JP2015068405A - Spherical belt-like seal body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a spherical belt-like seal body capable of preventing the surface of an opposite material from being damaged or roughed as much as possible in slide friction with the opposite material, and capable of preventing reduction in sealability and occurrence of friction noise.SOLUTION: In a spherical belt-like seal body 44, an external surface 45 of an external layer 43 is a flat surface 48 in which a surface 46 of a heat resistant material including an expansion graphite sheet 21 and a surface 47 comprising a plain weave wire netting 17, where intersection point groups 19a, 19d are arrayed in an axial direction Z and intersection point groups 19b, 19c are arrayed in a circumferential direction R, coexist and are exposed. The surface 47 in the intersections 19a, 19d and 19b, 19c is exposed so as to have an area ratio of 10-65% to the whole of the external surface 45 of the external layer 43.

Description

  The present invention relates to a ball-shaped seal body used for a spherical pipe joint of an automobile exhaust pipe.

  In FIG. 30 showing an example of the exhaust passage of the automobile engine, the exhaust gas generated in each cylinder (not shown) of the automobile engine is collected in the exhaust manifold catalytic converter 600, and the sub muffler 603 is passed through the exhaust pipe 601 and the exhaust pipe 602. Is further sent to a muffler (silencer) 606 through an exhaust pipe 604 and an exhaust pipe 605, and is released into the atmosphere through the muffler 606.

  These exhaust pipes 601, 602, 604, and 605 and the exhaust system members such as the sub-muffler 603 and the muffler 606 are repeatedly subjected to stress due to the roll behavior and vibration of the engine. Particularly in the case of a high-speed engine with high speed rotation, the stress applied to the exhaust system member becomes quite large, which may cause fatigue damage to the exhaust system member, and the engine vibration causes the exhaust system member to resonate, resulting in room quietness. May worsen. In order to solve such a problem, the connection portion 607 between the exhaust manifold catalytic converter 600 and the exhaust pipe 601 and the connection portion 608 between the exhaust pipe 604 and the exhaust pipe 605 are absorbed by vibrations such as an exhaust pipe spherical joint or a bellows type joint. By movably connecting the mechanism, the stress repeatedly applied to the exhaust system member due to the roll behavior and vibration of the automobile engine is absorbed, preventing fatigue failure of the exhaust system member and the vibration of the engine resonating the exhaust system member. The problem that the quietness in the passenger compartment is deteriorated is also solved.

JP 54-76759 A JP-A-58-34230 JP-A-6-123362

  The exhaust pipe joint described in Patent Document 1 as an example of the vibration absorbing mechanism described above and the seal body used for the exhaust pipe joint can reduce the manufacturing cost as compared with the bellows type joint, and are durable. This sealing body compresses a heat-resistant material made of expanded graphite and a reinforcing material made of a wire mesh, and fills the mesh of the wire mesh of the reinforcing material with the heat-resistant material. Since the reinforcement material is mixed and integrated, in addition to the problem of exhaust gas leakage through the seal body itself due to the ratio of the reinforcement material to the heat resistance material, the degree of compression of the heat resistance material and the reinforcement material, etc. There is a problem of the generation of frictional noise due to the presence of the heat-resistant material on the surface of the partially convex spherical surface that slidably contacts the material, for example, the proportion of the reinforcing material to the heat-resistant material is large, Reinforcement when the degree of pressure applied to the heat-resistant material is low In addition to reducing the degree of sealing with the heat-resistant material with respect to the micro passage (gap) generated around the surface, causing initial leakage, there is a risk of early exhaust gas leakage due to oxidation consumption of the heat-resistant material at high temperatures, Moreover, if the exposure ratio of the heat-resistant material to the reinforcing material on the partially convex spherical surface is extremely large, there is a possibility that a stick-slip phenomenon is caused and a frictional noise due to the stick-slip phenomenon is generated.

  In order to eliminate the drawbacks of the sealing body described above, the sealing body described in Patent Document 2 includes a reinforcing material and a reinforcing material made of a wire mesh whose sliding surfaces (outer surfaces of partially convex spherical surfaces) are deformed and intertwined. Since the solid lubricant filled and held in the mesh of the metal mesh is formed on a smooth and integrated surface, the portion of the seal body described in Patent Document 1 is slidably in contact with the mating material Although it has the advantage of avoiding as much as possible the disadvantage of the generation of frictional noise due to the presence of heat-resistant material on the outer surface of the convex spherical surface, the problem of exhaust gas leakage inherent in the sealing body is still Still not resolved.

  Similar to the seal body described in Patent Document 2, the seal body described in Patent Document 3 is a reinforcing material and a reinforcing material composed of a wire mesh in which the surface of the partially convex spherical surface that is the sliding surface is deformed and entangled The solid lubricant filled and held in the mesh of the metal mesh is formed on a smooth surface that is mixed and integrated. In particular, since the solid lubricant contains boron nitride, the sealing body described in Patent Document 2 It has superior sliding characteristics in the high temperature region and has the advantage that no abnormal noise is generated even when sliding with the mating material. When a small rocking motion or excessive axial input is applied for a long period of time, the reinforcing material attacks the mating material surface by sliding friction with the mating material and induces abrasive wear. To scrape off the surface of the mating material Cormorants Do roughened mating member surface damage, risk and to reduce significantly the sealing properties, there is a possibility to generate frictional noises.

  As a result of intensive studies in view of the above circumstances, the present inventors have focused on the outer surface of the partially convex spherical surface of the spherical belt-shaped sealing body that becomes the sliding friction surface with the counterpart material, and the reinforcement made of a wire mesh exposed on the outer surface When the sliding friction surface between the material and the concave spherical surface of the mating material was observed, the intersection of adjacent loops of the braided wire mesh forming the reinforcing material became a large lump-like lump, which is the sliding friction with the mating material. The knowledge that it is what damages the other party's surface was acquired.

  The present invention has been made on the basis of the above knowledge, and the object of the present invention is to prevent damage to the mating material surface or roughening as much as possible in sliding friction with the mating material, An object of the present invention is to provide a spherical belt-like sealing body that can prevent the deterioration of the sealing performance and the generation of abnormal frictional noise as much as possible.

  The spherical band-shaped sealing body of the present invention used for an exhaust pipe joint includes a spherical inner surface defined by a cylindrical inner surface, a partially convex spherical surface, an annular end surface on the large diameter side and a small diameter side of the partial convex spherical surface, An outer layer integrally formed on the partially convex spherical surface of the belt-shaped substrate, the spherical belt-shaped substrate is filled with a reinforcing material made of a wire mesh, and a mesh of the wire mesh of the reinforcing material, and the reinforcing material The outer layer is on one diagonal of a pair of diagonal lines connecting the intersections of adjacent vertical lines and adjacent horizontal lines forming a square mesh. One intersection group located on the other side is arranged in the axial direction, while the other intersection group located on the other diagonal line of the pair of diagonal lines is composed of a plain woven wire mesh arranged in the circumferential direction and compressed. At least a reinforcing material.

  According to the spherical belt-shaped sealing body of the present invention, the outer layer is located on one of the diagonal lines connecting the intersections of the adjacent vertical lines and the adjacent horizontal lines forming a square mesh. A pair of diagonal lines is arranged in the axial direction, while the other intersection group located on the other diagonal line of the pair of diagonal lines is composed of a plain woven wire mesh arranged in the circumferential direction and a compressed reinforcing material. Because it has at least, it is possible to eliminate large lumps-like lumps at the intersection group, and in the sliding friction with the counterpart material, induction of abrasive wear between the mesh intersection point and the counterpart material surface as much as possible In addition to reducing the roughening caused by damage to the surface of the counterpart material and preventing the deterioration of the sealing performance as much as possible, it is also possible to reduce such a large amount even when the outer surface of the outer layer is worn sequentially. Lump-like lump and mating material table The sliding is avoided between, it is possible to prevent the occurrence of frictional noises as much as possible.

  In the spherical belt-shaped sealing body of the present invention, the outer layer may be filled with a mesh of a plain woven wire mesh of a reinforcing material and may include a heat-resistant material mixed and integrated with the reinforcing material. The outer surface of the outer layer may be a smooth surface exposed by mixing the surface of the heat-resistant material and the surface of the reinforcing material, and the outer layer is filled with a mesh of a plain woven wire mesh of the reinforcing material. In addition, the outer surface of the outer layer may be a mixture of the solid lubricant surface and the reinforcing material surface. Then, it may be a smooth surface exposed.

  When the outer surface of the outer layer is a smooth surface exposed by mixing the surface of the heat-resistant material and the surface of the reinforcing material, the ball-shaped seal body of the present invention is the surface of the heat-resistant material, Because it slides on the surface of the reinforcing material made of plain weave wire mesh, it is possible to avoid the induction of abrasive wear and the generation of frictional noise without assuming initial wear, and excessive heat-resistant material coating is excessively applied to the surface of the mating material. When it is formed, frictional noise is generated as much as possible on the surface of the mating material due to the sliding friction through an appropriate film due to the action of scraping off the excessive film by the exposed reinforcing material. In addition to the above, if the outer surface of the outer layer is a smooth surface exposed by mixing the surface of the solid lubricant and the surface of one or the other intersection group in the plain woven wire mesh of the reinforcing material, Therefore, the surface of the solid lubricant reduces the initial frictional resistance and allows smooth sliding. It is possible.

  In order to exert the above effect more, in the spherical belt-shaped sealing body of the present invention, the plain woven wire mesh surface of the reinforcing material is preferably 10 to 65%, more preferably, the entire outer surface of the outer layer. It may be exposed on the outer surface of the outer layer with an area ratio of 15 to 60%.

  That is, when the surface of the plain woven wire mesh of the reinforcing material is exposed on the outer surface of the outer layer with an area ratio of 10 to 65% with respect to the entire outer surface of the outer layer, the exposed reinforcing material in the sliding friction with the counterpart material The action of scraping off the excessive coating caused by the material can reduce the induction of abrasive wear with the surface of the mating material as much as possible, and reduce the roughening caused by the damage of the mating material surface to reduce the sealing performance as much as possible. Can be prevented.

  Further, in the ball-shaped seal body of the present invention, the outer layer is filled with the mesh of the plain woven wire mesh of the reinforcing material and covers the heat-resistant material and the reinforcing material mixed with and integrated with the reinforcing material. The outer surface of the outer layer may be a smooth surface with the surface of the solid lubricant exposed, and according to such a ball-shaped seal body, the initial frictional resistance is further improved. It can reduce and can make smooth sliding.

  In a preferred example of the spherical belt-shaped sealing body of the present invention, the solid lubricant is a tetrafluoroethylene resin (hereinafter abbreviated as PTFE), a tetrafluoroethylene-hexafluoropropylene copolymer (hereinafter abbreviated as FEP). ) And hexagonal boron nitride (hereinafter abbreviated as “h-BN”).

  In a preferred example, the composition ratio of the solid lubricant is 10% by mass of PTFE, 10% by mass of FEP, and 80% by mass of h-BN in the ternary composition diagram of PTFE, FEP and h-BN, 10% by mass of PTFE, and FEP45. Composition point to be mass% and h-BN 45 mass%, composition point to be PTFE 45 mass%, FEP 45 mass% and h-BN 10 mass%, and composition point to be PTFE 40 mass%, FEP 10 mass% and h-BN 50 mass% It is in the numerical range corresponding to the area bounded by the rectangle.

  According to a preferred example of the ball-shaped seal body of the present invention in which the composition ratio of the solid lubricant is in a numerical range corresponding to a region bounded by a quadrangle having four composition points as vertices in the ternary composition diagram There is no risk of damaging the mating material surface. In particular, since the solid lubricant contains h-BN in addition to PTFE and FEP having different melting points, self-excited vibration can be reduced and frictional noise can be generated. In addition to being able to prevent, excellent slidability can be obtained in a high temperature region.

  That is, according to such an example, the FEP melts and softens, and elasticity is exhibited by its viscosity. On the other hand, when the PTFE is not melted and used in a temperature range in which it is in a solid state, the elasticity of the FEP is increased by PTFE in the solid state. Suppressed, stick-slip is suppressed in sliding with the mating material, and when used above the temperature at which PTFE melts and softens and elasticity is manifested by its viscosity, the viscosity of the FEP is further reduced by further melting. This causes an increase in lubricity, suppresses elasticity due to the viscosity of PTFE, and similarly prevents stick-slip in sliding with the mating material, and thus does not melt PTFE and FEP. To PTFE and FEP, where high melting temperature is achieved, self-excited vibration can be reduced by the synergistic effect of PTFE and FEP. In addition to the lubricity of PTFE, FEP, and h-BN, especially the high-temperature lubricity of h-BN, it can slide smoothly against other materials even at high temperatures. In addition, a stable sealing characteristic can be exhibited in cooperation with an outer layer reinforcing material made of expanded graphite and plain woven wire mesh.

  More preferably, the composition ratio of PTFE, FEP and h-BN in the solid lubricant is a composition point of PTFE 25% by mass, FEP 15% by mass and h-BN 60% by mass, PTFE 12% by mass, FEP28 in the ternary composition diagram. Composition point of mass% and h-BN 60 mass%, composition point of PTFE 10 mass%, FEP 40 mass% and h-BN 50 mass%, composition of PTFE 20 mass%, FEP 40 mass% and h-BN 40 mass%, PTFE 38 Numerical value corresponding to a region bounded by hexagons having apexes at composition points of mass%, FEP 22 mass% and h-BN 40 mass% and PTFE 35 mass%, FEP 15 mass% and h-BN 50 mass%. Within the range, still more preferably 25% PTFE, 25% FEP and hB 50 mass%.

  In the present invention, the solid lubricant may contain 20% by mass or less of alumina hydrate, preferably 0.05 to 10% by mass, and more preferably 0.05 to 10% by mass. Such an alumina hydrate itself does not exhibit any lubricity, but improves the adherence of the solid lubricant to the partially convex spherical surface of the spherical base and forms a strong outer layer. As well as promoting slippage between layers of hexagonal boron nitride plate-like crystals and exerting the role of drawing out the lubricity of hexagonal boron nitride.

Alumina hydrate is a compound represented by the composition formula Al ₂ O ₃ .nH ₂ O (where 0 <n <3), and in this composition formula, n is usually 0 (zero). The number is more than less than 3, preferably 0.5 to 2, more preferably about 0.7 to 1.5. Examples of the alumina hydrate include boehmite (Al ₂ O ₃ .H ₂ O) and diaspore. _{(Al 2 O 3 · H 2} O) alumina monohydrate such as (aluminum hydroxide oxide), gibbsite _{(Al 2 O 3 · 3H 2} O) and bayerite _{(Al 2 O 3 · 3H 2} O) , such as Alumina trihydrate, pseudo boehmite and the like can be mentioned, and at least one of them is preferably used.

  In the present invention, the solid lubricant may not be fired, but may be fired at a temperature equal to or higher than the melting point of FEP.

  In a preferred example of the spherical belt-shaped sealing body of the present invention, the heat-resistant material contains compressed expanded graphite, and in addition to expanded graphite, phosphate 0.1 to 16.0 mass as an oxidation inhibitor. % Or phosphorus pentoxide 0.05 to 5% by weight or phosphate 0.1 to 16.0% by weight and phosphorus pentoxide 0.05 to 5.0% by weight.

  The heat-resistant material containing at least one of phosphate and phosphorus pentoxide as an oxidation inhibitor and expanded graphite can improve the heat resistance and oxidation consumption resistance of the ball-shaped seal body itself, and the ball-shaped seal body It can be used in the high temperature range.

  In the ball-shaped seal body of the present invention, the wire mesh as a reinforcing material used for the ball-band shaped substrate includes, for example, a woven wire mesh and a braided wire mesh obtained by weaving or knitting metal fine wires. The fine metal wire forming the wire mesh may have a wire diameter of 0.15 to 0.32 mm.

  In the ball-shaped seal body of the present invention, the plain woven wire mesh as a reinforcing material used for the outer layer has a plurality of vertical lines and horizontal lines woven in a lattice shape, and has a square mesh surrounded by both. The vertical lines and horizontal lines preferably have a wire diameter of 0.15 to 0.28 mm, and such plain weave wire mesh is adjacent to adjacent vertical lines forming a square mesh. One intersection group located on one of the pair of diagonal lines connecting to each other is arranged in the width direction, the other intersection group located on the other diagonal line is arranged in the longitudinal direction, and both ends thereof are directed in the same oblique direction. It may be formed in a parallelogram shape in plan view so as to have an oblique side.

  According to the present invention, in sliding friction with the mating material, the reinforcing material can attack the mating material to reduce the induction of abrasive friction as much as possible, thereby reducing the roughening caused by damage to the mating material surface. Thus, it is possible to provide a ball-shaped seal body and a method for manufacturing the same, which can prevent the deterioration of the sealing performance as much as possible and can prevent the generation of frictional noise as much as possible.

FIG. 1 is a longitudinal sectional explanatory view of a preferred example of an embodiment of the present invention. FIG. 2 is a partially enlarged cross-sectional explanatory view of the example shown in FIG. FIG. 3 is an external explanatory view of the example shown in FIG. FIG. 4 is an explanatory diagram of a method for forming a reinforcing material for a spherical band substrate in the manufacturing process of the example shown in FIG. FIG. 5 is a perspective explanatory view of the heat-resistant material in the manufacturing process of the example shown in FIG. FIG. 6 is an explanatory plan view of a reinforcing material wire mesh in the manufacturing process of the example shown in FIG. 1. FIG. 7 is a perspective explanatory view of a polymer in the manufacturing process of the example shown in FIG. FIG. 8 is an explanatory plan view of the cylindrical base material in the manufacturing process of the example shown in FIG. FIG. 9 is a longitudinal sectional view of the cylindrical base material shown in FIG. FIG. 10 is an explanatory view of a plain woven wire mesh in the manufacturing process of the example shown in FIG. 1, (a) is an explanatory plan view thereof, and (b) is an explanatory side view thereof. FIG. 11 is an explanatory plan view of a reinforcing material for an outer layer made of the plain weave wire mesh shown in FIG. 12 is a perspective explanatory view of a heat-resistant material for the outer layer in the manufacturing process of the example shown in FIG. FIG. 13 is a perspective explanatory view showing a manufacturing process of the outer layer forming member in the manufacturing process of the example shown in FIG. FIG. 14 is an explanatory diagram of a method of forming the outer layer forming member in the manufacturing process of the example shown in FIG. FIG. 15 is an explanatory plan view of the outer layer forming member in the manufacturing process of the example shown in FIG. FIG. 16 is a cross-sectional explanatory view of a heat-resistant material for an outer layer provided with a solid lubricant coating layer in the manufacturing process of an example of another embodiment of the present invention. FIG. 17 is a perspective explanatory view showing a manufacturing process of the outer layer forming member in the manufacturing process of the example shown in FIG. 18 is an explanatory diagram of a method for forming an outer layer forming member in the manufacturing process of the example shown in FIG. FIG. 19 is an explanatory plan view of the outer layer forming member in the manufacturing process of the example shown in FIG. FIG. 20 is an explanatory plan view of a preliminary cylindrical molded body in the manufacturing process of the example shown in FIGS. 1 and 16. FIG. 21 is an external explanatory view of the preliminary cylindrical molded body shown in FIG. FIG. 22 is a cross-sectional explanatory view showing a state where a preliminary cylindrical molded body is inserted into a mold in the manufacturing process of the example shown in FIGS. 1 and 16. FIG. 23 is a partially enlarged cross-sectional explanatory view of a preferred example of another embodiment of the present invention. FIG. 24 is a partially enlarged cross-sectional explanatory view of a preferred example of still another embodiment of the present invention. FIG. 25 is a ternary composition explanatory diagram regarding the composition ratio of the solid lubricant in the spherical belt-shaped sealing body of the present invention. FIG. 26 is an explanatory plan view of a reinforcing material made of plain weave wire mesh in the outer layer forming member in Example 1 to Example 10. FIG. 27 is an explanatory plan view of a reinforcing material made of a strip-shaped wire mesh (braided wire mesh) in the composite sheet material in Comparative Example 1 and Comparative Example 2. FIG. 28 is an explanatory plan view of a reinforcing material made of plain weave wire mesh in the outer layer forming member in Comparative Example 3. FIG. 29 is a longitudinal cross-sectional explanatory view of an exhaust pipe spherical joint incorporating a preferred example of the ball-shaped seal body of the present invention. FIG. 30 is an explanatory diagram of the exhaust system of the engine.

  Next, the present invention and its embodiments will be described in more detail based on preferred embodiments shown in the drawings. In addition, this invention is not limited to these Examples at all.

  The constituent material in the preferable example of the spherical belt-shaped sealing body of the present invention and the manufacturing method of the example will be described.

<About heat-resistant material I and its manufacturing method>
While stirring concentrated sulfuric acid having a concentration of 98%, a 60% aqueous solution of hydrogen peroxide is added as an oxidizing agent to make a reaction solution. The reaction solution is cooled and maintained at a temperature of 10 ° C., and scale-like natural graphite powder having a particle size of 30 to 80 mesh is added to the reaction solution and reacted for 30 minutes. After the reaction, the acid-treated graphite powder is separated by suction filtration, and the washing operation of stirring the acid-treated graphite powder with water for 10 minutes and suction-filtering is repeated twice to sufficiently remove the sulfuric acid content from the acid-treated graphite powder. . Next, the acid-treated graphite powder from which sulfuric acid has been sufficiently removed is dried in a drying furnace maintained at a temperature of 110 ° C. for 3 hours to obtain an acid-treated graphite powder.

  The above-mentioned acid-treated graphite powder is heated (expanded) at a temperature of 950 to 1200 ° C. for 1 to 10 seconds to generate decomposition gas, and expanded between graphite layers by the gas pressure (expansion magnification). 240 to 300 times). The expanded graphite particles are supplied to a double roller apparatus adjusted to a desired roll gap and roll-molded to produce an expanded graphite sheet having a desired thickness. This expanded graphite sheet is used as a heat resistant material I.

<About heat-resistant material II and its manufacturing method>
While stirring the acid-treated graphite powder obtained in the same manner as the acid-treated graphite powder, an aqueous solution of primary aluminum phosphate [Al (H ₂ PO ₄ ) ₃ ] having a concentration of 50% as a phosphate is added to the acid-treated graphite powder. A solution diluted with methanol is blended in the form of a spray and stirred uniformly to prepare a mixture having wettability. The wettable mixture is dried for 2 hours in a drying oven maintained at a temperature of 120 ° C. Subsequently, this was heated (expanded) at a temperature of 950 to 1200 ° C. for 1 to 10 seconds to generate decomposition gas, and expanded graphite particles (expansion magnification: 240 to 300) expanded by expanding the graphite layer by the gas pressure. Times). In this expansion treatment step, water in the structural formula is released from the primary aluminum phosphate. The expanded graphite particles are supplied to a double roller apparatus adjusted to a desired roll gap and roll-molded to produce an expanded graphite sheet having a desired thickness. This expanded graphite sheet is used as a heat-resistant material II.

The heat-resistant material II thus produced contains primary aluminum phosphate in a proportion of 0.1 to 16% by mass in expanded graphite. The expanded graphite containing the phosphate improves the heat resistance of the expanded graphite itself and imparts an oxidation inhibiting action, so that it can be used in a high temperature region exceeding 600 ° C. to 600 ° C., for example. As the phosphate, in addition to primary aluminum phosphate, secondary lithium phosphate (Li ₂ HPO ₄ ), primary calcium phosphate [Ca (H ₂ PO ₄ ) ₂ ], secondary calcium phosphate (CaHPO ₄ ), second Aluminum phosphate [Al ₂ (HPO ₄ ) ₃ ] can be used.

<About heat-resistant material III and its manufacturing method>
While stirring the acid-treated graphite powder obtained by the same method as described above, the acid-treated graphite powder was mixed with a first aluminum phosphate aqueous solution having a concentration of 50% as a phosphate and orthophosphoric acid (H ₃ PO ₄ ) having a concentration of 84% as phosphoric acid. A solution obtained by diluting an aqueous solution with methanol is blended in a spray form, and stirred uniformly to prepare a wettable mixture. The wettable mixture is dried for 2 hours in a drying oven maintained at a temperature of 120 ° C. Subsequently, this was heated (expanded) at a temperature of 950 to 1200 ° C. for 1 to 10 seconds to generate decomposition gas, and expanded graphite particles (expansion magnification: 240 to 300) expanded by expanding the graphite layer by the gas pressure. Times). In this expansion treatment step, water in the structural formula is eliminated with primary aluminum phosphate, and dehydration reaction occurs with orthophosphoric acid to produce phosphorus pentoxide. The expanded graphite particles are supplied to a double roller apparatus adjusted to a desired roll gap and roll-molded to produce an expanded graphite sheet having a desired thickness. This expanded graphite sheet is used as a heat-resistant material III.

In the heat-resistant material III thus produced, the expanded graphite contains 0.1 to 16% by mass of primary aluminum phosphate and 0.05 to 5% by mass of phosphorus pentoxide. This expanded graphite containing phosphate and phosphorus pentoxide improves the heat resistance of the expanded graphite itself and imparts an oxidation inhibiting action, so that it can be used in a high temperature range, for example, 600 ° C. to over 600 ° C. To do. As phosphoric acid, in addition to the above orthophosphoric acid, metaphosphoric acid (HPO ₃ ), polyphosphoric acid and the like can be used.

The expanded graphite sheets of the heat-resistant materials I, II and III preferably have a density of about 1.0 to 1.15 Mg / m ^{3 and} a thickness of about 0.3 to 0.6 mm.

<Reinforcing material for spherical belt-shaped substrate>
Examples of the reinforcing material for the spherical belt-shaped substrate include austenitic SUS304, SUS310S, SUS316, ferritic SUS430, and the like, iron wire (JISG3532) or galvanized steel wire (JISG3547), or copper-based copper. Weaving formed by weaving or knitting one or more fine metal wires made of nickel alloy (white copper) wire, copper-nickel-zinc alloy (yoh white) wire, brass wire or beryllium copper wire A wire mesh such as a wire mesh or a braided wire mesh may be used.

  For the wire mesh, fine metal wires with a wire diameter in the range of 0.15 to 0.32 mm, specifically, fine metal wires of 0.15 mm, 0.17 mm, 0.20 mm, 0.28 mm or 0.32 mm are used. The braid shown in FIG. 6 has a mesh width of a metal mesh for a spherical band-shaped substrate formed of fine metal wires having the above-mentioned wire diameter, wherein the vertical width M = 4 to 6 mm and the horizontal width N = 3 to 5 mm. A wire mesh or a woven wire mesh comprising a plain weave wire mesh 17 shown in FIG. 10 is preferably used.

<Reinforcing material for outer layer>
The reinforcing material for the outer layer is similar to the reinforcing material for the spherical belt-shaped substrate, and is made of stainless steel such as austenitic SUS304, SUS310S, SUS316, ferrite SUS430, iron wire (JISG3532) or galvanized steel wire (JISG3547). ) Or copper-based metal wires with a wire diameter of 0.05 to 0.28 mm made of copper-nickel alloy (white copper) wire, copper-nickel-zinc alloy (white wire) wire, brass wire, and beryllium copper wire. A plain weave wire mesh 17 shown in FIG. 10 having a mesh width of about 2.0 to 3.5 mm in the longitudinal direction and a width N of about 2.0 to 3.5 mm in the lateral direction is preferably used. In particular, the reinforcing material for the outer layer uses a reinforcing material made of plain woven wire mesh 17 shown in FIGS. 10 and 26, and as shown in FIG. A plurality of vertical lines 14 and a plurality of horizontal lines 15 are formed in a quadrilateral shape and woven in a lattice shape, and adjacent vertical lines 14 and adjacent horizontal lines 15 forming a square mesh 16 are formed. One intersection group 19a and 19d located on one of the pair of diagonal lines connecting the intersection is arranged in the width direction X, and the other intersection group 19b and 19c located on the other diagonal is in the longitudinal direction Y. An arranged plain weave wire mesh 17 is preferably used.

<About solid lubricant>
The composition ratio of the solid lubricant containing PTFE, FEP and h-BN is preferably the content (mass%) of the right-hand side of FIG. 25 with respect to the composition ratio (mass%) of PTFE, FEP and h-BN. , A ternary composition diagram of equilateral triangles showing the content (mass%) of FEP on the bottom side and the content (mass%) of h-BN on the left oblique side of the paper, PTFE 10 mass%, FEP 10 mass% And h-BN 80 mass%, composition point A PTFE 10 mass%, FEP 45 mass% and h-BN 45 mass% composition point B, PTFE 45 mass%, FEP 45 mass% and h-BN 10 mass% composition point C and Within the numerical range corresponding to the region P bounded by the quadrilateral 51 with the composition point D at the apex of PTFE 40% by mass, FEP 10% by mass and h-BN 50% by mass Yes, more preferably, in the ternary composition diagram shown in FIG. 25, composition point E, PTFE 12 mass%, FEP 28 mass% and h-BN 60 mass%, which are PTFE 25 mass%, FEP 15 mass% and h-BN 60 mass% Composition point F, PTFE 10 mass%, FEP 40 mass% and h-BN 50 mass% Composition point G, PTFE 20 mass%, FEP 40 mass% and h-BN 40 mass% Composition point H, PTFE 38 mass%, FEP 22 mass% And within the numerical range corresponding to the region Q bounded by the hexagon 52 having the composition point J as the apex with the composition point J as h-BN 40 mass% and the composition point K as PTFE 35 mass%, FEP 15 mass% and h-BN 50 mass%. It is in.

  In the production process, this solid lubricant has PTFE powder having an average particle diameter of 0.01 to 1 μm, FEP powder having an average particle diameter of 0.01 to 1 μm, and h-BN having an average particle diameter of 0.1 to 20 μm. Used in the form of an aqueous dispersion comprising powder, surfactant and water.

  In the aqueous dispersion, the content ratio of the PTFE powder, the FEP powder, and the h-BN powder exhibiting excellent lubricity particularly in the high temperature region is preferably bounded by a rectangle 51 in the ternary composition diagram shown in FIG. In the numerical range corresponding to the region to be attached, more preferably in the numerical range corresponding to the region bounded by the hexagon 52 in the ternary composition diagram, and even more preferably, PTFE. They are 25 mass% of powder, 25 mass% of FEP powder, and 50 mass% of h-BN powder.

  An aqueous dispersion in which, for example, 4% by mass of a surfactant and 57% by mass of water are mixed with 39% by mass of the solid lubricant powder containing PTFE powder, FEP powder and h-BN powder having such a content ratio. However, the content of water in the aqueous dispersion may be increased or decreased depending on the mode of application of the aqueous dispersion to the expanded graphite sheet by means of roller coating, brush coating, spraying or the like.

  The surfactant contained in the aqueous dispersion may be any surfactant that can uniformly disperse the solid lubricant powder in water. Anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants Any surfactant can be used. For example, anionic surface activity such as sodium alkyl sulfate, sodium alkyl ether sulfate, triethanolamine alkyl sulfate, triethanolamine alkyl ether sulfate, ammonium alkyl sulfate, ammonium alkyl ether sulfate, sodium alkyl ether phosphate, sodium fluoroalkylcarboxylate, etc. Agents; cationic surfactants such as alkyl ammonium salts and alkyl benzyl ammonium salts; addition of polyoxyethylene alkyl ether, polyoxyethylene phenyl ether, polyoxyethylene alkyl ester, propylene glycol-propylene oxide copolymer, perfluoroalkyl ethylene oxide With 2-ethylhexanol ethylene oxide Nonionic surfactants such things; alkyl betaine, alkylamido betaine, amphoteric surfactants such as imidazolium betaine. In particular, anionic and nonionic surfactants are preferred. A particularly preferable surfactant is a nonionic surfactant having an oxyethylene chain with a small amount of thermal decomposition.

  In the aqueous dispersion, the surfactant content is, for example, 4% by mass with respect to 39% by mass of the solid lubricant powder. If the surfactant content is too small, the dispersion of the solid lubricant powder is not achieved. If it is not uniform and the content of the surfactant is too large, the decomposition residue of the surfactant due to baking increases and coloring occurs, and the heat resistance, non-adhesiveness and the like decrease.

  An aqueous dispersion containing PTFE powder, FEP powder, h-BN powder, surfactant and water is further used in the solid lubricant powder in place of part of the content of h-BN powder. You may contain the powder in the ratio of 20 mass% or less, Preferably it is 0.05-10 mass%, More preferably, it is 0.05-5 mass%.

  Aqueous dispersion containing PTFE powder, FEP powder, h-BN powder, surfactant and water or PTFE powder, FEP powder, h-BN powder, alumina hydrate powder, aqueous dispersion containing surfactant and water John may further contain a water-soluble organic solvent. Examples of the water-soluble organic solvent include alcohol solvents such as methanol, ethanol, butanol, isopropyl alcohol and glycerin, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ether solvents such as methyl cellosolve, cellosolve and butyl cellosolve, Examples include glycol solvents such as ethylene glycol, propylene glycol, triethylene glycol, and tetraethylene glycol; amide solvents such as dimethylformamide and dimethylacetamide; and lactam solvents such as N-methyl-2-pyrrolidone. The content of the water-soluble organic solvent is 0.5 to 50% by mass, preferably 1 to 30% by mass, based on the total amount of water. The water-soluble organic solvent has a function of wetting the PTFE powder and the FEP powder, forms a uniform mixture with the h-BN powder, and evaporates at the time of drying, so that it does not have an adverse effect.

As an aqueous dispersion of powder for solid lubricants,
(1) PTFE powder having an average particle size of 0.01 to 1 μm, FEP powder having an average particle size of 0.01 to 1 μm, and h-BN powder having an average particle size of 0.1 to 20 μm and shown in FIG. In the ternary composition diagram, 39% by mass of powder for solid lubricant having a composition ratio within a numerical range corresponding to the region P bounded by the rectangle 51, 4% by mass of surfactant, and 57% by mass of water An aqueous dispersion consisting of
(2) In the solid lubricant powder having the composition ratio of (1) above, an alumina water is used instead of a part of the h-BN powder content by securing a content of h-BN powder of 45% by mass or more. An aqueous dispersion comprising 39% by mass of the powder for solid lubricant of the above (1) containing 20% by mass or less of Japanese powder, 4% by mass of a surfactant and 57% by mass of water;
(3) An aqueous dispersion containing 0.1 to 22.5% by mass of a water-soluble organic solvent in addition to the aqueous dispersion of (1) above,
(4) In the aqueous dispersion of (2), any one of aqueous dispersions containing 0.1 to 22.5% by mass of a water-soluble organic solvent is used.

  The aqueous dispersion is composed of the adjacent vertical lines 14 and the adjacent horizontal lines forming one side of the parallelogram-shaped expanded graphite sheet 21 shown in FIG. 12 or the rectangular mesh 16 shown in FIG. One intersection group 19a and 19d located on one of the pair of diagonal lines connecting the intersection is arranged in the width direction X, and the other intersection group 19b and 19c located on the other diagonal is in the longitudinal direction Y. Roller coating, brush coating, or the like on one surface of the parallelogram-shaped outer layer forming member 27 in plan view where the surface 24 of the plain weave wire mesh 17 and the surface 25 of expanded graphite filled in the mesh 16 of the plain weave wire mesh 17 are exposed, It is applied by means such as spraying. After drying the aqueous dispersion, a parallelogram shape in a plan view in which one surface of the expanded graphite sheet 21 or the surface 24 of the plain weave wire mesh 17 and the surface 25 of the expanded graphite filled in the mesh 16 of the plain weave wire mesh 17 are exposed. A coating layer 28 of solid lubricant is formed on one surface of the outer layer forming member 27. After drying, the solid lubricant coating layer 28 is (T) to (T + 150 ° C.), preferably (T + 5 ° C.) to (T + 135 ° C.), more preferably, with respect to a melting point T of 245 ° C. in a heating furnace. It may be baked for 10 to 30 minutes at a temperature within the range of (T + 10 ° C.) to (T + 125 ° C.). By baking the coating layer of this solid lubricant, one surface of the expanded graphite sheet 21 or the outer layer forming member 27 A fired coating layer of solid lubricant is formed on one surface.

  Next, a method for manufacturing a spherical belt-shaped sealing body made of the above-described constituent materials will be described with reference to the drawings.

(First step)
As shown in FIG. 4, the mesh width formed by knitting thin metal wires having a wire diameter of 0.15 to 0.32 mm in a cylindrical shape has a vertical width M = 4 to 6 mm and a horizontal width N = about 3 to 5 mm (FIG. 6). A cylindrical braided wire mesh 1 of reference 2) is passed between the rollers 2 and 3 to produce a belt-like wire mesh 4 having a predetermined width d1, and a reinforcing material for a spherical belt-like substrate obtained by cutting the belt-like wire mesh 4 into a predetermined length L; A strip-shaped wire mesh 5 is prepared.

(Second step)
As shown in FIG. 5, the width d2 of (1.10 × d1) mm to (2.10 × d1) mm with respect to the width d1 of the wire mesh 5 and (1. A strip having a length l of 30 × L) mm to (2.70 × L) mm and a density of 1.0 to 1.5 Mg / m ³ , preferably 1.0 to 1.2 Mg / m ³ The expanded graphite sheet 6 (made of one of the heat-resistant material I, the heat-resistant material II, and the heat-resistant material III) is prepared.

(Third process)
In the spherical belt-shaped seal body 44 (see FIGS. 1 and 2), the heat-resistant material made of expanded graphite of the expanded graphite sheet 6 is entirely exposed on the annular end surface 40 on the large diameter side of the partially convex spherical surface 39. Accordingly, as shown in FIG. 7, the maximum is (0.10-0.80) × d1 mm from one edge 7 in the width direction of the wire mesh 5 which becomes the annular end surface 40 on the large diameter side of the partially convex spherical surface 39. Further, the expanded graphite sheet 6 has a protruding amount δ1 larger than the protruding amount δ2 from the other end 8 in the width direction of the wire mesh 5 which becomes the annular end surface 41 (see FIG. 1) on the small diameter side of the partially convex spherical surface 39. And the expanded graphite sheet 6 for the sphere-like base member protrudes from the one edge 9 in the length direction of the wire mesh 5 in the length direction by a maximum of (0.30 to 1.70) × L mm. The other edge 10 in the length direction of the wire mesh 5 and the expanded graphite corresponding to the edge 10 Is matched and the edge 11 in the longitudinal direction of the over preparative 6 to obtain a polymer 12 obtained by superimposing each other and wire mesh 5 for expanded graphite sheet 6 and the spherical annular base member for the spherical annular base body.

(Fourth process)
As shown in FIG. 8, the polymer 12 is wound so that the expanded graphite sheet 6 is spiraled and the expanded graphite sheet 6 is increased once, and the expanded graphite is formed on both the inner peripheral side and the outer peripheral side. A cylindrical base material 13 with the sheet 6 exposed is formed. As the expanded graphite sheet 6, (1.30 × L) mm with respect to the length L of the wire mesh 5 so that the number of turns of the expanded graphite sheet 6 in the cylindrical base material 13 is larger than the number of turns of the wire mesh 5. To (2.70 × L) mm having a length l is prepared in advance. In the cylindrical base material 13, as shown in FIG. 9, in the cylindrical base material 13, the expanded graphite sheet 6 protrudes from the one edge 7 of the wire mesh 5 by δ 1 in the width direction on one edge side in the width direction. On the other edge side in the width direction of the expanded graphite sheet 6, only δ2 protrudes from the other edge 8 of the wire mesh 5 in the width direction.

(Fifth process)
As shown in FIG. 10, a plurality of vertical lines 14 and horizontal lines 15 are woven in a lattice shape, and a rectangular mesh 16 surrounded by adjacent vertical lines 14 and adjacent horizontal lines 15 is formed. A plain weave wire mesh 17 is prepared. Using a plain weave wire mesh 17, adjacent vertical lines 14 and adjacent horizontal lines 15 are woven in a lattice shape so as to form a square mesh 16 having both ends composed of oblique sides 18 inclined in the same direction, One intersection group 19a located on one diagonal line of a pair of diagonal lines connecting the intersections at each mesh 16 in the intersection groups 19a, 19b, 19c and 19d of the adjacent vertical lines 14 and adjacent horizontal lines 15. And 19d are arranged in the width direction X, and the other intersection groups 19b and 19c are arranged in the longitudinal direction Y and have a length (l−L + Δ) between both ends, as shown in FIG. A plain weave wire mesh 17 is prepared.

(Sixth process)
Plan view as an outer layer heat-resistant material as shown in FIG. 12 which has both ends composed of oblique sides 20 inclined in the same direction and has the same shape as the plain woven wire mesh 17 having a parallelogram shape in plan view and similar to the expanded graphite sheet 6. A parallelogram-shaped expanded graphite sheet 21 is prepared.

(Seventh step)
As an aqueous dispersion,
(1) PTFE powder having an average particle size of 0.01 to 1 μm, FEP powder having an average particle size of 0.01 to 1 μm, and h-BN powder having an average particle size of 0.1 to 20 μm and shown in FIG. In the ternary composition diagram, 39% by mass of powder for solid lubricant having a composition ratio within a numerical range corresponding to the region P bounded by the rectangle 51, 4% by mass of surfactant, and 57% by mass of water An aqueous dispersion consisting of
(2) In the solid lubricant powder having the composition ratio of (1) above, an alumina water is used instead of a part of the h-BN powder content by securing a content of h-BN powder of 45% by mass or more. An aqueous dispersion comprising 39% by mass of powder for solid lubricant (1), 4% by mass of surfactant and 57% by mass of water, containing 20% by mass or less of Japanese powder,
(3) An aqueous dispersion containing 0.1 to 22.5% by mass of a water-soluble organic solvent in the aqueous dispersion of (1) above, and (4) Further aqueous soluble in the aqueous dispersion of (2) above. An aqueous dispersion containing 0.1 to 22.5% by mass of an organic solvent,
Prepare one of them.

(Eighth process)
<First method>
As shown in FIG. 13, the expanded graphite sheet 21 is sandwiched between two plain woven wire meshes 17 with the hypotenuses 18 and 20 being matched, and then, as shown in FIG. The plain weave wire mesh 17 is pressed by a pair of rollers 22 and 23, and as shown in FIG. 15, the mesh 16 of the plain weave wire mesh 17 is a flat shape in which expanded graphite sheet 21 is filled with expanded graphite, and adjacent vertical lines 14 and a horizontal mesh 15 surrounded by adjacent horizontal lines 15 and intersection groups 19a, 19b, 19c, and 19d at the intersections 19a, 19b, 19c, and 19d of the vertical lines 14 and the horizontal lines 15, respectively. One intersection group 19a and 19d located on one of the pair of diagonal lines connecting the intersections 19d and 19d are arranged in the width direction X, and the other intersection group 19b and 19 located on the other diagonal line. Are exposed on the surface 24 of the plain woven wire mesh 17 arranged in the longitudinal direction Y and the surface 25 of the expanded graphite sheet 21 filled in the mesh 16 of the plain woven wire mesh 17, and the oblique sides 26 and 26 whose both ends are inclined in the same oblique direction. The outer layer forming member 27 having a parallelogram shape in plan view is formed.

<Second method>
As shown in FIG. 16, the aqueous dispersions (1) to (4) are brush-coated on one surface of each of the four outer-layer expanded graphite sheets 21 formed in a parallelogram shape in plan view. This is applied by means of roller coating, spraying, etc., and dried at a temperature of 100 ° C. to form a coating layer 28 of solid lubricant. As shown in FIG. 17, the outer layer provided with the coating layer 28 of solid lubricant Each of the expanded graphite sheets 21 for use is sandwiched between the two plain weave wire meshes 17 so that the hypotenuses 18 and 20 are aligned with each other, and then, as shown in FIG. 18, the expanded graphite sheet 21 and the two plain weave wire meshes 17. Is pressed with a pair of rollers 22 and 23, and as shown in FIG. 19, the mesh 16 of the plain weave wire mesh 17 is filled with the expanded graphite of the expanded graphite sheet 21 and the solid lubricant of the coating layer 28, Adjacent to adjacent vertical lines 14 Each of the intersection groups 19a, 19b, 19c and 19d at each mesh 16 in the intersection groups 19a, 19b, 19c and 19d of the vertical line 14 and the horizontal line 15 has a square mesh 16 surrounded by the horizontal line 15. One intersection group 19a and 19d located on one of the pair of diagonal lines connecting the two is arranged in the width direction X, and the other intersection group 19b and 19c located on the other diagonal line is arranged in the longitudinal direction Y The surface 24 of the plain weave wire mesh 17 and the surface 25a of the solid lubricant filled in the mesh 16 of the plain weave wire mesh 17 are exposed and parallel four sides in plan view having both ends composed of the oblique sides 26 and 26 inclined in the same oblique direction. The outer layer forming member 27a having a shape is formed.

<Third method>
Each of the aqueous dispersions (1) to (4) is brush-coated, roller-coated, sprayed, etc. on one surface of each of the four parallelogram-shaped outer layer forming members 27 obtained in the first method. The solid lubricant coating layer 28 is formed by drying at a temperature of 100 ° C. and covering the surface of the expanded graphite sheet 21 and the surface of the plain weave wire mesh 17. An outer layer forming member (not shown) having a parallelogram shape in a plan view and exposed is formed.

  In the first, second and third methods, the gap Δ1 between the pair of rollers 22 and 23 is suitably about 0.4 to 0.6 mm.

(Ninth process)
The outer layer forming member 27 obtained in this way is one surface thereof, and the outer layer forming member 27a is the one surface where the surface 25a of the solid lubricant and the surface 24 of the plain weave wire mesh 17 are exposed or an outer layer forming member (not shown). As shown in FIGS. 20 and 21, the exposed surface of the coating layer 28 of the solid lubricant is arranged on the outer peripheral surface of the cylindrical base material 13 and slightly between the hypotenuses 26 and 26 at both ends in the circumferential direction. A pre-cylindrical molded body 29 wound with a gap is formed.

(10th process)
The inner wall includes a cylindrical wall surface 30, a partially concave spherical wall surface 31 continuous to the cylindrical wall surface 30, and a through hole 32 continuous to the partially concave spherical wall surface 31. A hollow core 33 is hollowed by inserting a stepped core 33 into the through hole 32. A mold 36 shown in FIG. 22 in which a cylindrical portion 34 and a spherical hollow portion 35 continuous with the hollow cylindrical portion 34 are formed is prepared, and a preliminary cylindrical molded body 29 is inserted into the stepped core 33 of the mold 36.

A pre-cylindrical molded body 29 disposed in the hollow cylindrical portion 34 and the spherical belt-shaped hollow portion 35 of the mold 36 is compression-molded in the axial direction Z at a pressure of 98 to 294 N / mm ² (1 to 3 ton / cm ² ), As shown in FIGS. 1 to 3 and FIGS. 23 and 24, a through hole 37 defined by a cylindrical inner surface 38 is provided at the center, and the cylindrical inner surface 38, the partially convex spherical surface 39, and the partially convex spherical surface 39 are formed. A spherical belt-like sealing body comprising a spherical belt-like base body 42 defined by the annular end surfaces 40 and 41 on the large-diameter side and the small-diameter side, and an outer layer 43 formed integrally with the partially convex spherical surface 39 of the spherical belt-like base body 42. 44 is produced.

  By this compression molding, in the ball-shaped seal body 44 in the first method, as shown in FIGS. 2 and 3, the mesh of the metal mesh 5 and the mesh of the metal mesh 5 is filled and integrated with the metal mesh 5. The spherical band-shaped substrate 42 provided with the expanded graphite sheet 6 is formed such that the expanded graphite sheet 6 and the wire mesh 5 are compressed and entangled with each other to have structural integrity, and the outer layer 43 has a rectangular shape. One of a group of intersecting points 19a and 19d located on one of the pair of diagonal lines connecting the intersecting points of the adjacent vertical lines 14 and the adjacent horizontal lines 15 forming the mesh 16 is arranged in the axial direction Z. The crossing point groups 19b and 19c located on the other diagonal line of the pair of diagonal lines are composed of a plain woven wire mesh 17 arranged in the circumferential direction R and compressed, and the plain woven wire mesh 17 of this reinforcing material Fills mesh 16 And a heat-resistant material containing expanded graphite that is compressed together with the reinforcing material and integrated with the reinforcing material, and the outer surface 45 of the outer layer 43 is made of a heat-resistant material containing the expanded graphite sheet 21. A smooth surface in which the surface 46 and the reinforcing material surface 47 made of a plain woven wire mesh 17 in which the intersection groups 19a and 19d are arranged in the axial direction Z and the intersection groups 19b and 19c are arranged in the circumferential direction R are exposed. The surface 47 at the intersection groups 19a and 19d and 19b and 19c is preferably 10 to 65%, more preferably 15 to 60% with respect to the entire outer surface 45 of the outer layer 43. It is exposed with an area ratio.

  Further, by this compression molding, in the ball-shaped seal body 44 in the second method, as shown in FIG. 23, the expansion of the metal mesh 5 and the mesh of the metal mesh 5 is filled and integrated with the metal mesh 5. The spherical base 42 having the graphite sheet 6 is formed such that the expanded graphite sheet 6 and the wire mesh 5 are compressed and entangled with each other to have structural integrity, and the outer layer 43 has a square mesh. While intersecting point groups 19a and 19d located on one of the pair of diagonal lines connecting the intersecting points of the adjacent vertical lines 14 and the adjacent horizontal lines 15 forming 16 are arranged in the axial direction Z, The intersection group 19b and 19c located on the other diagonal line of the pair of diagonal lines is composed of a plain woven wire mesh 17 arranged in the circumferential direction R and is compressed, and the mesh of the plain woven wire mesh 17 of the reinforcing material 16 And expanded graphite which is compressed together with the reinforcing material and mixed and integrated with the reinforcing material, and a solid lubricant, and the outer surface 45 of the outer layer 43 includes a surface 49 made of a solid lubricant, Intersection groups 19a and 19d are arranged in the axial direction Z, and the planes 50 of the reinforcing material made of plain woven wire mesh 17 in which the intersection groups 19b and 19c are arranged in the circumferential direction R are mixed and exposed to form a smooth surface 50. The surface 47 at the intersection groups 19a and 19b and 19b and 19c preferably has an area ratio of 10 to 65%, more preferably 15 to 60% with respect to the entire outer surface 45 of the outer layer 43. Exposed.

  Further, by this compression molding, in the ball-shaped seal body 44 in the third method, the mesh of the metal mesh 5 and the mesh of the metal mesh 5 is filled and integrated with the metal mesh 5 as shown in FIG. The spherical band-shaped substrate 42 provided with the expanded graphite sheet 6 is formed such that the expanded graphite sheet 6 and the wire mesh 5 are compressed and entangled with each other to have structural integrity, and the outer layer 43 has a rectangular shape. One of a group of intersecting points 19a and 19d located on one of the pair of diagonal lines connecting the intersecting points of the adjacent vertical lines 14 and the adjacent horizontal lines 15 forming the mesh 16 is arranged in the axial direction Z. The intersecting point groups 19b and 19c located on the other diagonal line of the pair of diagonal lines are composed of the plain weave wire mesh 17 arranged in the circumferential direction R and compressed, and the plain weave wire mesh 17 of the reinforcement material In mesh 16 An expanded graphite that is filled and integrated with the reinforcing material, and a solid lubricant that covers the surface 46 of the expanded and integrated graphite and the surface 47 of the plain weave wire mesh 17. The outer surface 45 of 43 is a smooth surface 54 with the surface 53 of the solid lubricant exposed.

  In the fourth step, instead of winding the polymer 12 in a spiral shape with the expanded graphite sheet 6 on the inside, the polymer base 12 is wound in a spiral shape with the wire mesh 5 made of the belt-like wire mesh 4 inside. When formed, the ball-shaped seal body 44 in which the reinforcing material made of the wire mesh 5 is exposed on the cylindrical inner surface 38 of the ball-shaped base 42 can be produced.

  In the exhaust pipe spherical joint shown in FIG. 29 in which the ball-shaped seal body 44 is incorporated, the flange 200 stands on the outer peripheral surface of the upstream exhaust pipe 100 connected to the engine side, leaving the pipe end portion 101. A spherical band-shaped seal body 44 is fitted to the tube end portion 101 at a cylindrical inner surface 38 that defines the through hole 37, and the spherical band-shaped seal body 44 is flanged 200 on the large-diameter annular end surface 40. Is connected to the upstream exhaust pipe 100 and connected to the muffler side, and is connected to the concave spherical surface portion 302 and the concave spherical surface portion 302. The enlarged diameter portion 301 integrally provided with the flange portion 303 is fixed, and the inner surface 304 of the concave spherical surface portion 302 is a smooth surface 48, 50 or the outer surface 45 of the outer layer 43 of the ball-shaped seal body 44. It is in sliding contact with the 4.

  In the exhaust pipe spherical joint shown in FIG. 29, a pair of bolts 400 having one end fixed to the flange 200 and the other end inserted through the flange portion 303 of the enlarged diameter portion 301 and the enormous head and flange portion of the bolt 400. A spring force is always applied to the downstream side exhaust pipe 300 in the direction of the upstream side exhaust pipe 100 by the pair of coil springs 500 arranged between 303. The exhaust pipe spherical joint has a smooth surface 48, 50 or 54 as a sliding surface of the outer layer 43 of the ball-shaped seal body 44 and a downstream side against a relative angular displacement occurring in the upper and downstream exhaust pipes 100, 300. This is allowed by sliding contact with the inner surface 304 of the concave spherical portion 302 of the enlarged diameter portion 301 formed at the end of the side exhaust pipe 300.

  Next, the present invention will be described in detail based on examples. The present invention is not limited to these examples.

Example 1
Using a single austenitic stainless steel wire (SUS304) with a wire diameter of 0.28 mm as a thin metal wire, a cylindrical braided wire net having a mesh width of 4 mm and a width of 5 mm is produced, and this is placed between a pair of rollers. A belt-like wire mesh was made to pass through, and this was made a wire mesh as a reinforcing material for a spherical belt-like substrate. As the heat-resistant material, an expanded graphite sheet (heat-resistant material I) having a density of 1.12 Mg / m ³ and a thickness of 0.38 mm was used. A cylindrical base material in which an expanded graphite sheet is wound in a spiral shape, and then a wire mesh for a spherical belt-like substrate is superimposed on the inner side of the expanded graphite sheet, and the expanded graphite sheet is positioned on the outermost periphery by winding in a spiral shape. Was made. In this cylindrical base material, both end portions in the width direction of the expanded graphite sheet protrude (extrude) in the width direction of the wire net for the spherical base.

  Using a plain woven wire mesh woven with a square mesh having a mesh width of 1.5 mm and a width of 1.5 mm using a metal fine wire having the same wire diameter of 0.28 mm as described above, both ends faced in the same direction. One intersection group located on one diagonal line of a pair of diagonal lines having diagonal sides and connecting the intersection points of adjacent vertical lines and adjacent horizontal lines is arranged in the width direction and positioned on the other diagonal line Thus, a reinforcing material for an outer layer made of a plain woven wire mesh shown in FIG. 26 having a parallelogram shape in plan view in which the other intersection group is arranged in the longitudinal direction was produced.

  Using an expanded graphite sheet similar to the expanded graphite sheet, an expanded graphite sheet for outer layers having a parallelogram shape in plan view having the same shape as the reinforcing material for outer layers was produced.

  Such an expanded graphite sheet for the outer layer is inserted between the two plain outer wire meshes for the outer layer so that each side is matched, and then the expanded graphite sheet for the outer layer and the two plain weave metal meshes are paired with a pair of rollers. Pressurized, flattened with a plain woven wire mesh filled with expanded graphite, the surface of the plain woven wire mesh and the surface of the expanded graphite filled with the mesh of the plain woven wire mesh are exposed and both ends are oriented in the same oblique direction. An outer layer forming member having a parallelogram shape in plan view having an oblique side was formed.

  The outer layer forming member is placed on the outer peripheral surface of the cylindrical base material, and the outer surface of the cylindrical base material is exposed between the plain weave wire mesh surface and the expanded graphite surface. The outer layer forming member was wound while maintaining a slight gap in the circumferential direction to prepare a preliminary cylindrical molded body.

After inserting the preliminary cylindrical molded body into the stepped core of the mold and placing the preliminary cylindrical molded body in the hollow portion of the mold, the preliminary cylindrical molded body was axially moved to 294 N / mm ² (3 ton / cm ² ) And a spherically shaped base defined by a cylindrical inner surface, a partially convex spherical surface, and a large-diameter and small-diameter annular end surface of the partially convex spherical surface, and a partially convex spherical shape of the spherically shaped substrate. A spherical belt-like seal body provided with an outer layer integrally formed on the surface was obtained.

  In the obtained spherical belt-shaped sealing body, the spherical belt-shaped substrate is formed such that a heat-resistant material containing expanded graphite and a reinforcing material made of a wire mesh are compressed and intertwined with each other, and the outer layer is formed. The expanded graphite for the outer layer and the reinforcing material made of plain woven wire mesh are compressed, and the expanded graphite for the outer layer is filled into the mesh of the reinforcing material, and the reinforcing material and the heat-resistant material are mixed and integrated. One of the outer surfaces is located on one of a pair of diagonal lines connecting the intersections of the surface of the heat-resistant material made of expanded graphite and the adjacent vertical lines forming the rectangular mesh and the adjacent horizontal lines Are formed as a smooth surface that is exposed in a mixed manner with a surface of a reinforcing material made of plain woven wire mesh in which the other intersection group located on the other diagonal line is arranged in the circumferential direction. The outer surface of the outer layer is a plain woven wire mesh for the outer layer. That the surface of the reinforcing member was exposed throughout with an area ratio of 41% with respect to the outer surface of the outer surface.

Example 2
Using a plain woven wire mesh having a square mesh having a mesh width of 2.0 mm in length and 2.0 mm in width woven using the same fine metal wires as in Example 1, the outer layer similar to that in Example 1 is used for the outer layer. A reinforcing material was produced, and an outer layer forming member having a parallelogram shape in plan view was formed from the reinforcing material for the outer layer and the expanded graphite sheet for the outer layer similar to Example 1 in the same manner as in Example 1. A spherical belt-like sealing body similar to that in Example 1 was obtained in the same manner as in Example 1. In the obtained spherical belt-shaped sealing body, the surface of the plain woven wire mesh was exposed on the outer surface of the outer layer with an area ratio of 34% with respect to the entire outer surface.

Example 3
As the heat-resistant material for the outer layer, an expanded graphite sheet (heat-resistant material I) having a density of 0.5 Mg / m ³ and a thickness of 1.00 mm is used, and has the same shape as the reinforcing material for the outer layer similar to Example 1. An expanded graphite sheet for an outer layer having a parallelogram shape in plan view is produced, and the parallelogram shape in plan view is obtained in the same manner as in Example 1 from the expanded graphite sheet for outer layer and the reinforcing material for outer layer similar to Example 1. The outer layer forming member was formed, and the same spherical belt-like sealing body as in Example 1 was obtained in the same manner as in Example 1. In the obtained spherical belt-shaped sealing body, the surface of the plain woven wire mesh was exposed on the outer surface of the outer layer with an area ratio of 32% with respect to the entire outer surface.

Example 4
Using a plain woven wire mesh having a square mesh having a mesh width of 2.5 mm and a width of 2.5 mm woven using the same fine metal wire as in Example 1, the outer layer similar to that in Example 1 is used for the outer layer. A reinforcing material is produced, and the outer layer having a parallelogram shape in plan view is formed from the reinforcing material for the outer layer similar to that of Example 1 and the expanded graphite sheet for the outer layer similar to that of Example 3 in the same manner as in Example 1. A member was formed, and a spherical belt-like sealing body similar to that in Example 1 was obtained in the same manner as in Example 1 below. In the obtained spherical belt-shaped sealing body, the surface of the reinforcing material made of plain woven wire mesh for the outer layer was exposed on the outer surface with an area ratio of 27% with respect to the entire outer surface. .

Example 5
Using a plain woven wire mesh having a square mesh having a mesh width of 3.0 mm and a width of 3.0 mm woven using the same fine metal wires as in Example 1, the outer layer similar to that in Example 1 is used for the outer layer. A reinforcing material is prepared, and an outer layer forming member having a parallelogram shape in plan view is formed from the reinforcing material for the outer layer similar to Example 1 and the expanded graphite sheet similar to Example 1 in the same manner as in Example 1. Thereafter, the same spherical belt-like sealing body as in Example 1 was obtained in the same manner as in Example 1. In the obtained spherical belt-shaped sealing body, the surface of the reinforcing material made of plain woven wire mesh for the outer layer was exposed on the outer surface at an area ratio of 25% with respect to the entire outer surface. .

Example 6
Using a plain woven wire mesh woven with a square mesh having a mesh width of 1.5 mm and a width of 1.5 mm using the same austenitic stainless steel wire as in Example 1 having a wire diameter of 0.32 mm as a thin metal wire Then, a reinforcing material for the outer layer similar to that of Example 1 is produced, and an outer layer having a parallelogram shape in plan view is formed from the reinforcing material for the outer layer and the expanded graphite sheet similar to that of Example 1 in the same manner as in Example 1. A member was formed, and a spherical belt-like sealing body similar to that in Example 1 was obtained in the same manner as in Example 1 below. In the obtained spherical belt-shaped sealing body, the surface of the reinforcing material made of plain woven wire mesh for the outer layer was exposed on the outer surface at an area ratio of 45% with respect to the entire outer surface. .

Example 7
Using the same austenitic stainless steel wire as in Example 6 and a plain woven wire mesh woven with a square mesh having a mesh width of 2.0 mm in length and 2.0 mm in width, the same for the outer layer as in Example 1 A planar parallelogram-shaped reinforcing material is produced in the same manner as in Example 1 from the outer layer reinforcing material and an expanded graphite sheet for the parallelogram-like outer layer in planar view similar to Example 1. A parallelogram-shaped outer layer forming member was formed, and a spherical belt-like sealing body similar to that in Example 1 was obtained in the same manner as in Example 1 below. In the obtained spherical belt-shaped sealing body, the surface of the reinforcing material made of plain woven wire mesh for the outer layer was exposed on the outer surface with an area ratio of 39% with respect to the entire outer surface. .

Example 8
Using the same austenitic stainless steel wire as in Example 6 and using a plain woven wire mesh woven with a square mesh having a mesh width of 2.5 mm and a width of 2.5 mm, the outer layer is the same as in Example 1. And forming an outer layer forming member having a parallelogram shape in plan view in the same manner as in Example 1 from the reinforcing material for outer layer and the expanded graphite sheet for outer layer similar to Example 1. In the same manner as in Example 1, the same spherical belt-like sealing body as in Example 1 was obtained. In the obtained spherical belt-shaped sealing body, the surface of the reinforcing material composed of a plain woven wire mesh for the outer layer was exposed on the outer surface at an area ratio of 31% with respect to the entire outer surface. .

Example 9
Using the same austenitic stainless steel wire as in Example 6 and a plain woven wire mesh woven with a square mesh having a mesh width of 3.0 mm and a width of 3.0 mm, the outer layer is the same as in Example 1. And forming an outer layer forming member having a parallelogram shape in plan view in the same manner as in Example 1 from the reinforcing material for outer layer and the expanded graphite sheet for outer layer similar to Example 1. In the same manner as in Example 1, the same spherical belt-like sealing body as in Example 1 was obtained. In the obtained spherical belt-shaped sealing body, the surface of the reinforcing material made of plain woven wire mesh for the outer layer was exposed on the outer surface at an area ratio of 25% with respect to the entire outer surface. .

Example 10
Using a plain woven wire mesh woven with a square mesh having a mesh width of 1.5 mm and a width of 1.5 mm using the same austenitic stainless steel wire as in Example 1 having a wire diameter of 0.15 mm as a thin metal wire. Then, a reinforcing material for the outer layer similar to that in Example 1 was produced, and the parallelogram shape in plan view was obtained in the same manner as in Example 1 from the reinforcing material for such outer layer and the expanded graphite sheet for outer layer similar to that in Example 1. The outer layer forming member was formed, and the same spherical belt-like sealing body as in Example 1 was obtained in the same manner as in Example 1. In the obtained spherical belt-shaped sealing body, the surface of the reinforcing material made of plain woven wire mesh for the outer layer was exposed on the outer surface at an area ratio of 25% with respect to the entire outer surface. .

Example 11
Similar to Example 1 produced using a plain weave wire mesh woven with a square mesh having a mesh width of 2.0 mm and a width of 2.0 mm using the same austenitic stainless steel wire as in Example 10. An outer layer forming member having a parallelogram shape in plan view is formed from the reinforcing material for the outer layer and the expanded graphite sheet for the outer layer similar to that in Example 1 in the same manner as in Example 1. Hereinafter, the same method as in Example 1 is used. A spherical belt-like seal body similar to that of Example 1 was obtained. In the obtained spherical belt-shaped sealing body, the surface of the reinforcing material made of plain woven wire mesh for the outer layer was exposed on the outer surface with an area ratio of 21% with respect to the entire outer surface. .

Example 12
Similar to Example 1 formed using a plain weave wire mesh woven with a square mesh having a mesh width of 2.5 mm and a width of 2.5 mm using the same austenitic stainless steel wire as in Example 10. An outer layer forming member having a parallelogram shape in plan view is formed from the reinforcing material for the outer layer and the expanded graphite sheet similar to that of the first embodiment in the same manner as in the first embodiment. The same spherical belt-like seal body was obtained. In the obtained spherical belt-shaped sealing body, the surface of the reinforcing material made of a plain woven wire mesh for the outer layer was exposed on the outer surface at an area ratio of 18% with respect to the entire outer surface. .

Example 13
Using the same austenitic stainless steel wire as in Example 10 and using a plain woven wire mesh woven with a square mesh having a mesh width of 3.0 mm and a width of 3.0 mm, the same outer layer as in Example 1 In the same manner as in Example 1, an outer layer forming member having a parallelogram shape in plan view is formed from the reinforcing material for outer layer and the expanded graphite sheet similar to that of Example 1, and hereinafter, Examples 1 was obtained in the same manner as in Example 1. In the obtained spherical belt-shaped sealing body, the surface of the reinforcing material made of plain woven wire mesh for the outer layer was exposed on the outer surface at an area ratio of 15% with respect to the entire outer surface. .

Example 14
Using a plain woven wire mesh woven with a square mesh having a mesh width of 2.0 mm and a width of 2.0 mm using the same austenitic stainless steel wire as in Example 1 having a wire diameter of 0.42 mm as the metal thin wire. Then, a reinforcing material for the outer layer similar to that in Example 1 was produced, and the parallelogram shape in plan view was obtained in the same manner as in Example 1 from the reinforcing material for such outer layer and the expanded graphite sheet for outer layer similar to that in Example 1. The outer layer forming member was formed, and the same spherical belt-like sealing body as in Example 1 was obtained in the same manner as in Example 1. In the obtained spherical belt-shaped sealing body, the surface of the reinforcing material made of plain woven wire mesh for the outer layer was exposed on the outer surface at an area ratio of 45% with respect to the entire outer surface. .

Example 15
Using a plain woven wire mesh woven with a square mesh having a mesh width of 1.5 mm and a width of 1.5 mm using the same austenitic stainless steel wire as in Example 1 having a wire diameter of 0.50 mm as a thin metal wire. Then, a reinforcing material for the outer layer similar to that in Example 1 was produced, and the parallelogram shape in plan view was obtained in the same manner as in Example 1 from the reinforcing material for such outer layer and the expanded graphite sheet for outer layer similar to that in Example 1. The outer layer forming member was formed, and the same spherical belt-like sealing body as in Example 1 was obtained in the same manner as in Example 1. In the obtained spherical belt-shaped sealing body, the surface of the reinforcing material composed of a plain woven wire mesh for the outer layer was exposed on the outer surface at an area ratio of 60% with respect to the entire outer surface. .

  In the above Examples 2 to 15, the outer layer is compressed with the expanded graphite for the outer layer and the reinforcing material made of plain woven wire mesh, and the expanded graphite for the outer layer is filled in the reinforcing material mesh, The outer surface of the outer layer is formed of a pair of diagonal lines connecting the intersections of the heat-resistant material made of expanded graphite and the adjacent vertical lines and the adjacent horizontal lines of the square mesh. One intersection group located on one diagonal line is arranged in the axial direction, and the surface of the reinforcing material consisting of a plain woven wire mesh for the outer layer in which the other intersection group located on the other diagonal line is arranged in the circumferential direction. It is a smooth surface that is exposed in a mixed manner.

Example 16
An interface with 25% by mass of PTFE powder having an average particle size of 0.20 μm, 15% by mass of FEP powder having an average particle size of 0.15 μm, and 39% by mass of a lubricating composition powder containing 60% by mass of h-BN powder having an average particle size of 8 μm Aqueous dispersion (PTFE 9.75 mass%, FEP 5.85 mass% and h-BN 23.4 mass%) comprising 4 mass% of polyoxyethylene alkyl ether (nonionic surfactant) and 57 mass% of water as an activator. 4% by weight of a nonionic surfactant and 57% by weight of water) are applied to one surface of an expanded graphite sheet for an outer layer similar to that of Example 1, dried at a temperature of 100 ° C., and dried with PTFE, FEP and A coating layer of a solid lubricant (25% by mass of PTFE, 15% by mass of FEP and 60% by mass of h-BN) made of a lubricating composition of h-BN is formed, and for an outer layer provided with such a coating layer A parallelogram shape in plan view in the same manner as in Example 1 from the reinforcing material for the outer layer similar to that in Example 1 produced using the tension graphite sheet and the plain woven wire mesh having the same square mesh as in Example 2. The outer layer forming member is formed, and the outer layer forming member is formed on the outer peripheral surface of the cylindrical base material in the same manner as in Example 1 with the surface exposed by mixing the plain weave wire mesh surface and the solid lubricant surface facing outside. A pre-cylindrical molded body was produced by winding, and a spherical belt-shaped sealing body was obtained in the same manner as in Example 1 below. In the obtained spherical belt-shaped sealing body, the outer layer is expanded graphite and a reinforcing material composed of a plain woven wire mesh, and the expanded graphite and PTFE are 25% by mass, FEP 15% by mass and h-BN 60% by mass. % Of the expanded graphite and the solid lubricant are mixed and integrated, and the outer surface of the outer layer has a reinforcing material made of a plain woven wire mesh for the outer layer. It was exposed on the outer surface with an area ratio of 36% with respect to the whole.

Example 17
39% by mass of powder for solid lubricant containing 12% by mass of PTFE powder having an average particle size of 0.20 μm, 28% by mass of FEP powder having an average particle size of 0.15 μm and 60% by mass of h-BN powder having an average particle size of 8 μm; Aqueous dispersion (PTFE 4.68% by mass, FEP 10.92% by mass and h-BN 23.4% by mass) comprising 4% by mass of polyoxyethylene alkyl ether (nonionic surfactant) as a surfactant and 57% by mass of water. %, Nonionic surfactant 4% by mass, water 57% by mass) on one surface of the expanded graphite sheet for the outer layer as in Example 3, and in the same manner as in Example 16, PTFE, FEP And a coating layer of a solid lubricant (PTFE 12 mass%, FEP 28 mass% and h-BN 60 mass%) comprising a lubricating composition of h-BN, and an outer layer provided with such a coating layer In the same manner as in Example 1, the parallelogram in plan view was obtained from the expanded graphite sheet of Example 2 and the reinforcing material having a parallelogram shape in plan view for the outer layer produced using a plain weave wire mesh having the same square mesh as in Example 2. An outer layer forming member having a shape was formed, and a spherical belt-like sealing body was obtained in the same manner as in Example 16. In the obtained spherical belt-shaped sealing body, the outer layer is a solid containing expanded graphite and PTFE 12% by mass, FEP 28% by mass and h-BN 60% by mass in which the expanded graphite for the outer layer and the plain woven wire mesh are compressed. Filled with lubricant, the expanded graphite and solid lubricant are mixed and integrated. On the outer surface of the outer layer, the surface of the reinforcing material composed of a plain woven wire mesh for the outer layer is relative to the entire outer surface of the outer layer. It was exposed on the outer surface of the outer layer with an area ratio of 32%.

Example 18
39% by mass of powder for solid lubricant containing 10% by mass of PTFE powder having an average particle size of 0.20 μm, 40% by mass of FEP powder having an average particle size of 0.15 μm and 50% by mass of h-BN powder having an average particle size of 8 μm; Aqueous dispersion (PTFE 3.9% by mass, FEP 15.6% by mass and h-BN 19.5% by mass) comprising 4% by mass of polyoxyethylene alkyl ether (nonionic surfactant) and 57% by mass of water as a surfactant. %, Nonionic surfactant 4 mass%, water 57 mass%) on one surface of the expanded graphite sheet for the outer layer as in Example 4, and coated with PTFE, FEP in the same manner as in Example 16. And a solid lubricant (PTFE 10% by mass, FEP 40% by mass and h-BN 50% by mass) comprising a lubricating composition of h-BN, and for an outer layer provided with such a coating layer In the same manner as in Example 1, a parallelogram shape in plan view is obtained from the reinforcing material for the outer layer similar to that of Example 1 manufactured using the tension graphite sheet and the plain woven wire mesh having the same square mesh as in Example 4. The outer layer forming member was formed, and a spherical belt-like sealing body was obtained in the same manner as in Example 16. In the obtained spherical belt-shaped sealing body, the outer layer is a solid containing expanded graphite and plain woven wire mesh for outer layer compressed so that the expanded woven wire mesh mesh contains expanded graphite and PTFE 10% by mass, FEP 40% by mass and h-BN 50% by mass. Filled with lubricant, the expanded graphite and solid lubricant are mixed and integrated. On the outer surface of the outer layer, the surface of the reinforcing material composed of a plain woven wire mesh for the outer layer is relative to the entire outer surface of the outer layer. It was exposed on the outer surface of the outer layer with an area ratio of 25%.

Example 19
39% by mass of powder for solid lubricant containing 20% by mass of PTFE powder having an average particle size of 0.20 μm, 40% by mass of FEP powder having an average particle size of 0.15 μm and 40% by mass of h-BN powder having an average particle size of 8 μm; Aqueous dispersion (PTFE 7.8% by mass, FEP 15.6% by mass and h-BN 15.6% by mass) comprising 4% by mass of polyoxyethylene alkyl ether (nonionic surfactant) and 57% by mass of water as a surfactant. %, Nonionic surfactant 4% by mass, water 57% by mass) on one surface of the expanded graphite sheet for the outer layer as in Example 1, and in the same manner as in Example 16, PTFE, FEP And a coating layer of a solid lubricant (PTFE 20% by mass, FEP 40% by mass and h-BN 40% by mass) comprising a lubricating composition of h-BN, and for an outer layer provided with such a coating layer A parallelogram shape in plan view in the same manner as in Example 1 from the reinforcing material for the outer layer similar to that of Example 1 produced using the tension graphite sheet and the plain woven wire mesh having the same square mesh as in Example 7. The outer layer forming member was formed, and a spherical belt-like sealing body was obtained in the same manner as in Example 16. In the obtained spherical belt-like sealing body, the outer layer is a solid containing expanded graphite and 20% by mass of PTFE, 40% by mass of FFE, and 40% by mass of h-BN, by compressing the expanded graphite and plain woven wire mesh for the outer layer. Filled with lubricant, the expanded graphite and solid lubricant are mixed and integrated. On the outer surface of the outer layer, the surface of the reinforcing material composed of a plain woven wire mesh for the outer layer is relative to the entire outer surface of the outer layer. It was exposed on the outer surface of the outer layer with an area ratio of 42%.

Example 20
39% by mass of powder for solid lubricant containing 38% by mass of PTFE powder having an average particle size of 0.20 μm, 22% by mass of FEP powder having an average particle size of 0.15 μm, and 40% by mass of h-BN powder having an average particle size of 8 μm; Aqueous dispersion (PTFE 14.82% by mass, FEP 8.58% by mass, and h-BN 15.6% by mass) comprising 4% by mass of polyoxyethylene alkyl ether (nonionic surfactant) as a surfactant and 57% by mass of water. %, Nonionic surfactant 4% by mass, water 57% by mass) on one surface of the expanded graphite sheet for the outer layer as in Example 1, and PTFE, FEP and Forming a coating layer of solid lubricant (38% by mass of PTFE, 22% by mass of FEP and 40% by mass of h-BN) comprising a lubricating composition of h-BN, and for an outer layer provided with such a coating layer From the expanded graphite sheet and the reinforcing material for the outer layer similar to Example 1 manufactured using the plain woven wire mesh having the same square mesh as in Example 11, the parallelogram shape in plan view was the same as in Example 1. The outer layer forming member was formed, and a spherical belt-like sealing body was obtained in the same manner as in Example 16. In the obtained spherical belt-shaped sealing body, the outer layer is a solid containing expanded graphite and a plain woven wire mesh compressed for outer layer, and the expanded woven wire mesh mesh contains expanded graphite and 38% by mass of PTFE, 22% by mass of FEP and 40% by mass of h-BN. Filled with lubricant, the expanded graphite and solid lubricant are mixed and integrated. On the outer surface of the outer layer, the surface of the reinforcing material composed of a plain woven wire mesh for the outer layer is relative to the entire outer surface of the outer layer. The area ratio of 22% was exposed on the outer surface of the outer layer.

Example 21
39% by mass of powder for solid lubricant containing 35% by mass of PTFE powder having an average particle size of 0.20 μm, 15% by mass of FEP powder having an average particle size of 0.15 μm and 50% by mass of h-BN powder having an average particle size of 8 μm; Aqueous dispersion (PTFE 13.65% by mass, FEP 5.85% by mass and h-BN 19.5% by mass) comprising 4% by mass of polyoxyethylene alkyl ether (nonionic surfactant) and 57% by mass of water as a surfactant. %, Nonionic surfactant 4% by mass, water 57% by mass) on one surface of the expanded graphite sheet for the outer layer as in Example 1, and PTFE, FEP and Forming a coating layer of a solid lubricant (PTFE 35% by mass, FEP 15% by mass and h-BN 50% by mass) comprising a lubricating composition of h-BN, and for an outer layer provided with such a coating layer From the expanded graphite sheet and the reinforcing material for the outer layer similar to Example 1 manufactured using the plain woven wire mesh having the same square mesh as in Example 2, the parallelogram shape in plan view is the same as in Example 1. The outer layer forming member was formed, and a spherical belt-like sealing body was obtained in the same manner as in Example 16. In the obtained spherical belt-shaped sealing body, the outer layer is a solid containing expanded graphite and PTFE 35% by mass, FEP 15% by mass and h-BN 50% by mass in which the expanded graphite for the outer layer and the plain woven wire mesh are compressed. Filled with a lubricant, the expanded graphite and the solid lubricant are mixed and integrated.On the outer surface of the outer layer, the one intersection group is arranged in the axial direction, and the other intersection group is arranged in the circumferential direction. The surface of the reinforcing material comprising the arranged plain woven wire mesh for the outer layer was exposed on the outer surface of the outer layer with an area ratio of 32% with respect to the entire outer surface of the outer layer.

Example 22
23% by mass of PTFE powder having an average particle size of 0.20 μm, 23% by mass of FEP powder having an average particle size of 0.15 μm, 47% by mass of h-BN powder having an average particle size of 8 μm, and boehmite (Al ₂ O ₃ as hydrated alumina) An aqueous solution comprising 39% by mass of powder for solid lubricant containing 7% by mass of H ₂ O), 4% by mass of polyoxyethylene alkyl ether (nonionic surfactant) as a surfactant and 57% by mass of water Dispersion (PTFE 8.97 mass%, FEP 8.97 mass%, h-BN 18.33 mass%, boehmite 2.73 mass%, nonionic surfactant 4 mass%, water 57 mass%) and Example 1 Using the same expanded graphite sheet, one surface of the expanded graphite sheet for the outer layer similar to that in Example 1 was roller-coated, and in the same manner as in Example 16, PTFE, FEP and h-BN were coated. Forming a coating layer of a solid lubricant (PTFE 23% by mass, FEP 23% by mass, h-BN 47% by mass and boemat 7% by mass) comprising a lubricating composition, and an expanded graphite sheet for an outer layer provided with such a coating layer An outer layer forming member having a parallelogram shape in plan view was obtained in the same manner as in Example 1 from the reinforcing material for outer layer similar to that in Example 1 produced using a plain weave wire mesh having the same square mesh as in Example 2. Thereafter, a spherical belt-like sealing body was obtained in the same manner as in Example 16. In the obtained spherical belt-like sealing body, the outer layer was expanded with expanded graphite and plain woven wire mesh for the outer layer, and expanded graphite and PTFE 23% by mass, FEP 23% by mass, h-BN 47% by mass and Boemat 7 The expanded lubricant and the solid lubricant are mixed and integrated with a solid lubricant containing mass%, and the outer surface of the outer layer is a surface of a reinforcing material made of a plain woven wire mesh for the outer layer. It was exposed on the outer surface of the outer layer with an area ratio of 35% with respect to the whole.

Example 23
PTFE powder 22% by mass with an average particle size of 0.20 μm, 22% by mass of FEP powder with an average particle size of 0.15 μm, 53% by mass of h-BN powder with an average particle size of 8 μm, and 3% by mass of boehmite powder as alumina hydrate. Aqueous dispersion (PTFE 8.58% by mass, FEP8) comprising 39% by mass of powder for solid lubricant, 4% by mass of polyoxyethylene alkyl ether (nonionic surfactant) as a surfactant and 57% by mass of water 58 mass%, h-BN 20.67 mass%, boehmite 1.17 mass%, nonionic surfactant 4 mass%, water 57 mass%) A solid lubricant (PTFE 22 mass%, FEP 22 mass%) comprising a lubricating composition of PTFE, FEP and h-BN in the same manner as in Example 16 h-BN 53% by mass and boehmite 3% by mass), using an expanded graphite sheet for the outer layer provided with such a coating layer, and a plain weave wire mesh having a square mesh similar to Example 2. An outer layer forming member having a parallelogram shape in plan view is formed from the manufactured reinforcing material for the outer layer similar to that in Example 1 in the same manner as in Example 1. Hereinafter, a spherical belt-like sealing body is formed in the same manner as in Example 16. Obtained. In the obtained spherical belt-shaped sealing body, the outer layer was expanded with expanded graphite and plain woven wire mesh for the outer layer, and expanded graphite and PTFE 22% by mass, FEP 22% by mass, h-BN 53% by mass and boehmite 3 The expanded lubricant and the solid lubricant are mixed and integrated with a solid lubricant containing mass%, and the outer surface of the outer layer is a surface of a reinforcing material made of a plain woven wire mesh for the outer layer. It was exposed on the outer surface of the outer layer with an area ratio of 34% with respect to the whole of the above.

Example 24
The same plane as in Example 1 using a reinforcing material for the outer layer similar to that in Example 1 and an expanded graphite sheet similar to that in Example 1 using a plain weave wire mesh having a square mesh similar to that in Example 2. An expanded graphite sheet for an outer layer having a parallelogram view shape is produced, and an outer layer forming member material having a parallelogram shape for a plan view view using the plain woven wire mesh for the outer layer and the expanded graphite sheet for the outer layer in the same manner as in Example 1. Formed. On the surface of the outer layer forming member material, the surface of the reinforcing material made of plain woven wire mesh was exposed on the surface of the outer layer forming member at an area ratio of 24%. An aqueous dispersion similar to Example 16 (PTFE 9.75 mass%, FEP 5.85 mass% and h-BN 23.4 mass%, nonionic surfactant 4 mass%, water 57 mass%) was prepared, and plain weave The outer layer forming member material having a parallelogram shape in a plan view in which the aqueous dispersion is roller-coated on one surface of the outer layer forming member material exposed at a surface ratio of 24% of the reinforcing material made of a wire mesh at a temperature of 100 ° C. Dried to form an outer layer forming member having a parallelogram shape in plan view, which is provided with a coating layer of a solid lubricant of PTFE, FEP and h-BN (PTFE 25 mass%, FEP 15 mass% and h-BN 60 mass%). An outer layer forming member provided with such a solid lubricant coating layer is wound on the outer peripheral surface of the cylindrical base material in the same manner as in Example 1 with the solid lubricant coating layer on the outside to produce a preliminary cylindrical molded body. And Lower, to obtain a spherical annular seal member in the same manner as in Example 1. In the obtained spherical belt-shaped sealing body, the outer layer is one intersection point located on one diagonal line of a pair of diagonal lines connecting the intersection points of adjacent vertical lines and adjacent horizontal lines forming a square mesh. A group of plains arranged in the axial direction, and the other intersections located on the other diagonal line are made of plain weave wire mesh arranged in the circumferential direction and compressed, and the mesh of the plain weave wire mesh of this reinforcement material It is equipped with a heat-resistant material containing expanded graphite that is filled and compressed and integrated with the reinforcing material, and a solid lubricant that covers these reinforcing material and heat-resistant material. The surface of the agent is a smooth surface exposed.

Example 25
An aqueous dispersion similar to Example 16 (PTFE 9.75% by mass, FEP 5.85% by mass and h-BN 23.4% by mass, nonionic surfactant 4% by mass, water 57% by mass) was prepared. The aqueous dispersion is roller-coated on one surface of a heat-resistant material made of an expanded graphite sheet for an outer layer having a parallelogram shape in plan view similar to that of Example 2 manufactured using the expanded graphite sheet similar to Example 1. The solid lubricant coating layer thus formed was dried at a temperature of 100 ° C. and then baked in a heating furnace at a temperature of 340 ° C. for 20 minutes. PTFE 25% by mass and FEP 15% by mass on one surface of the heat-resistant material for the outer layer % And h-BN 60% by mass of a solid lubricant fired coating layer was prepared, and an expanded graphite sheet having such a solid lubricant fired coating layer was prepared as Example 2. Each side was sandwiched between two plain quadrilateral wire meshes in a plan view in parallel with the two outer layers similar to Example 1 manufactured using a plain weave wire mesh woven with a similar square mesh. Thereafter, the expanded graphite sheet and the two plain weave wire meshes are pressed with a pair of rollers, and the plain weave wire mesh is filled with expanded graphite and a fired solid lubricant. An outer layer forming member having a parallelogram shape in plan view in which the surface of the fired solid lubricant filled in the mesh is exposed is formed, and the surface of the plain woven wire mesh and the surface of the fired solid lubricant are exposed in the outer layer forming member. A pre-cylindrical molded body was produced by winding the outer surface of the cylindrical base material in the same manner as in Example 1 with the surface facing outside, and a spherical belt-shaped sealing body was obtained in the same manner as in Example 1 below. In the obtained spherical belt-shaped sealing body, the outer layer is a fired solid lubricant containing expanded graphite and a plain woven wire mesh compressed into a mesh of the plain woven wire mesh and containing expanded graphite and PTFE 25% by mass, FEP 15% by mass and h-BN 60% by mass. The expanded graphite and the fired solid lubricant are mixed and integrated so that the surface of the reinforcing material made of plain woven wire mesh is 32% of the entire outer surface of the outer layer. It was exposed with an area ratio.

Example 26
Aqueous dispersion similar to Example 23 (PTFE 8.58% by mass, FEP 8.58% by mass, h-BN 20.67% by mass, boehmite 1.17% by mass, nonionic surfactant 4% by mass, water 57% by mass) %) Of the expanded graphite sheet for outer layer having a parallelogram shape in plan view similar to that in Example 1 produced by using the expanded graphite sheet similar to that in Example 1 and having one surface coated with a roller. After drying at a temperature of 340 ° C. for 20 minutes at a temperature of 340 ° C., and firing with a solid lubricant containing PTFE 22% by mass, FEP 22% by mass, h-BN 53% by mass and boehmite 3% by mass on one surface Example 1 in which an expanded graphite sheet for an outer layer provided with a layer was formed, and the expanded graphite sheet for the outer layer was produced using a plain woven wire mesh having a square mesh similar to Example 2. After sandwiching the same two sides between the same two sides of a plain parallel wire mesh for the outer layer in plan view, the expanded graphite sheet for the outer layer and the two plain weave wire meshes are pressed with a pair of rollers. A flat parallel plane in which the plane weave wire mesh is filled with expanded graphite and a fired solid lubricant, and the surface of the plain weave wire mesh and the face of the fired solid lubricant filled in the mesh of the plain weave wire mesh are exposed. An outer layer forming member having a shape is formed, and the outer layer forming member is formed with a surface of a reinforcing material made of plain woven wire mesh and a surface made of a fired solid lubricant mixed and exposed, and the outer peripheral surface of the cylindrical base material. Then, a preliminary cylindrical molded body wound with a slight gap in the circumferential direction between the hypotenuses at both ends was prepared, and a spherical belt-shaped sealing body was obtained in the same manner as in Example 1 below. In the obtained spherical belt-shaped sealing body, the expanded graphite and the plain woven wire mesh are compressed to expand the expanded graphite and PTFE 22% by mass, FEP 22% by mass, h-BN 53% by mass and boehmite 3% by mass. The expanded graphite and the calcined solid lubricant are mixed and integrated, and the surface of the reinforcing material made of plain weave wire mesh is formed on the entire outer surface of the outer layer. It was exposed with an area ratio of 31%.

  In each of the above Examples 16 to 23, in the obtained ball-shaped seal body, the outer surface of the outer layer is adjacent to the surface made of the solid lubricant and the adjacent vertical lines forming the square mesh. Outer layer in which one intersection group located on one of the pair of diagonal lines connecting the intersection with the horizontal line is arranged in the axial direction, and the other intersection group located on the other diagonal line is arranged in the circumferential direction The surface of the reinforcing material made of plain woven wire mesh is a smooth surface exposed in a mixed manner. In each of Examples 25 and 26, the outer surface of the outer layer was fired in the obtained spherical belt-shaped sealing body. One intersection point group located on one of the pair of diagonal lines connecting the intersections of the surface made of the solid lubricant and the adjacent vertical lines and the adjacent horizontal lines forming a square mesh is the axial direction The other intersection located on the other diagonal line There has been a smooth surface in which the surface of the reinforcing material made of a plain weave wire mesh arranged circumferentially exposed mixed.

Comparative Example 1
A heat-resistant material composed of the same expanded graphite sheet as in Example 1 was prepared separately, and a solid lubricant composed of 85% by mass of h-BN powder and 15% by mass of alumina powder as a solid content on one surface of the heat-resistant material. An aqueous dispersion (h-BN 25.5% by mass, alumina 4.5% by mass, moisture 70% by mass) dispersed by weight was applied with a roller and dried at a temperature of 100 ° C. three times. A solid lubricant coating layer (85% by mass of h-BN and 15% by mass of alumina) was formed on one surface of the heat-resistant material.

  After using austenitic stainless steel wire (SUS304) with a wire diameter of 0.28 mm to form a cylindrical braided wire net having a mesh width of 3.5 mm and a width of 2.5 mm, this is passed between rollers. A composite sheet in which a prepared wire mesh is prepared, a heat-resistant material provided with the coating layer is inserted into the wire mesh, and these are integrated by passing between rollers, and a solid lubricant and a wire mesh are mixed on one side A material was prepared. In this composite sheet material, the area ratio at which the surface of the reinforcing material was exposed together with the heat-resistant material on one surface of the composite sheet material was 43.4%.

  On the outer peripheral surface of the cylindrical base material, a pre-cylindrical molded body is produced by winding this composite sheet material with the surface where the coating layer of the solid lubricant and the metal mesh are mixed outward. A spherical band-shaped substrate formed by compression molding in the same manner as in Example 1 and defined by the cylindrical inner surface, the partially convex spherical surface, and the large-diameter and small-diameter annular end surfaces of the partially convex spherical surface; A ball-shaped seal body having an outer layer integrally formed on the convex spherical surface was obtained.

  In the obtained spherical belt-shaped sealing body, the outer layer is a solid lubrication containing expanded graphite and PTFE 60% by mass, h-BN 34% by mass and alumina 6% by mass in which the expanded graphite and the braided metal mesh are compressed. The expanded graphite and the solid lubricant are mixed and integrated, and the outer surface of the outer layer is formed from the smooth surface of the sliding layer in which the reinforcing material made of the wire mesh and the solid lubricant of the coating layer are mixed. In addition, a reinforcing material made of a wire mesh was exposed on the outer surface of the outer layer with an area ratio of 47.7% with respect to the entire outer surface of the outer layer.

Comparative Example 2
A heat-resistant material composed of the same expanded graphite sheet as in Example 1 was separately prepared, and 100 parts by mass of a solid lubricant composed of 85% by mass of h-BN powder and 15% by mass of alumina powder on one surface of the heat-resistant material. In addition, an aqueous dispersion (h-BN10.10) containing 30% by weight of a solid lubricant (h-BN 34% by mass, PTFE 60% by mass, and 6% by mass of alumina) dispersed and containing 150 parts by mass of PTFE powder as a solid content. 2 mass%, PTFE 18 mass%, alumina 1.8 mass%, moisture 70 mass%) are coated with a roller and dried at a temperature of 100 ° C. three times to repeat the coating operation three times. A lubricant coating layer (34% by mass of h-BN, 60% by mass of PTFE, and 6% by mass of alumina) was formed.

  After forming a cylindrical braided wire mesh having a mesh width of 3.5 mm and a width of 2.5 mm using an austenitic stainless steel wire (SUS304) having a wire diameter of 0.28 mm as in Example 1. A belt-shaped wire mesh produced by passing between the rollers is prepared, a heat-resistant material provided with the coating layer is inserted into the belt-shaped wire mesh, and these are integrated by passing between the rollers. A composite sheet material mixed with and was prepared. In this composite sheet material, the area ratio at which the surface of the reinforcing material was exposed together with the surface of the heat resistant material on one surface of the composite sheet material was 43.2%.

  A pre-cylindrical molded body is produced by winding the composite sheet material around the outer peripheral surface of the cylindrical base material with the surface where the coating layer of the solid lubricant and the wire mesh are mixed outward. And a spherically shaped base defined by a cylindrical inner surface, a partially convex spherical surface, a large-diameter side and a small-diameter annular end surface of the partially convex spherical surface, and a partially convex spherical surface of the spherically-shaped substrate. A spherical belt-like sealing body provided with an outer layer integrally formed on the surface.

  In the obtained spherical band-shaped sealing body, a spherical band-shaped reinforcing material made of compressed wire mesh, and a sphere made of expanded graphite which is packed together with the reinforcing material mesh and is compressed integrally with the reinforcing material. The outer layer surface is a smooth surface of a sliding layer in which a reinforcing material and a solid lubricant are mixed, and the outer surface of the outer layer is a reinforcement made of a wire mesh. The material was exposed with an area ratio of 51.8% with respect to the entire surface of the outer layer.

  As a reinforcing material for the composite sheet material in Comparative Examples 1 and 2, a braided wire mesh was used as shown in FIG.

Comparative Example 3
A heat-resistant material composed of the same expanded graphite sheet as in Example 1 was separately prepared, and a coating layer of solid lubricant (h-BN 34 mass%, PTFE 60 mass% and alumina similar to Comparative Example 2) was formed on one surface of the heat-resistant material. 6% by mass).

  A plain woven wire mesh forming a square mesh having a mesh width of 2.0 mm in length and 2.0 mm in width woven using the same fine metal wires as in Example 1, as shown in FIG. The reinforcing material for the rectangular outer layer was produced using the horizontal lines in parallel with the longitudinal direction.

  Using a heat-resistant material made of an expanded graphite sheet similar to that in Example 1, a heat-resistant material for a rectangular outer layer was produced.

  One surface of such an expanded graphite sheet is coated with an aqueous dispersion made of the same solid lubricant as in Comparative Example 2, and coated with a solid lubricant containing 34% by mass of h-BN, 60% by mass of PTFE and 6% by mass of alumina. An expanded graphite sheet with a layer was prepared. The expanded graphite sheet provided with the coating layer of the solid lubricant is inserted between the reinforcing materials made of two plain weave wire meshes with each side being matched, and then the expanded graphite sheet and the reinforcing material made of two plain weave wire meshes A rectangular outer layer is formed in which a flat weave wire mesh is filled with expanded graphite and a solid lubricant, and a square mesh is arranged in parallel in the width direction and the longitudinal direction. A member was prepared. In the outer layer forming member, the area ratio at which the surface of the reinforcing material made of plain woven wire mesh was exposed was 25%.

  The outer layer forming member is wound around the outer peripheral surface of the cylindrical member with the surface of the reinforcing material made of plain woven wire mesh and the surface made of solid lubricant mixed and exposed to produce a preliminary cylindrical molded body did.

  Hereinafter, in the same manner as in Example 1, a spherical base defined by the cylindrical inner surface, the partially convex spherical surface, and the large-diameter side and small-diameter annular end surfaces of the partially convex spherical surface, and a portion of the spherical base A ball-shaped seal body having an outer layer integrally formed on the convex spherical surface was obtained.

  In the obtained spherical belt-shaped sealing body, the outer layer is a solid lubrication containing expanded graphite and 60% by mass of PTFE, 34% by mass of PTFE, 34% by mass of alumina, and 6% by mass of alumina. The expanded graphite and the solid lubricant are mixed and integrated, and the outer surface of the outer layer is the surface made of the solid lubricant, and the vertical lines forming the mesh are in the width direction, and the mesh is also the same. The horizontal line group to be formed is a smooth surface exposed by mixing with the surface of the reinforcing material made of plain woven wire mesh arranged in the circumferential direction, and the vertical line group is in the width direction on the outer surface of the outer layer. The surface of the reinforcing material made of plain woven wire mesh in which horizontal line groups are arranged in the circumferential direction was exposed with an area ratio of 35%.

  In the above Example 2 to Example 26 and Comparative Example 1 to Comparative Example 3, the cylindrical base material similar to Example 1 manufactured in the same manner as in Example 1 is used as the cylindrical base material. In each of the obtained spherical belt-shaped sealing bodies, the spherical belt-shaped substrate was formed so that the expanded graphite and the wire mesh were mutually compressed and entangled with each other in the same manner as in Example 1. .

  Next, the spherical belt-like seal bodies obtained in Examples 1 to 26 and Comparative Examples 1 to 3 are incorporated in the exhaust pipe joint shown in FIG. 29, and the surface roughness of the surface of the mating member is determined by a rocking test. Change, presence / absence of generation of abnormal noise and gas leakage (l / min).

<Test conditions for rocking test>
Temperature (temperature of the surface of the enlarged diameter portion 301 shown in FIG. 29) 300 ° C.
Amplitude (oscillation angle) ± 2 °
Excitation frequency 25Hz
Excitation time 42Hr
Set load by coil spring 650N
Number of vibrations 3,740,000 Counterpart material (material of diameter enlarged portion 301 shown in FIG. 29) SUS304

<Test conditions for presence or absence of frictional noise>
Temperature (temperature of the surface of the enlarged diameter portion 301 shown in FIG. 29) Room temperature (RT = 25 ° C.) to 500 ° C.
Excitation frequency 25Hz
Sliding distance (amplitude) ± 0.05 to ± 2.05mm
Excitation time 40 minutes (1 cycle)
Set load by coil spring 650N

<Test method>
29, the upstream side exhaust pipe 100 of the exhaust pipe joint shown in FIG. 29 is fixed, and high temperature gas is circulated through the upstream side exhaust pipe 100 to raise the surface temperature of the counterpart material (diameter enlarged portion 301 shown in FIG. 29) to 300 ° C. When the surface temperature of the counterpart material reaches 300 ° C., the downstream side exhaust pipe 300 is subjected to a swinging motion with an amplitude of ± 2 ° at an excitation frequency of 25 Hz for 42 hours (excitation frequency: 374 times). First, the temperature is lowered to room temperature (rocking test). Subsequently, the surface temperature of the counterpart material is raised to 500 ° C. in 10 minutes, and when the surface temperature of the counterpart material reaches 500 ° C., vibration is performed for 10 minutes under conditions of a frequency of 25 Hz and an amplitude of ± 0.05 mm. Next, the amplitude of the mating material was varied from ± 0.05 mm to ± 2.05 mm while lowering the surface temperature of the counterpart material from 500 ° C. to room temperature, and the presence or absence of frictional noise at the amplitude was measured (frictional abnormality). Test for the presence of sound).

<Test conditions for gas leakage>
Pressing force with a coil spring (spring set force): 650 N
Oscillation angle: ± 2 °
Excitation frequency (oscillation speed): 5Hz
Temperature (diameter enlarged portion 301 shown in FIG. 29): Room temperature (RT = 25 ° C.) to 500 ° C.
Number of swings: 1 million times Counterpart material (material of the enlarged diameter portion 301 shown in FIG. 29): SUS304

<Test method>
After performing a rocking test under the conditions of the rocking test, the temperature of the mating member was raised to 500 ° C while continuing rocking motion of ± 2 ° at an excitation frequency of 5 Hz at room temperature. (1) Before starting the test, (2) After 250,000 swings, (3) After 500,000 swings, and (4) 1 million swings The amount of gas leakage at the time of reaching was measured.

<Measurement method of gas leakage>
The opening of the exhaust pipe 100 on the upstream side of the exhaust pipe joint shown in FIG. 29 is closed, and dry air is introduced from the downstream side of the exhaust pipe 200 at a pressure of 49 kPa (0.5 kgf / cm 2). A sliding contact portion between the outer surface 45 of the outer layer of the seal body 44 and the inner surface 304 of the concave spherical surface portion 302, a fitting portion between the cylindrical inner surface 38 of the ball-shaped seal body 44 and the pipe end portion 101 of the upstream side exhaust pipe 100, and an annular shape. The amount of gas leakage from the end face 40 and the flange portion 200 erected on the upstream side exhaust pipe 100) is measured with a flow meter (1) before the start of the test, and (2) the number of oscillations reaches 250,000 times. The amount of gas leakage was measured when (3) the number of oscillations reached 500,000 times and (4) the number of oscillations reached 1 million times.

  Tables 1 to 6 show the above test results, and Tables 7 to 12 show the friction differences for Example 7, Example 4, Example 7, Example 8, Example 16, Example 23, and Comparative Example 3. The test progress and test results of sound are shown. In addition, the determination level of frictional noise was performed according to the following criteria.

<Friction noise judgment level>
Symbol: 0 No friction noise was generated.
Symbol: 0.5 Friction noise can be confirmed on the sound collecting pipe.
Symbol: Generation of frictional noise can be confirmed at a position about 0.2 m away from the sliding portion of the exhaust pipe spherical joint.
Symbol: 1.5 Generation of abnormal noise can be confirmed at a position about 0.5 m away from the sliding portion of the exhaust pipe spherical joint.
Symbol: 2 Generation | occurrence | production of friction noise can be confirmed in the position about 1 m away from the sliding site | part of the exhaust pipe spherical joint.
Symbol: 2.5 Generation | occurrence | production of friction noise can be confirmed in the position about 2 m away from the sliding site | part of the exhaust pipe spherical joint.
Symbol: 3 Generation | occurrence | production of friction noise can be confirmed in the position about 3 m away from the sliding site | part of the exhaust pipe spherical joint.
Symbol: 3.5 Generation | occurrence | production of friction noise can be confirmed in the position about 5 m away from the sliding site | part of the exhaust pipe spherical joint.
Symbol: 4 Generation | occurrence | production of friction noise can be confirmed in the position about 10 m away from the sliding site | part of the exhaust pipe spherical joint.
Symbol: 4.5 Generation | occurrence | production of friction noise can be confirmed in the position about 15 m away from the sliding site | part of the exhaust pipe spherical joint.
Symbol: 5 Generation | occurrence | production of friction noise can be confirmed in the position about 20 m away from the sliding site | part of the exhaust pipe spherical joint.

  In the overall judgment of the above judgment levels, it is judged that the symbol 0 to the symbol 2.5 is no occurrence of the frictional noise (pass), and the symbol 3 to the symbol 5 is the occurrence of the frictional noise (not good). Passed).

  From the test results shown in Tables 1 to 12, the spherical band-shaped sealing body of Examples 1 to 26 is comparative example 1 in terms of roughening the surface of the counterpart material, evaluating the occurrence of frictional noise, and the amount of gas leakage. It turns out that it is superior to the spherical belt-shaped sealing body which consists of thru | or comparative example 3. The surface of the mating member is exposed to the outer surface of the outer layer of the spherical belt-shaped sealing body made of Comparative Example 3 in spite of the same plain woven wire mesh as that of the spherical belt-shaped sealing body of Examples 1 to 26 being exposed. The increase in the surface roughness is that the adjacent vertical line groups forming the rectangular mesh of the plain weave wire mesh are arranged along the axial direction, and the adjacent horizontal line groups are arranged along the circumferential direction. The surface of the mating material is presumed to be due to sliding in direct contact with the vertical line group and horizontal line group of the plain woven wire mesh always in the sliding direction.

  As described above, according to the spherical belt-shaped sealing body of the present invention, it is possible to eliminate a large lump-like lump in the intersection group, and in the sliding friction with the counterpart material, the mesh intersection point and the counterpart material surface The induction of the abrasive wear during the period can be reduced as much as possible, the roughening due to the damage of the surface of the counterpart material can be reduced, and the deterioration of the sealing performance can be prevented as much as possible.

  In addition, even when the reinforcing material made of plain woven wire mesh exposed on the outer surface of the outer layer is worn, it shifts to friction sliding with the reinforcing material made of plain woven wire mesh located in the lower layer, and the counterpart material is always expanded graphite. Since the sliding of the surface of the heat-resistant material including the surface and the surface of the reinforcing material made of plain woven wire mesh is exposed, the sliding between the counterpart material and the heat-resistant material including the expanded graphite alone is avoided. Generation of abnormal noise can be prevented as much as possible.

  In the example of the manufacturing method of the spherical belt-shaped sealing body of the present invention, a preliminary cylindrical molded body is created by winding an outer layer forming member with a gap between the oblique sides of the end face in the longitudinal direction on the outer peripheral surface of the cylindrical base material, Since the outer layer forming member is sometimes compressed while being stretched in the circumferential direction, the gap between both ends of the outer layer forming member can be eliminated, and the end of the outer layer forming member is at least partially convex spherical on the spherical base Thus, the outer layer forming member can be prevented from being peeled off from the spherical band-shaped substrate starting from the end.

DESCRIPTION OF SYMBOLS 1 Braided wire mesh 4 Strip | belt-shaped wire mesh 5 Wire mesh 6 Expanded graphite sheet 12 Polymer 14 Vertical line 15 Horizontal line 16 Mesh 17 Plain woven wire mesh 18 Oblique side 19a, 19b, 19c, 19d Intersection 21 Expanded graphite sheet 27, 27a Outer layer forming member 28 Cover layer 29 Preliminary Cylindrical molded body 36 Mold 38 Cylindrical inner surface 39 Partial convex spherical surface 40, 41 Annular end surface 42 Spherical band base 44 Spherical band sealing body

Claims (14)

  A spherical belt-shaped sealing body used for an exhaust pipe joint, comprising a cylindrical inner surface, a partially convex spherical surface, and a spherical belt-shaped substrate defined by an annular end surface on the large-diameter side and small-diameter side of the partially convex spherical surface, An outer layer integrally formed on a partially convex spherical surface of the base, and the ball-shaped base is filled with a reinforcement made of a wire mesh and a mesh of the reinforcement mesh and mixed with the reinforcement The outer layer is on one diagonal line of a pair of diagonal lines connecting the intersections of adjacent vertical lines and adjacent horizontal lines forming a square mesh. One intersection group located is arranged in the axial direction, while the other intersection group located on the other diagonal line of the pair of diagonal lines is composed of a plain woven wire mesh arranged in the circumferential direction and compressed Spherical belt-shaped sealing body having at least a reinforcing material   The outer layer is provided with a heat-resistant material that is filled with a reinforcing woven plain mesh and mixed with the reinforcing material, and the outer surface of the outer layer includes a surface of the heat-resistant material and a surface of the reinforcing material. The spherical belt-shaped sealing body according to claim 1, which has a smooth surface exposed by mixing.   The outer layer includes a heat-resistant material and a solid lubricant mixed and integrated with the reinforcing material and filled with a plain woven wire mesh of a reinforcing material, and the outer surface of the outer layer includes a surface of a solid lubricant, The spherical belt-shaped sealing body according to claim 1, which is a smooth surface exposed by mixing with a surface of a reinforcing material.   The sphere according to any one of claims 1 to 3, wherein the surface of the reinforcing material made of plain woven wire mesh is exposed on the outer surface of the outer layer with an area ratio of 10 to 65% with respect to the entire outer surface of the outer layer. Strip seal body.   The outer layer includes a heat-resistant material filled and mixed with the reinforcing material plain weave wire mesh, and a solid lubricant covering the heat-resistant material and the reinforcing material. The spherical surface-shaped sealing body according to claim 1, wherein the outer surface is a smooth surface with the surface of the solid lubricant exposed.   The ball-shaped seal body according to claim 3 or 5, wherein the solid lubricant contains a tetrafluoroethylene resin, a tetrafluoroethylene-hexafluoropropylene copolymer, and a hexagonal boron nitride.   The composition ratios of the tetrafluoroethylene resin, tetrafluoroethylene-hexafluoropropylene copolymer and hexagonal boron nitride in the solid lubricant are tetrafluoroethylene resin, tetrafluoroethylene-hexafluoropropylene copolymer and hexagonal crystal. In the ternary composition diagram of boron nitride, a composition point of 10% by mass of tetrafluoroethylene resin, 10% by mass of tetrafluoroethylene-hexafluoropropylene copolymer and 80% by mass of hexagonal boron nitride, tetrafluoroethylene resin 10 mass%, composition point of 45 mass% tetrafluoroethylene-hexafluoropropylene copolymer and 45 mass% hexagonal boron nitride, 45 mass% tetrafluoroethylene resin, tetrafluoroethylene-hexafluoropropylene copolymer 45 Composition points of 10% by mass and hexagonal boron nitride 10% by mass Numerical range corresponding to a region bounded by a quadrangle whose apex is a composition point of 40% by mass of tetrafluoroethylene resin, 10% by mass of tetrafluoroethylene-hexafluoropropylene copolymer and 50% by mass of hexagonal boron nitride. The spherical belt-shaped sealing body according to claim 6, which is inside.   The composition ratios of the tetrafluoroethylene resin, tetrafluoroethylene-hexafluoropropylene copolymer and hexagonal boron nitride in the solid lubricant are tetrafluoroethylene resin, tetrafluoroethylene-hexafluoropropylene copolymer and hexagonal crystal. In the ternary composition diagram of boron nitride, the composition point of 25% by mass of tetrafluoroethylene resin, 15% by mass of tetrafluoroethylene-hexafluoropropylene copolymer and 60% by mass of hexagonal boron nitride, tetrafluoroethylene resin 12 mass%, composition point of tetrafluoroethylene-hexafluoropropylene copolymer 28 mass% and hexagonal boron nitride 60 mass%, tetrafluoroethylene resin 10 mass%, tetrafluoroethylene-hexafluoropropylene copolymer 40 4% by mass and a composition point of hexagonal boron nitride 50% by mass, Composition point of ethylene fluoride resin 20% by mass, tetrafluoroethylene-hexafluoropropylene copolymer 40% by mass and hexagonal boron nitride 40% by mass, tetrafluoroethylene resin 38% by mass, tetrafluoroethylene-hexafluoropropylene A composition point of 22% by mass of copolymer and 40% by mass of hexagonal boron nitride, 35% by mass of tetrafluoroethylene resin, 15% by mass of tetrafluoroethylene-hexafluoropropylene copolymer and 50% by mass of hexagonal boron nitride; The spherical belt-shaped sealing body according to claim 6 or 7, which is in a numerical range corresponding to a region bounded by a hexagon having a composition point as a vertex.   The ball-shaped seal body according to claim 7 or 8, wherein the solid lubricant further contains alumina hydrate in a proportion of 20% by mass or less.   The ball-shaped seal body according to any one of claims 3 and 5 to 9, wherein the solid lubricant is unfired.   The ball-shaped seal body according to any one of claims 3 and 5 to 9, wherein the solid lubricant is fired.   The spherical belt-shaped sealing body according to any one of claims 1 to 11, wherein the heat-resistant material includes compressed expanded graphite.   The ball-shaped seal body according to any one of claims 1 to 12, wherein the heat-resistant material contains a phosphate in a proportion of 0.1 to 16% by mass.   The ball-shaped seal body according to any one of claims 1 to 13, wherein the heat-resistant material contains phosphorus pentoxide in a proportion of 0.05 to 5 mass%.

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