained by stirring. A predetermined amount of a papermaking chemical is added thereto, and papermaking is performed using a normal paper machine. Press-dried, flame-retardant, heat-resistant, moisture-resistant, water-resistant, high-strength, high-modulus, and high-internal-loss excellent speaker cone paper can be obtained.

A. The following are used as the above fiber materials. Phenol fiber Short fiber Kainol 3mm × 1.5De 80 parts Meta-aromatic polyamide fiber Fibrillated fiber 20 parts (Teijin “Cornex pulp” fibrillated fiber or Unitika “Apier pulp” fibrillated fiber) Super beaten wood pulp (micro fiber 10 parts b. The following papermaking chemicals are used: The same as Example 1. c. The physical properties and performance obtained are as follows. Same as in Example 1. d. Results of flame retardancy test Test method According to JIS D 1201 "Test method for flame retardancy of organic materials for automobile interiors". It does not reach the mark and is self-extinguishing.

[Example 7] Organic sulfur-containing fiber polyphenylene sulfide fiber PPS
As a fibrous binder, 0.5-50% of fibrillated fiber of meta-aromatic polyamide fiber is added to short fiber (2.0De) obtained by cutting (Teijin) into 3 mm, and further, ultra-beaten wood pulp (microfiber) Was added to form a uniform slurry by stirring, a predetermined amount of a papermaking chemical was added to the slurry, papermaking was performed using a normal papermaking machine, and press drying was performed.
An excellent speaker cone paper having flame retardancy, heat resistance, moisture resistance, water resistance, high strength, high elastic modulus and high internal loss can be obtained.

A. The following materials are used as the above fiber material. Polyphenylene sulfide fiber Short fiber PPS fiber 3mm × 2.0De 80 parts Meta-based aromatic polyamide fiber Fibrillated fiber 20 parts (Teijin “Cornex pulp” fibrillated fiber or Unitika “Apier pulp” fibrillated fiber) Super beaten Wood pulp (microfiber) 10 parts b. The following chemicals are used for papermaking. The same as Example 1. c. The physical properties and performance obtained are as follows. Same as in Example 1. d. Results of flame retardancy test Test method According to JIS D 1201 "Test method for flame retardancy of organic materials for automobile interiors". It does not reach the mark and is self-extinguishing.

Example 8 Flame-retardant rayon fiber, flame-retardant vinylon-based fiber (flame-retardant fiber with high degree of saponification), flame-retardant polyethylene terephthalate (PET) fiber, flame-retardant general-purpose fiber A fibrillated fiber of meta-aromatic polyamide fiber is added as a fibrous binder to a short fiber obtained by cutting a reinforced polypropylene (PP) fiber or the like into 3 mm, and a fibrillated fiber of super-beaten wood (microfiber) is further added. Of 0.5 to 30%, and agitated to obtain a uniform slurry. A predetermined amount of a papermaking chemical is added to the slurry, papermaking is carried out with a normal paper machine, and press-dried, flame-retardant and heat-resistant, An excellent speaker cone paper having humidity resistance, water resistance, high strength, high elastic modulus and high internal loss can be obtained.

A. The following materials are used as the above fiber material. a-1 Flame retardant rayon fiber Short fiber 3mm × 1.5De 80 parts Daiwabo “Flame retardant rayon” Meta-based aromatic polyamide fiber Fibrillated fiber 20 parts (Teijin “Cornex pulp” fibrillated fiber or Unitika “Apierre” Pulp "fibrillated fiber" Super beaten wood pulp (microfiber) 10 parts a-2 Flame retardant vinylon fiber short fiber 3mm x 1.5De 80 parts Kuraray "PBX" Meta-based aromatic polyamide fiber fibrillated fiber 20 parts (Teijin Cornex pulp ”fibrillated fiber or Unitika“ Apier pulp ”fibrillated fiber) Ultra-beaten wood pulp (microfiber) 10 parts a-3 Flame retardant PET fiber Short fiber 3mm × 1.5De 80 parts Teijin (flame retardant tetron) ) Meta-based aromatic polyamide fiber fibrillated fiber 20 parts (Teijin “Cornex pulp” fibrillated fiber) Other Unitika "Pierre pulp" fibrillation fiber) ultra-beaten wood pulp (microfiber) 10 parts

B. The following chemicals are used as papermaking chemicals. The same as Example 1. c. The physical properties and performance obtained are as follows. Same as in Example 1. d. Results of flame retardancy test Test method According to JIS D 1201 "Test method for flame retardancy of organic materials for automobile interiors". It does not reach the mark and is self-extinguishing.

Example 9 Various properties can be further improved by impregnating the corn paper obtained in Examples 1 to 8 with the following solution substances.

1. Aromatic polyamide, imide compound Aromatic polyamide resin Flame retardancy Heat resistance High strength High elastic modulus Aromatic polyamide imide resin 〃 〃 芳香 Aromatic polyester imide resin 〃 〃 〃 Aromatic polyester amide imide resin 〃 〃 〃 ポ リ イ ミ ド Aromatic polyimide resin 〃 〃 〃 〃 Aromatic polyhydratoin compound 〃 〃 〃 〃 Aromatic benzimidazole compound 〃 〃 〃 〃 Aromatic polybenzothiazole compound 〃 〃 〃 〃 Aromatic polypyromellitimide compound 〃 〃 〃 〃 Silicon imide compound 〃 〃 〃 〃 Polyparabanic acid compound 〃 〃 〃 〃

2. Organometallic polymer compound Organic silicon-containing compound Heat resistance Flame retardant High elastic modulus Organic containing boron, silicon compound 〃 〃 Organic titanium-containing, silicon compound 〃 〃 Organic aluminoxane compound 〃 〃 Organic phosphazene compound 〃 〃 〃 Organosol Alumina sol 〃 〃 シ リ カ Silica sol 〃 〃 〃

3. Inorganic compounds Alkali metal silicates (sodium, potassium, lithium salts) Heat resistance Flame retardancy High elastic modulus Polyaluminoxane ガ 〃 Organosol Alumina sol 〃 〃 Organosol Silica sol 〃 Excellent weather resistance.

[0062]

As described above, according to the present invention, aromatic polyamide, imide-based fibers, organic sulfur-containing fibers, polybenzimidazole fibers, phenol fibers, or other short fibers of flame-retardant general-purpose fibers are used as main fibers. As fibrillated fiber or milled fiber of aromatic polyamide fiber and ultra-beaten wood pulp were added as fibrous binder, paper-formed and press-dried to make corn paper, physical properties such as high elastic modulus and high internal loss It is possible to obtain a flame-retardant cone paper having excellent flame retardancy, heat resistance, humidity resistance and water resistance and excellent mass productivity.

Further, since the above-mentioned material is impregnated with a solution of an aromatic polyamide, an imide compound, an organometallic polymer compound, an inorganic compound, a flame-retardant resin compound or the like in order to improve the properties, a high elastic modulus and a high It is possible to obtain a flame-retardant corn paper having excellent physical properties such as internal loss and having excellent flame resistance, heat resistance, humidity resistance and water resistance and excellent mass productivity.

Claims (2)

(57) [Claims] 1. A main fiber is a short fiber of an aromatic polyamide, an imide-based fiber, an organic sulfur-containing fiber, a polybenzimidazole fiber, a phenol fiber or other flame-retardant general-purpose fibers having flame retardancy and heat resistance. A pulp-like fibril fiber obtained by finely fibrillating an aromatic polyamide fiber as a fibrous binder, or a mechanically pulverized milled fiber and wood pulp obtained by ultrabeating 10.0 m ² / g or more
Paper made by adding binding fibers such as ultra-beaten wood pulp having a specific surface area of, has flame retardancy and heat resistance, has moisture resistance and water resistance, and has high strength, high elastic modulus, high internal Flame-retardant corn paper characterized by having a loss. 2. The flame-retardant cone paper according to claim 1, which is impregnated with a solution of a flame-retardant and heat-resistant aromatic polyamide, imide compound, organometallic polymer compound, inorganic compound, flame-retardant resin or the like. Flame-retardant cone with high strength, high elastic modulus, and high internal loss by impregnating and coating it to further improve various properties such as flame retardancy, heat resistance, water resistance, and humidity resistance A flame-retardant cone paper, wherein the strength and the elastic modulus of the fiber paper are improved by hot pressing at the same temperature as the paper and the fiber having a thermal softening point.