CN106397895B - Sealing element - Google Patents

Sealing element Download PDF

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Publication number
CN106397895B
CN106397895B CN201610619820.8A CN201610619820A CN106397895B CN 106397895 B CN106397895 B CN 106397895B CN 201610619820 A CN201610619820 A CN 201610619820A CN 106397895 B CN106397895 B CN 106397895B
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base
fabric
seal
rubber composition
shaped
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CN106397895A (en
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南畅
上田彰
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Walka Corp
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Walka Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C08L15/005—Hydrogenated nitrile rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
    • B29C70/34—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/54—Component parts, details or accessories; Auxiliary operations, e.g. feeding or storage of prepregs or SMC after impregnation or during ageing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D99/00—Subject matter not provided for in other groups of this subclass
    • B29D99/0082—Producing articles in the form of closed loops, e.g. rings
    • B29D99/0085—Producing articles in the form of closed loops, e.g. rings for sealing purposes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J9/00—Piston-rings, e.g. non-metallic piston-rings, seats therefor; Ring sealings of similar construction
    • F16J9/12—Details
    • F16J9/20—Rings with special cross-section; Oil-scraping rings
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J9/00—Piston-rings, e.g. non-metallic piston-rings, seats therefor; Ring sealings of similar construction
    • F16J9/28—Piston-rings, e.g. non-metallic piston-rings, seats therefor; Ring sealings of similar construction of non-metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/26—Sealing devices, e.g. packaging for pistons or pipe joints
    • B29L2031/265—Packings, Gaskets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2309/02—Copolymers with acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2315/00—Characterised by the use of rubber derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2401/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2477/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Sealing Material Composition (AREA)
  • Sealing Devices (AREA)
  • Laminated Bodies (AREA)
  • Woven Fabrics (AREA)
  • Actuator (AREA)

Abstract

The present invention provides a seal material, which is an annular seal material obtained by molding and crosslinking a belt-shaped base cloth, wherein the belt-shaped base cloth is obtained by embedding a base material formed of a woven fabric or the like in a rubber composition, the rubber composition contains 60 mass% or more of hydrogenated nitrile rubber as a rubber component, and the content of acrylonitrile in the hydrogenated nitrile rubber is 25 mass% to 50 mass%.

Description

Sealing element
Technical Field
The present invention relates to an annular seal formed by molding a base fabric in which a base material is embedded in a rubber composition, and more particularly to a seal having a substantially V-shaped or U-shaped cross section, for example, which is disposed between a piston and a cylinder. Annular seals are used in a wide range of industrial fields such as electric power plants, chemical plants, tire industries, and sealing of sliding portions of various devices and apparatuses.
Background
Conventionally, in the field of industrial equipment, factories, and the like, sealing materials have been used in which a plurality of sheets obtained by impregnating a fabric material made of woven asbestos, cotton, glass, or other fibers with a rubber composition are laminated and vulcanization-molded into a predetermined shape.
When a seal using a cotton cloth material or a glass fiber cloth material is used in an environment exposed to high-temperature steam, the seal is not resistant to the high-temperature steam and cannot be continuously used for a long time. Therefore, a seal obtained by laminating and molding rubber layers reinforced with asbestos cloth is used in an environment exposed to steam at high temperature. However, asbestos is harmful to the human body, and thus its use tends to be limited worldwide, and development of alternative products thereof is desired.
In addition, when carbon fiber cloth is used as a raw material, although the carbon cloth has good heat resistance, the carbon cloth is rigid and is difficult to be given a predetermined shape, and thus there is a problem that interlayer peeling occurs.
In addition, in the case of a sealing material obtained by molding a nitrile rubber layer reinforced with cotton cloth, the sealing material has low heat resistance and cannot be used at high temperatures. In the case of a seal material obtained by molding a fluororubber layer reinforced with cotton cloth, the heat resistance is improved, but the abrasion resistance is poor. In particular, when these seals are used for water-glycol-based hydraulic oil, leakage of the hydraulic oil may occur due to low wear resistance.
Japanese patent No. 4712486 discloses the following method: the sealing material is produced by laminating a sealing material-forming tape obtained by cutting a carbon cloth by a specific method on a mold, easily forming the tape into a predetermined shape, and vulcanizing the tape.
Further, Japanese patent publication No. 42-20943 discloses a seal ring obtained by: a sheet material is formed into a cylindrical shape by impregnating and coating a cloth such as kapok or rayon with an uncured rubber or the like, spirally winding the sheet material, cutting the sheet material into a predetermined length, and bending one circumferential end of the cylindrical shape inward to form a U-shape.
Further, japanese unexamined patent publication No. 59-174456 discloses a ring-shaped seal in which a core portion is formed of fibers impregnated with a rubber-like elastic material, and an outer peripheral portion of the core portion is formed of a base fabric impregnated with a resin material.
However, in the seal rings described in patent documents 2 and 3, since a general-purpose rubber is used for the rubber composition constituting the base fabric, there are problems as follows: the sealing property and the sealing life are poor, and the heat resistance is poor, so that the sealing material is not suitable for use in a high-temperature and high-steam environment.
Disclosure of Invention
The invention provides a sealing member which can be used in a high-temperature and steam environment, has excellent wear resistance, sealing performance and sealing life, and solves the problem of environmental pollution when asbestos is used.
In addition, in an embodiment of the present invention, there is provided a method of manufacturing a seal member: the base fabric for forming the seal member is provided with flexibility to be able to be preformed into a desired shape. And the molded shape is maintained by releasing the molding pressure after preforming to reduce the restoring force, and the appearance and physical properties after vulcanization are excellent.
The present invention relates to a seal material having an annular shape obtained by molding and crosslinking a tape-shaped base fabric obtained by embedding a base material in a rubber composition containing 60 mass% or more of hydrogenated nitrile rubber as a rubber component.
Here, the content of acrylonitrile in the hydrogenated nitrile rubber is preferably in the range of 25 to 50 mass%. Furthermore, the elongation of the base fabric after crosslinking is in the range of 35 to 60%, and the required properties of the sealing member can be effectively exhibited. Further, it is desirable that the base material constituting the base fabric is formed of a cord fabric or a plain weave fabric of aramid fibers including warp and weft of aramid fibers.
In the seal member of the present invention, it is preferable that the seal member is formed of a laminate of a plurality of band-shaped base cloths, and the threads of the base material intersect each other between the laminates. Further, the cross section of the seal member is preferably V-shaped or U-shaped.
The present invention also relates to a method for manufacturing a seal using an annular mold, the method comprising:
(a) a step for preparing a base fabric obtained by impregnating a base material with a solution of a hydrogenated nitrile rubber composition and embedding the base material in the rubber composition;
(b) preparing a plurality of strip-shaped base cloths obtained by cutting the base cloths into oblique strips with a predetermined size;
(c) sequentially arranging the band-shaped base cloths on the surface of the annular die along the circumferential direction of the annular die on the whole circumference;
(d) pressing the band-shaped base cloths in the direction of a mold so as to enable the band-shaped base cloths to be mutually adhered to form a preformed body; and
(e) and a step of crosslinking the preform by applying pressure and heat to the preform.
The above and other objects, features, aspects and advantages of the present invention will become apparent from the following detailed description of the present invention, which is to be read in connection with the accompanying drawings.
Drawings
Fig. 1 is a sectional view of a hydraulic piston cylinder showing a state in which an annular seal is disposed.
Fig. 2 is a cross-sectional view of the annular seal cut in the radial direction.
Fig. 3 is a perspective view of a seal molded in an annular mold.
Fig. 4 is a sectional view a-a of fig. 3.
Fig. 5 is a schematic view of a long base fabric in which a base material of a cord fabric is embedded in a rubber composition.
FIG. 6 is a cross-sectional view of a base fabric obtained by embedding a cord fabric in a rubber composition.
Fig. 7 is a sectional perspective view of a mold for molding the seal.
Fig. 8 is a sectional perspective view of a mold for molding the seal.
Fig. 9 is a sectional perspective view of a mold for molding the seal.
Detailed Description
The present invention is an annular seal obtained by molding and crosslinking a belt-shaped base fabric obtained by embedding a base material in a rubber composition containing 60 mass% or more of hydrogenated nitrile rubber as a rubber component.
In the seal of the present invention, for example, in a cross-sectional view of the hydraulic piston cylinder 1 shown in fig. 1, a plurality of annular seals 4 are disposed between the cylinder 2 and the piston 3. In fig. 1, 4, 16 ring-shaped seals 4 are arranged between the female adapter 5 and the male adapter 6. The annular seal of the present invention has sufficient durability under high temperature and high humidity conditions when the piston in the cylinder operates, and maintains high sealing performance even after a long operating distance.
< shape of seal >
Fig. 2 shows a cross-sectional shape obtained by cutting the annular seal 41 in the radial direction. The cross section of the seal member has a substantially V-shape, and is formed from 2 laminated bodies of an outer base cloth 4a disposed outside the seal member and an inner base cloth 4b disposed inside the seal member.
The annular seal 41 having a substantially V-shaped cross section, which is formed by laminating the base fabrics, is formed, for example, with an inner diameter R1 of 30 to 500mm, a height h of 2 to 20mm, and a width W of 5 to 30 mm.
The cross-sectional shape of the seal 41 may be substantially U-shaped or substantially circular, in addition to the substantially V-shaped shape shown in fig. 2. These cross-sectional shaped seals are manufactured by shaping and cross-linking the strip in a shaping die of corresponding cross-sectional shape. The cross-sectional shape of the seal of the present invention is not particularly limited, and corresponds to the cross-sectional shape of the molding die, and for example, the cross-section is a triangular shape with a convex portion 10A as shown in fig. 7, a cross-section is a shape of "く" 10B as shown in fig. 8, or a cross-section is a C-shape (10C) as shown in fig. 9.
< substrate >
In the present invention, a base fabric is produced by embedding a base material in a rubber composition. The substrate used herein may be a woven fabric such as a woven fabric, a plain woven fabric, a twill woven fabric, a nonwoven fabric or the like. In addition, a thick woven fabric (a slightly thick woven fabric using a doubled or plied yarn) or a satin woven fabric (a weave having a repeat structure including at least 5 warps and wefts, in which the same warp and weft are interlaced only 1 time and the number of flights of the weft is 1 or more) may be suitably used. In addition, as the fiber, an organic fiber such as aramid, polyester, nylon, rayon, or cotton, and an inorganic fiber such as a carbon fiber or a glass fiber can be used. Particularly, aramid fibers are suitable from the viewpoint of heat resistance and sealing properties.
Fig. 5 is a schematic view showing a long base fabric obtained by embedding a base material of a cord fabric in a rubber composition. Here, the thickness of the woven or knitted fabric as the base material before the impregnation with the rubber composition is, for example, 0.2 to 0.80mm, and the weight per unit area of the base material before the impregnation with the rubber composition is, for example, 100 to 300g/m2。
For the fabric, it is desirable that the fabric density, expressed in the number of fibers used in the width of 1cm each in the warp direction and the weft direction, is, for example, 3 to 15, preferably 4 to 10 pieces/cm. In the case of a cord fabric, the fabric is flat, the substrate has a small thickness, the fabric density is small unlike a square structure in which the substrate has a three-dimensional thickness, the rubber composition easily infiltrates into the fabric, the interfacial peeling between the rubber and the fiber is not easily caused, and the surface smoothness of the molded sealing material is excellent.
In the present invention, the use of fine fibers for the base material makes it possible to maintain the flexibility of the base fabric, to make the base fabric, which is obtained by impregnating and adhering the base fabric with the rubber composition, less likely to peel off from the rubber, to provide excellent processability into a desired sealing material, and to provide excellent surface smoothness of the sealing material after molding. When the fiber diameter is too large and the fabric density is high, the base fabric becomes rigid, and the molding processability in a mold becomes difficult.
< base cloth >
The base fabric is produced by embedding the base material in the rubber composition or impregnating the base material with a solution of the rubber composition. FIG. 6 is a cross-sectional view of a base fabric obtained by embedding a cord fabric in a rubber composition. In the figure, the warp yarns 13 are arranged at regular intervals in the longitudinal direction, and the fine weft yarns 14 are alternately arranged above and below the warp yarns 13 therebetween, so that the positional relationship of the warp yarns 13 is maintained. In the base fabric 11, a base material composed of warp and weft is embedded in the rubber composition 12.
The content of the rubber composition in the base fabric is in the range of 40 to 80 mass%, preferably 50 to 70 mass%. The content of the rubber composition is adjusted so as to maintain physical properties required for the sealing material, for example, appropriate elasticity, mutual adhesiveness of base fabrics at the time of molding, a shape of a laminate of the base materials before crosslinking into a desired shape, and molding into a preform under pressure.
When the content of the rubber composition in the base fabric is small, the physical properties of the rigidity of the sheet or the laminate thereof have an excessively strong adverse effect on the entire seal, and it is difficult to form a seal having appropriate elasticity as a sealing material, and delamination of the base material is likely to occur. In addition, in the production process, it is difficult to impart a shape, and workability to a preform or the like is also deteriorated. On the other hand, if the content of the rubber composition in the base fabric exceeds the above range, the soft physical properties of the rubber component greatly affect the physical properties of the entire seal, and the reinforcing effect of the base fabric with the filler becomes insufficient, so that it is difficult to obtain a so-called laminate-molded seal of a base fabric having high stiffness.
(tape-shaped base cloth)
A plurality of strip-shaped base cloths 11 are produced by cutting a long base cloth, which is obtained by embedding a base material in a rubber composition, into oblique strips at a predetermined angle and a predetermined width in the longitudinal direction. The width m of the strip-shaped base fabric is, for example, 10 to 30mm, and the bias cutting angle theta is usually set in the range of 30 to 60 deg.
(elongation of base cloth)
The elongation of the base fabric in a tape form is preferably in the range of 35 to 60%. In this range, the base fabric for forming the seal member is provided with flexibility so as to be able to be preformed into a desired shape. And the molded shape is maintained by reducing the restoring force by releasing the molding pressure after preforming, and a seal excellent in wear resistance and sealing resistance can be obtained after vulcanization.
< rubber composition >
The rubber composition for the embedded substrate is produced by dissolving a rubber composition such as hydrogenated nitrile rubber or nitrile rubber in a solvent. As the solvent, a rubber solvent such as acetone, toluene, and methyl isobutyl ketone (MIBK) can be used.
The compounding ratio of the rubber component and the solvent in the rubber composition is not particularly limited, and the rubber component is contained in an amount of, for example, 15 to 25 parts by weight and the solvent is contained in the remaining amount of, for example, 85 to 75 parts by weight in 100 parts by weight of the rubber composition.
In the present invention, the rubber component contains 60% by mass or more of hydrogenated nitrile rubber (hereinafter, also referred to as "H-NBR"). Here, the acrylonitrile content in the hydrogenated nitrile rubber is in the range of 25 to 50 mass%.
Hydrogenated nitrile rubbers are polymers obtained by hydrogenation of double bond portions of butadiene units in nitrile rubbers, and heat resistance and aging resistance are improved by hydrogenation. Here, a polymer having a hydrogenation ratio of 60 to 98% is commercially available and can be suitably used.
In view of moldability required for the rubber composition, mechanical properties required for the crosslinked rubber, light transmittance, and the like, various hydrogenated nitrile-butadiene rubber (H-NBR) can be suitably used. Specifically, trade names manufactured by Zeon Corporation can be exemplified: trade name of ZETPOL system, Bayer (Bayer): the Therban series, etc.
In the present invention, these hydrogenated nitrile rubbers may be used alone, or 2 or more kinds of H-NBR may be used in combination for the purpose of adjusting the Mooney viscosity, the vulcanization rate, the amount of oil, and the like.
Alternatively, the H-NBR may be mixed with other rubber components. As the other rubber component, for example, ethylene-propylene-diene rubber (EPDM), ethylene-propylene rubber (EPM), nitrile rubber (NBR; acrylonitrile butadiene rubber), butyl rubber (IIR), fluorine rubber (FKM), silicone rubber and the like can be used. Among them, nitrile rubber (NBR), EPDM, FKM and the like are preferable from the viewpoint of sealing property. The rubber component may be composed of only 1 type, or may contain 2 or more types.
When these rubber components are used, they are compounded in an amount of less than 40% by mass of the entire rubber components.
< crosslinking agent >
In the present invention, sulfur, organic sulfur compounds, disulfides, organic peroxides, and the like can be used as the crosslinking agent. Examples of the organic peroxide used in EPDM and H-NBR include: 2, 5-dimethyl-2, 5-di (t-butylperoxy) -3-hexane, di-t-butylperoxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, t-butylcumylperoxide, 1, 3-bis (t-butylperoxyisopropyl) benzene, dicumylperoxide, butyl 4, 4-di (t-butylperoxy) valerate, 2-di (t-butylperoxy) butane, 1-di-t-butylperoxy-3, 3, 5-trimethylcyclohexane, dibenzoyl peroxide, bis (o-methylbenzoyl) peroxide, bis (p-methylbenzoyl) peroxide, t-butylperoxy-benzilate and the like.
The crosslinking agent is compounded in an amount of 1 or more in the range of 0.5 to 5 parts by mass per 100 parts by mass of the rubber component.
< production of sealing Material >
The seal of the present invention is manufactured by the following steps using an annular mold.
(a) And a step of preparing a base fabric in which a solution of a hydrogenated nitrile rubber composition is impregnated into a base material and the base material is embedded in the rubber composition.
(b) Preparing a plurality of band-shaped base cloths obtained by cutting the base cloths into oblique strips with a predetermined size.
(c) And a step of arranging the band-shaped base cloths on the surface of the annular mold in sequence along the circumferential direction of the annular mold.
(d) And a step of pressing the band-shaped base cloths in the direction of a mold to make the band-shaped base cloths mutually and tightly adhere to each other to form a preform.
(e) And a step of crosslinking the preform by applying pressure and heat to the preform.
Hereinafter, a method of manufacturing the annular seal of the present invention will be described with reference to the drawings. Fig. 3 is a perspective view of a seal molded in an annular mold. Fig. 4 is a sectional view a-a of fig. 3.
< step of preparing a tape-shaped base Fabric >
In fig. 5, a long base fabric 150 is bias-cut at a predetermined angle θ (X direction) in the longitudinal direction of the base fabric to produce a plurality of pieces of strip-shaped base fabrics 11 having a parallelogram plane in the strip-shaped base fabric 11.
Fig. 5 shows a schematic view of a long base fabric 150 obtained by embedding a base material in a rubber composition, and fig. 6 shows a cross-sectional view of the base fabric 150. In fig. 5 and 6, a long base fabric 150 extending to the left and right of the paper surface is cut at a bias cutting angle θ of, for example, 30 ° to 60 ° with respect to the longitudinal direction (the direction transverse to the paper surface), to obtain a strip-shaped base fabric 11 having a parallelogram shape.
In fig. 5, a woven fabric of warp yarns 13 and weft yarns 14 is used, and a base fabric 150 is woven such that the warp yarns 13 are arranged in the longitudinal direction of the base material and the weft yarns 14 are arranged in the width direction of the base material.
The size of the strip-shaped base cloth 11 varies depending on the inner diameter and outer diameter of the piston shaft to be sealed, the place of use, the depth of the required groove, the size of the seal, and the like, and is not generally determined, and for example, the width m of the base cloth is 10mm to 30 mm. The thickness of the base material before impregnation of the rubber composition is 0.2mm to 0.8 mm. The length of the base fabric is not particularly limited.
The base material before impregnation with the rubber composition has a weight per unit area of 100 to 300g/m2Preferably 150 to 250g/m2. When the weight per unit area is larger than the above range, the weight per unit area becomes too large, and the surface appearance of the seal tends to be poor and the elasticity tends to be poor.
< step of preforming >
In fig. 3 and 4, a strip-shaped base fabric 11 having a parallelogram-shaped plane, which is obtained by cutting the base fabric into diagonal strips, is arranged in a spiral shape on the outer peripheral surface of a molding die 10 in this order along the circumferential direction. The tape-shaped base cloths 11, which are arranged and laminated in the circumferential direction of the forming die 10, are pressed or fitted to the outer die along the surface shape of the die, and are preformed. In this case, an adhesive may be used to temporarily adhere the band-shaped base cloths to the mold 10 and to adhere the band-shaped base cloths 11 to each other. The adhesive used here may be a sizing agent having the same composition as the rubber composition used for the sealing material, for example.
In the present invention, a preform obtained by laminating 1 or more pieces of the base cloths 11 in a band shape on the surface of a mold through an adhesive as necessary is pressurized from the outside of the molding mold 10 side, and the base cloths 11 in a band shape are closely adhered to each other.
In this pressing, an outer mold that can be molded into a desired shape by sandwiching the preform may be used in combination with the molding mold 10. The cross-sectional shape of the outer mold is preferably matched to the shape of the outer peripheral surface of the annular molding die 10, and the outer mold has a shape of a void such as a triangle with a circular recess in cross section, a shape of "く" in cross section, or a C-shape in cross section.
In the present invention, the forming die 10 is used for forming, and the forming die 10 shown in fig. 4 has a convex portion G' corresponding to the groove G of the seal in fig. 2, and the cross section of the forming die 10 is triangular and the planar shape is annular. The use of the forming die 10 enables the forming into a desired shape to be carried out reliably and easily.
< crosslinking step >
Fig. 2 shows a seal 41 having a substantially V-shaped cross section, which is obtained by heating a shaped preform under pressure in a mold to crosslink and mold the preform. The crosslinking/molding conditions vary depending on the type of the rubber component of the rubber composition and cannot be determined in general, and for example, the composition containing 100 parts of hydrogenated nitrile rubber is held at a temperature of 120 to 170 ℃ for 1 to 40 minutes. The seal 41 obtained by crosslinking and molding has excellent surface smoothness of appearance, excellent tensile strength, flexibility against bending, and interlayer peeling resistance during use, and can withstand long-term use.
< production of sealing Member for product >
In the case where the seal 41 of the present invention is formed of a laminate, the warp threads (or weft threads) of the base material are arranged in diagonal lines on the same plane as the circumferential direction of the annular member at any portion of the outer surface of the annular member (for example, the rotary shaft) to be sealed.
In the method for producing a sealing material of the present invention, the fibers constituting the band-shaped base fabric after bias-cutting are arranged as bias stripes between the layers of the laminate, whereby the preforming of the sealing material is easier to shape and the efficiency is better than the conventional base material fibers. And prevents the peeling of the base fiber of the sealing material, and has excellent balance of appearance, tensile strength, bending and the like.
[ examples ]
The annular seals of examples and comparative examples and the manufacturing methods thereof will be specifically described.
< substrate >
The substrates used in the examples and comparative examples shown in table 2 are as follows.
(1) Substrate (Cotton)
Thick fabric, warp density: 10 threads/cm, weft density: 10 roots/cm, substrate thickness: 0.7mm,
Weight per unit area: 61g/m2
(2) Base material (aramid 1)
Plain weave, warp density: 12 threads/cm, weft density: 12 roots/cm, substrate thickness: 0.42mm,
Weight per unit area: 66g/m2
(3) Base material (aramid fiber 2)
Satin, warp density: 29 pieces/cm, weft density: 20 roots/cm, substrate thickness: 0.65mm, unit area weight: 66g/m2
< preparation of base Fabric >
The impregnation liquids of the rubber compositions of formulations a to C shown in table 1 were applied to various substrates, and dried at normal temperature to produce base fabrics. Here, the mass of the rubber composition was 66 mass% of the mass of the base fabric.
(rubber impregnation solution)
The rubber compositions of formulations a to C shown in table 1 and the solvent (MIBK: methyl isobutyl ketone) were mixed in an amount of 78 parts by mass of the solvent to 22 parts by mass of the rubber composition (solid content: 22% by mass).
(production of Belt-shaped base Fabric)
Subsequently, the long base fabric was cut at an angle of about 45 ° to the longitudinal direction (θ: 45 ° in fig. 5) and at an interval of 20mm in width m to obtain a strip-shaped base fabric having a width of 20 mm.
(production of seal Member)
Next, as shown in fig. 3 and 4, a tape-shaped base fabric is arranged in a circular shape such that one end of the base fabric cut into oblique stripes is aligned in the circumferential direction of the upper surface of the molding die 10, and is bonded and laminated with a sizing agent (the same composition as the rubber impregnation liquid) while being shaped, thereby obtaining a preform having a substantially V-shaped cross section.
Subsequently, the shaped preform was placed in a mold for hot press molding, and the pressure was applied at a temperature of 160 ℃ and a pressure of 10MPa for about 25 minutes to produce a crosslinked and molded sealing material. Referring to FIG. 2, the resulting seal has a height h of 8.5mm, an inner diameter R1 of 98.7mm, and a width W of 11.3 mm.
[ Table 1]
Formulation A Formulation B Formulation C
H-NBR 100 - -
NBR - 100 -
FKM - - 100
Crosslinking agent A 8 - -
Crosslinking agent B - 3 -
Crosslinking agent C - 1 -
Crosslinking agent D - - 3
The compounding amount indicates a mass part per 100 mass parts of the rubber component.
(Note 1) H-NBR: hydrogenated nitrile rubber (hydrogenation rate 91 wt%: acrylonitrile content 36 wt%: trade name "ZETPOL 2020", manufactured by Zeon Corporation)
(Note 2) NBR: acrylonitrile rubber (acrylonitrile content 33 wt%; manufactured by Zeon corporation "NIPOL 042")
(Note 3) FKM: fluororubber (trade name "DAI-EL G501" DAIKIN INDUSTRIES, Ltd.)
(Note 4) crosslinking agent A: PEROXYMON F-40 (di (t-butylperoxy) diisopropylbenzene, manufactured by NOF corporation)
(Note 5) crosslinking agent B: sulfur
(Note 6) crosslinking agent C: DNP (dibenzothiazyl disulfide, produced by Dai-Innovation chemical industry Co., Ltd.)
(Note 7) crosslinking agent D: v3 polyamine (DAIKIN INDUSTRIES, Ltd., N-Dicinnamaldehyde-1, 6-hexanediamine)
< method for evaluating physical Properties >
The material evaluation and the working test evaluation of the seal were carried out by the following methods, and the results are shown in table 2. Evaluation was performed on a scale of 1 to 5, with a scale of 5 being the most excellent.
(1) Heat resistance
And carrying out comprehensive evaluation according to the respective results of the material evaluation and the working test.
(a) Evaluation test of materials
A dumbbell test piece having a length of 100mm multiplied by a thickness of 2 to 3mm is produced using a base fabric, and a deterioration test according to JIS B2403 is performed in an environment of 120 to 160 ℃. The test piece was immersed in the working oil for MAX 1000 hours. The degree of material deterioration was evaluated by measuring the properties such as hardness, tensile strength, elongation, and volume.
(b) Working test
The seals were tested for operation at ambient temperature 100 ℃. The working conditions here are: the load pressure was 21MPa, the working speed was about 200 mm/sec, and the stroke was 50 mm. The test is as follows: the test piece for evaluation was assembled to a rod seal part of a through-rod type test apparatus (as shown in fig. 1 of JIS B2409), and a working test was performed by driving a rod directly while applying a pressure between both seals by a hydraulic pressure source. The amount of leakage (cc/100m) was measured at 0-100 km operation to evaluate the durability.
(2) Steam resistance
A dumbbell test piece having a length of 100mm multiplied by a thickness of 2 to 3mm is produced using a base fabric, and a deterioration test according to JIS K6258 is performed in an environment of 120 to 180 ℃. The degree of material deterioration was evaluated by measuring the properties such as hardness, tensile strength, elongation, and volume.
(3) Wear resistance
And carrying out comprehensive evaluation on a working test and a cylinder body working durability test.
(a) Working test
The working tests were carried out at ambient temperature 100 ℃. The working conditions are as follows: the load pressure was 21MPa, the working speed was about 200 mm/sec, the stroke was 50mm, and the working oil was water-glycol-based working oil. The test is as follows: the test piece for evaluation was assembled to a rod seal part of a through-rod type test apparatus (as shown in fig. 1 of JIS B2409), and a working test was performed by driving a rod directly while applying a pressure between both seals by a hydraulic pressure source. The abrasion resistance was evaluated from dimensional changes of the seal and the breakage of the appearance.
(b) Cylinder operation endurance test
The operation was carried out under a release pressure of 21MPa, an oil temperature of 60 ℃, a working speed of about 100 mm/sec, a stroke of 250mm, a working distance of 1000km, and a working oil of water-glycol system. This test is performed by using a double-acting cylinder, assembling an evaluation sample to a rod seal portion (or a piston portion), and operating the cylinder based on the pressure of a hydraulic pressure source. The abrasion resistance was evaluated from dimensional changes of the seal and the breakage of the appearance.
(4) Sealing property
And carrying out comprehensive evaluation on a working test and a cylinder body working durability test.
(a) Working test
The working tests were carried out at ambient temperature 100 ℃. The working conditions are as follows: the load pressure was 21MPa, the working speed was about 200 mm/sec, the stroke was 50mm, and the working oil was water-glycol-based working oil. The test is as follows: the test piece for evaluation was assembled to a rod seal part of a through-rod type test apparatus (as shown in fig. 1 of JIS B2409), and a working test was performed by driving a rod directly while applying a pressure between both seals by a hydraulic pressure source. The amount of external leakage (cc/100m) was measured at 0-100 km operation time to evaluate the sealing property.
(b) Cylinder operation endurance test
The operation was carried out under a release pressure of 21MPa, an oil temperature of 60 ℃, a working speed of about 100 mm/sec, a stroke of 250mm, a working distance of 1000km, and a working oil of water-glycol system. This test is performed by using a double-acting cylinder, assembling an evaluation sample to a rod seal portion (or a piston portion), and operating the cylinder based on the pressure of a hydraulic pressure source. The amount of external leakage (cc/100m) at 0-1000 km operation was measured to evaluate the sealing property.
(5) Sealing life property
And performing comprehensive evaluation of a material evaluation test and a working test.
(a) Evaluation test of materials
The test is a deterioration test using a cloth-sandwiched dumbbell (JIS B2403) at 120 to 160 ℃, and is carried out by immersing in a working oil for MAX 1000 hours. The properties such as hardness, tensile strength, elongation and volume were measured to evaluate the seal life.
(b) Working test
The working tests were carried out at ambient temperature 100 ℃. The working conditions are as follows: the load pressure was 21MPa, the working speed was about 200 mm/sec, the stroke was 50mm, and the working oil was water-glycol-based working oil. The test is as follows: the test piece for evaluation was assembled to a rod seal part of a through-rod type test apparatus (as shown in fig. 1 of JIS B2409), and a working test was performed by driving a rod directly while applying a pressure between both seals by a hydraulic pressure source. The amount of external leakage (cc/100m) was measured at 0-100 km operation time to evaluate the sealing life.
(6) Measurement of elongation of base Fabric
A dumbbell test piece having a length of 100mm and a thickness of 2 to 3mm was produced using a base fabric, and a tensile test according to JIS B2403 was carried out to measure the elongation at that time.
[ Table 2]
Figure BDA0001064538880000161
Evaluation results were as follows: the best results were scored as 5 points and the worst results were scored as 1 point.
The embodiments of the present invention have been described, but it should be understood that the embodiments disclosed herein are illustrative and not restrictive in all respects. The scope of the present invention is defined by the claims, and all modifications equivalent in meaning and scope to the claims are intended to be included therein.

Claims (5)

1. A sealing material is an annular sealing material obtained by molding and crosslinking a belt-shaped base fabric, wherein the belt-shaped base fabric is obtained by embedding a base material in a rubber composition, and the rubber composition contains 60 mass% or more of hydrogenated nitrile rubber as a rubber component;
the elongation of the crosslinked base fabric is within the range of 35-60%;
the base material is formed of a cord fabric or a plain weave fabric of aramid fibers, which includes warp and weft of aramid fibers.
2. The seal according to claim 1, wherein the hydrogenated nitrile rubber has an acrylonitrile content in the range of 25 to 50 mass%.
3. The sealing member according to claim 1, which is formed of a laminate of a plurality of strip-shaped base cloths, and the threads of the base materials constituting the base cloths intersect with each other between the laminates.
4. The seal of claim 1, having a V-shaped or U-shaped cross-section.
5. A method for manufacturing the seal according to claim 1, using an annular mold, the method comprising:
(a) a step for preparing a base fabric obtained by impregnating a base material with a solution of a hydrogenated nitrile rubber composition and embedding the base material in the rubber composition;
(b) preparing a plurality of strip-shaped base cloths obtained by cutting the base cloths into oblique strips with a predetermined size;
(c) sequentially arranging the strip-shaped base fabrics on the surface of the annular die along the circumferential direction of the annular die on the whole circumference;
(d) pressing the band-shaped base cloths in the direction of a mold so as to enable the band-shaped base cloths to be mutually adhered to form a preformed body; and
(e) and a step of crosslinking the preform by applying pressure and heat to the preform.
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