KR20040089076A - Sliding member and pump - Google Patents

Abstract

A sliding member comprising an epoxy resin composition and a carbon fiber reinforced plastic containing carbon fibers, the sliding member having a dimensional change rate by swelling of the cured product of the epoxy resin composition at 25 ° C. using petroleum, pure water, and alkaline aqueous solution at all 0.5% or less; and A pump with this is provided.

In the case of using various fluids such as petroleum, water, and aqueous alkali solution, the sliding member of the present invention is a sliding member which is small in dimensional change due to swelling of the fluid and can maintain a clearance within a certain range. In addition, the pump of the present invention is a pump with good efficiency and excellent stability.

Description

Sliding Member and Pump {SLIDING MEMBER AND PUMP}

In general pumps for handling fluids, bearings, wear rings, bushes, sleeves, seal rings, vanes, and the like are widely used as sliding members, and these parts are required for dimensional stability because they are important parts of the pump function and structure.

In the past, these parts were made of metal, ceramics, plastic, carbon or the like. However, since the metal is large in thermal expansion and the ceramic is brittle, there is a difficulty in using it for a long time, and the plastic is deteriorated in the sliding property due to thermal expansion or swelling, and there is a need to improve the efficiency of the pump.

Japanese Laid-Open Patent Publication No. 2001-82484 describes a carbon fiber reinforced plastic having a small thermal expansion coefficient in the radial direction. In this case, the dimensional change with respect to temperature change is small, and the effect which improves the efficiency of a pump is recognized. However, depending on the type of fluid, the matrix resin of carbon fiber reinforced plastics may swell, causing dimensional changes comparable to thermal expansion.

The present invention relates to a sliding member, and in particular, the sliding member can be suitably used for cylindrical bearings, wear rings, bushes, sleeves, sealing rings, etc. used in pumps, aberrations, and the like, and plate-shaped vanes. The invention also relates to a pump.

1 is a schematic diagram for explaining the thermal expansion in the radial direction of the cylindrical sliding member.

2 is an exemplary cross-sectional view of a centrifugal pump for showing the use place of the sliding member.

3 is a detailed view of a seal portion of the pump shown in FIG. 2.

4 is a sectional view of an example of an impeller-type pump for indicating a position where a sliding member is used.

FIG. 5 is a detailed view of the impeller portion of the pump shown in FIG. 4.

6 is an exemplary cross-sectional view of the vertical pump to indicate the position where the sliding member is used.

7 is an exemplary cross-sectional view of the vane pump for indicating the position at which the sliding member is used.

8 is a schematic diagram for explaining the clearance of vanes.

9 is a graph showing the relationship between the discharge amount of a pump and the pump efficiency of Examples and Comparative Examples.

10 is a graph showing the relationship between the discharge amount and the total pressure of pumps of Examples and Comparative Examples.

11 is a graph showing the relationship between the discharge amount and the axial power of the pumps of Examples and Comparative Examples.

Explanation of symbols on the main parts of the drawings

1: impeller 2a, 2b: case

3: spindle 4: case wearing ring

4a: suction side case wear ring 4b: rear case wear ring

5: impeller wear ring 5a: suction side impeller wear ring

5b: rear impeller wear ring 7: impeller body

8: case body 21: bushing

22: wear ring 23: seal

31: sealing 41: impeller

61: sleeve 71: vane

72: rotor 73: clearance

Best Mode for Carrying Out the Invention

[Dimension Change Rate]

In the present invention, the dimensional change rate due to swelling is measured as follows. First, the 60 mm x 10 mm x 3 mm plate-shaped test body which consists of hardened | cured material of an epoxy resin composition is prepared, and the length of the long side (60 mm side) after vacuum-degassing this test body at 100 degreeC for 5 hours is made into L1. do. Next, the test piece is brought into contact with a fluid to measure the length of the long side at the point where the swelling reaches equilibrium. At this time, the dimensional change rate is expressed as (L2-L1) / L1 x 100 (%). A series of tests are carried out at 25 ° C.

As said fluid, it can select suitably according to the use environment of the sliding member of this invention. Petroleum (crude oil, naphtha, light oil, kerosene, LPG), pure water, aqueous alkali solution, etc. are typical examples. Sliding member using an epoxy resin composition having a dimensional change rate of 0.5% or less with respect to any one of crude oil, naphtha, diesel oil, kerosene, and LPG, and a dimensional change rate of 0.5% or less with respect to pure and alkaline aqueous solution (12% by mass sodium hydroxide solution) Is preferable because it can be used satisfactorily under various usage environments. From the same point of view, a sliding member using an epoxy resin composition having a dimensional change rate of 0.5% or less for each of them, namely, crude oil, naphtha, diesel oil, kerosene, LPG, pure water, and all of the aqueous alkali solution, is more preferable.

The sliding member made of carbon fiber reinforced plastic containing an epoxy resin composition having a dimensional change rate as in the present invention is excellent in maintaining clearance between the sliding members, corrosion resistance, abrasion resistance, and bendability.

Epoxy Resin Composition

An epoxy resin composition means the composition containing at least 1 sort (s) of epoxy resin and a hardening | curing agent.

It is preferable that the epoxy resin composition used for the sliding member of this invention is excellent in heat resistance, and the glass transition point of the hardened | cured material is 170 degreeC or more, More preferably, it is 200 degreeC or more. If the glass transition point is less than 170 ° C., it is disadvantageous in that deformation occurs when used in a pump using a high temperature fluid.

Moreover, it is preferable that the epoxy resin composition used for the sliding member of this invention is excellent in moisture absorption resistance with respect to a used fluid. The water absorption of the cured product of the epoxy resin composition is preferably 5% or less, more preferably 3% or less, and the oil absorption is preferably 3% or less, and more preferably 1% or less. If the water absorption exceeds 5%, it is disadvantageous in that the dimensional change rate for pure water tends to be out of the above range, and if the oil absorption rate is less than 3%, it is disadvantageous in that the dimensional change rate for petroleum tends to be out of the above range. .

Here, the water absorption rate and the oil absorption rate are the mass W2 when the mass of the epoxy resin composition whose W1 (test body: 60 mm x 10 mm x 3 mm) is immersed in water or petroleum, and the moisture absorption reaches equilibrium. It is a numerical value calculated from: (W2-W1) / W1 x 100 (%).

As an epoxy resin composition, the dimension change rate by swelling at 25 degreeC after hardening may be 0.5% or less. Especially, the epoxy resin composition containing (A) epoxy resin and (C) diamino diphenyl sulfone (hardening agent), or (A) epoxy resin, (B) thermoplastic resin, and (C) diamino diphenyl sulfone The resin composition to contain is preferable.

As said epoxy resin (A), the epoxy resin which consists of a combination selected from the components (a1), (a2), (a3), and (a4) shown next, or these 2 or more types can be used.

Component (a1): bisphenol A type epoxy resin,

Component (a2): bisphenol F type epoxy resin,

Component (a3): Component (a3-1) and / or Component (a3-1)

Component (a3-1): phenol novolak type epoxy resin

Component (a3-2): cresol novolak-type epoxy resin,

Component (a4): tetrafunctional glycidylamine type epoxy resin.

As the thermoplastic resin (B), a single or a combination of two or more thereof selected from the following components (bl) to (b3) can be used.

Component (bl): phenoxy resin,

Component (b2): polyvinyl formal resin,

Component (b3): Copolyester resin.

It is preferable that the compounding ratio of (a1) component used in this invention is 20-40 mass parts, More preferably, it is 25-35 mass parts. When the component (a1) is less than 20 parts by mass, the viscosity of the resin composition is increased, so that impregnation with fiber bundles such as carbon fibers tends to be difficult, and viscosity when the prepreg is an intermediate material tends to be lost. Is disadvantageous. When more than 40 parts by mass, the viscosity of the prepreg becomes stronger, the handling tends to be difficult, and the composite physical properties of the composite material are inferior, and heat resistance and moisture resistance tend to decrease. It is disadvantageous.

It is preferable that the compounding ratio of the component (a2) used as an epoxy resin component in this invention is 20-40 mass parts, More preferably, it is 25-35 mass parts. When the component (a2) is more than 40 parts by mass, it is difficult to adjust the viscosity of the resin compound, making it difficult to manufacture a suitable prepreg, and also disadvantageous in that the glass transition temperature of the cured product is lowered and the heat resistance tends to be lowered. Do.

It is preferable that the compounding ratio of a component (a3) is 20-70 mass parts, More preferably, it is 30-55 mass parts. When the component (a3) is less than 20 parts by mass, the heat resistance as CFRP tends to be lowered. When the component (a3) is more than 70 parts by mass, the viscosity of the epoxy resin component is increased, so that It is disadvantageous in that the impregnation tends to be difficult.

In this invention, it is preferable that the compounding ratio of the component (a4) used as a tetrafunctional glycidylamine type | mold epoxy resin is 35 mass parts or less, More preferably, it is 15-25 mass parts. When the component (a4) is more than 35 parts by mass, it is disadvantageous in that the storage stability and moisture resistance of the prepreg tend to be deteriorated.

It is preferable that the compounding ratio of the component (B) used for this invention is 5-20 mass parts, More preferably, it is 10-15 mass parts. When component (B) is used, 5 mass parts or more are preferable at the point which can prevent the viscosity fall at the time of shaping | molding process, and prevent the leakage, seepage, etc. of resin. When it exceeds 20 mass parts, a viscosity becomes high and it is disadvantageous in the point that there exists a tendency for resin impregnation to CF tow to become difficult at the time of manufacture of a prepreg.

The preferable compounding ratio with respect to component (a1)-(a4) and component (B) demonstrated above shows these preferable relative amounts at the time of using 2 or more types of these. For example, when using components (a2), (a3), (a4) and (B) without using component (a1), 20-40 mass parts, 20-70 mass parts, 35 mass parts or less, respectively, It is preferable to mix | blend in the relative ratio of 5-20 mass parts. For example, when using only (a1) as a component (A) and using a component (B), it is preferable to mix | blend in the range of 20-40 mass parts and 5-20 mass parts, respectively. When only (a1) is used as a component (A) and a component (B) is not used, all of a component (A) becomes a component (a1).

When the compounding ratio of the component (C) used for this invention makes the total amount of the said component (A) and (B) 100 mass parts, it is preferable that it is 20-45 mass parts with respect to this, More preferably, it is 30-40 mass It is wealth. If the component (C) is less than 20 parts by mass, the heat resistance is lowered, which is disadvantageous in that it tends to be difficult to obtain an appropriate molded article. If it exceeds 45 parts by mass, it is disadvantageous in that storage stability, dimensional change rate and moisture resistance tend to be deteriorated.

As the bisphenol A epoxy resin of the component (a1) in the present invention, any one or a combination of two or more solid, semisolid, liquid bisphenol A epoxy resins can be used at room temperature, and a liquid bisphenol A epoxy resin can be used. It can be used preferably.

For example, the liquid phase is Epicoat 825, Epicoat 827, Epicoat 828 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), Efototo YD128 (trade name, manufactured by Toto Chemical Co., Ltd.), Epiclone 840, Epiclone 850, Epiclone 855 (trade names, manufactured by Dainippon Ink and Chemicals, Inc.), DER 330, DER 331, DER 332 (trade names, manufactured by Dow Chemical, Inc.), Araldite CY205, Araldite CY230, Araldite CY232, Araldite CY221 , Araldite GY257, Araldite GY252, Araldite GY255, Araldite GY250, Araldite GY260, Araldite GY280 (trade name, each manufactured by Asahi Kasei Epoxy Co., Ltd.) and the like, and the semi-solid is Epi Coat 834 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) and the like can be used, and the solid ones are Epicoat 1001, Epicoat 1002, Epicoat 1004, Epicoat 1009 (trade names, manufactured by Japan Epoxy Resin Co., Ltd.), Efototo YD011 , Efototo YD012, Efototo YD014, Efototo YD017, Efototo YD019, Efototo YD020 (trade name, manufactured by Toto Chemical Co., Ltd.), Epiclone 860, Epiclone 1050, Epiclone 3050, Epiclone 4050, Epiclone 7050 (each Brand name, Dainippon Ink and Chemicals Co., Ltd.), DER 662, DER 662U, DER 663U (trade name, Dow Chemical Co., Ltd.), Araldite GY6071, Araldite GY7071, Araldite GY7072 (trade name, Asahi Kasei epoxy company, respectively) Production) can be used.

When a liquid bisphenol A type epoxy resin or (a2) bisphenol F type epoxy resin is used as part of component (A), the viscosity of the resin composition of the present invention can be easily adjusted, and the carbon fiber can be easily impregnated to prepreg It becomes suitable for manufacture or shaping | molding.

Hereinafter, resin which is liquid at 20 degreeC means resin which is 100-1000000 mPa * s, Preferably it is 1000 to 50000 mPa * s in 20 degreeC.

Examples of the bisphenol F type epoxy resin of the component (a2) in the present invention include Epicoat 806, Epicoat 807 (manufactured by Japan Epoxy Resin Co., Ltd.), Efototo YDF170 (manufactured by Toto Kasei Co., Ltd.), Epiclone 830, Epiclone 830S, What is marketed by brand names, such as Epiclone 830LVP, Epiclone 835, and Epiclone 835LV (made by Dainippon Ink Chemical Co., Ltd.), These are all liquid at 20 degreeC. ·

As a phenol novolak-type epoxy resin and / or cresol novolak-type epoxy resin of component (a3), what is liquid, semi-solid, or solid phase can be used individually or in combination suitably at normal temperature.

As said phenol novolak-type epoxy resin, a liquid, semi-solid, and solid thing can be used at 20 degreeC, As a liquid thing, Epicoat 152 (brand name, the Japan epoxy resin company make), DEN 431, DEN 438 (brand name, respectively) Dow Chemical Co., Ltd., Epiclone N-738 (brand name, the Nippon Chemical Co., Ltd.), etc. can be used, As a semi-solid thing, Epicoat 154 (brand name, Japan Epoxy Resin company), Efototo YDPN-638 ( Trade name, manufactured by Toto Chemical Co., Ltd., DEN 439 (trade name, manufactured by Dow Chemical Co., Ltd.), epiclon N-740 (trade name, manufactured by Nippon Kayaku Co., Ltd.), and the like. Phototo YDPN-602 (trade name, manufactured by Toto Chemical Co., Ltd.), Epiclone N-770, Epiclone N-775, and EPPN-201 (trade name, manufactured by Nippon Kayaku Co., Ltd.) may be used.

As said cresol novolak-type epoxy resin, it is known that it is solid at 20 degreeC normally, Efototo YDCN701, Efototo YDCN702, Efototo YDCN703, Efototo YDCN704 (brand name, Toto Kasei Co., Ltd. make), Epiclone N-660, Epiclone N-665, Epiclone N-667, Epiclone N-670, Epiclone N-673, Epiclone N-680, Epiclone N-690, Epiclone N-695 (trade name, Die, respectively) Nippon Ink Chemical Co., Ltd.), ESCN-195X, ESCN-220 (trade name, manufactured by Sumitomo Chemical Co., Ltd.), EOCN-1020, EOCN-1025, EOCN-1027, EOCN-102S, EOCN-103S, EOCN-104S (each brand name, Nippon Kayaku Co., Ltd.) etc. can be used.

Examples of the tetrafunctional glycidylamine type epoxy resin of the component (a4) include YH434 (trade name, manufactured by Toto Chemical Co., Ltd.), YH434L (trade name, manufactured by Toto Chemical Co., Ltd.), Sumiepoxy ELM434, Sumiepoxy ELM434HV (trade name, Sumitomo Chemical Co., Ltd.) Epicoat 604 (brand name, the Japan epoxy resin company make), MY720 (brand name, the Chiba Corporation company), etc. are mentioned.

Examples of the phenoxy resin of the component (B) are phenotot YP-50, phenotot YP-70 (trade name, manufactured by Toto Chemical Co., Ltd.), Epicoat OL-53 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), and Sumiepoxy ESP. -50 (brand name, the Sumitomo Chemical Co., Ltd. product) etc. are mentioned.

As diaminodiphenyl sulfone of component (C), both 4,4'- diamino diphenyl sulfone and 3,3'- diamino diphenyl sulfone can be used, A mixture thereof may be sufficient.

The diaminodiphenylsulfone is powdery at room temperature, and the upper limit of the particle size is preferably 20 µm or less, more preferably 17 µm or less, even more preferably 12 µm or less, and the lower limit of the particle size is preferably O.O1. The proportion of the powder particles of more than 0.1 µm, more preferably 0.1 µm or more, and more preferably 1 µm or more, in the whole powder particles of diaminodiphenylsulfone is preferably 65 mass% or more, more preferably 70 mass % More than. More preferably, a uniform hardened | cured material is obtained as it is a particle size distribution of 80 mass% or more.

In the case of using an epoxy resin composition composed of 100 parts by mass (the amount of component (B) may be 0 (zero)) and 20 to 45 parts by mass of component (C) in the sum of components (A) and (B), It is preferable because the effect of is remarkably exhibited. Moreover, in the epoxy resin composition of this invention, a toughening agent, a filler, a coloring agent, etc. can also mix | blend epoxy resins other than the said components (a1)-(a4) in the range which does not impair the performance.

As epoxy resins other than the said components (a1)-(a4) which can be contained as desired in the resin composition of this invention, a cyclic aliphatic epoxy resin, a triglycidyl methane type epoxy resin, and trifunctional glycidylamine Type epoxy resin, halogenated bisphenol A type epoxy resin, etc. are mentioned.

As the toughening resin which can be contained in the resin composition of the present invention as desired, a reactive elastomer, a high-car CTBN modified epoxy resin, a urethane modified epoxy resin, a nitrile rubber-added epoxy resin, a crosslinked acrylic rubber fine particle-added epoxy resin, a silicone-modified epoxy resin, Thermoplastic elastomer addition epoxy resin etc. are mentioned.

Fillers which can be contained in the resin composition of the present invention as desired include inorganic fine particles such as mica, alumina, talc, finely divided silica, wollastonite, calcite, basic magnesium sulfate, zinc powder, aluminum powder, organic fine particles such as acrylic fine particles, Epoxy resin microparticles | fine-particles, polyurethane microparticles | fine-particles, etc. can be used.

As a coloring agent which can be contained as desired in the resin composition of this invention, an organic pigment, such as an azo pigment, a phthalocyanine pigment, a quinacridone pigment, an anthraquinone type pigment, etc., Inorganic pigments, such as titanium dioxide, sulfur lead, cobalt violet, bengal, etc. Can be mentioned.

In addition to the curing agent of component (C), other curing agents and curing accelerators may be added as necessary. As a hardening | curing agent which can be mix | blended other than component (C), As a hardening accelerator which can be mix | blended other than component (C), such as dicyandiamide and diaminodiethylbenzene, a fluoro fluoromonoethylamine complex and a fluoromonoethyl chloride trichloride. BF ₃ complexes, such as these, etc. are mentioned.

[Manufacturing method of epoxy resin composition]

Although there is no restriction | limiting in particular in the manufacturing method of an epoxy resin composition, Resin components except (a4), for example, (a1), (a2), (a3), and (B) are heat-mixed at 140-200 degreeC, and are cooled or cooled. After lowering to 120 degrees C or less by adding a component (a4), and after that the temperature of a resin mixture becomes 90 degrees C or less, the method of adding a hardening component (C) is used preferably. In addition, when mixing the said hardening component (C), the method of vacuum degassing with stirring for the purpose of reducing generation | occurrence | production of the void after shaping | molding is employ | adopted preferably.

According to this method, the component (C) becomes a system uniformly dispersed in the resin composition and is excellent in storage stability. On the other hand, when a resin temperature is higher than 90 degreeC, when a hardening component (C) is added and mixed, a part of hardening component (C) will melt | dissolve in resin, resin and a hardening | curing agent will react easily, and a reinforcing fiber may be made to the said resin composition. It is disadvantageous in that there is a tendency to impair the storage stability of the intermediate material for composite materials that can be impregnated.

Dissolving diphenyldiaminosulfone (C) at 135 DEG C with tetrafunctional glycidylamine type epoxy resin (a4) as a main component requires safety considerations due to rapid reaction during mixing, It is disadvantageous in that removal becomes difficult, and when mixed with other resin, there exists a tendency for the moisture resistance of a molding and the storage stability of a resin composition to fall.

[Carbon fiber]

As the carbon fibers, those having a tensile modulus of 45 to 950 GPa are preferably used, and particularly preferably 200 to 650 GPa. In addition, the tensile strength of the carbon fiber is preferably 1100 to 4700 MPa, and particularly preferably 2400 to 4500 MPa. As thermal expansion rate (linear expansion rate in a fiber direction) of carbon fiber, it is preferable that they are -1.5 * 10 <^-6> -4 * 10 <^-6> / degreeC. By using the carbon fibers of such physical properties, the expansion of the matrix resin is suppressed to reduce the thermal expansion coefficient of the carbon fiber reinforced plastic itself, and when the sliding member is cylindrical, the expansion and contraction of the gas to which the cylindrical sliding member is attached is prevented. Since it can also suppress, the thermal expansion coefficient of the radial direction as a cylindrical sliding member can be set to a desired value.

Pitch type carbon fiber, PAN type carbon fiber, etc. can be used as carbon fiber. It can also use together and form a carbon fiber reinforced plastic as needed. It is preferable to select so that a desired expansion ratio can be obtained as the sliding member in consideration of the position to be used and the raw material of the sliding member (relative member) on the opposite side to be paired.

As carbon fiber, it is preferable to use continuous carbon fiber rather than short carbon fiber.

Here, the continuous carbon fibers are carbon fibers other than short fibers such as chopped, milled or pulverized carbon fibers or whiskey carbon fibers. The short carbon fiber means that the length is usually 0.1 to 10 mm.

[Sliding member]

The sliding member of the present invention is composed of a carbon fiber reinforced plastic containing an epoxy resin composition and carbon fiber, and impregnated with carbon resin to heat the carbon fiber to obtain a carbon fiber reinforced plastic. Can be.

More specifically, said component (A) (preferably including at least one of components (a1), (a2), (a3) and (a4)) and component (C), further components as needed The resin composition containing (B) is impregnated with carbon fiber to give an intermediate material (prepreg) for a composite material, which is cured to form a carbon fiber reinforced plastic, and a sliding member can be obtained by appropriately molding it.

As for the volume content of the carbon fiber in a carbon fiber reinforced plastics, about 45-70 volume% is preferable, and 50-65 volume% is especially preferable. It is preferable that the volume content of carbon fiber is 45 volume% or more from a viewpoint of fully exhibiting the characteristic by the elasticity modulus and thermal expansion coefficient of a carbon fiber. If the volume content exceeds 70% by volume, the resin is less, which is disadvantageous in that a good molded article tends to be difficult to be obtained.

As a shape of a sliding member, although a cylindrical shape and a plate shape are mentioned as a typical example, other shapes may be sufficient as it.

The cylindrical sliding member can be used as a bearing, a wear ring, a bush, a sleeve, a seal ring, and the like, and the plate-shaped sliding member can be used as a vane or the like, and all of these can be used as constituent members of a pump, for example.

On the other hand, the sliding member is used in a rotary device such as a pump or a reciprocating device or the like as one side of a pair of members each having a pair of sliding surfaces that can slide relative to each other. One side of the sliding member is fixed, and one side often performs rotation or reciprocating motion. The sliding member of the present invention may be a fixed sliding member, a moving side, or both.

[Cylindrical sliding member]

It is preferable that the thermal expansion coefficient of the cylindrical sliding member in the radial direction is -1 * 10 <^-6> -30 * 10 <^-6> / degreeC.

A method of obtaining the thermal expansion coefficient in the radial direction of the cylindrical sliding member will be described as an example in which the sliding member is used for the wear ring. FIG. 1A shows the case where the cylindrical sliding member is an impeller wear ring 5 attached to the outer circumferential surface of the impeller main body 7, that is, the inner cylinder side sliding member, and the impeller wear ring outer diameter Ø1 is a temperature change of Δt ° C. When changed into (Ø1 + ΔØ1) by, the thermal expansion coefficient is obtained by ΔØ1 / (Ø1 · Δt). 1B has shown the case where the cylindrical sliding member is the case wear ring 4 arrange | positioned at the inner peripheral surface of the case main body 8, ie, the case where it is an outer cylinder side sliding member. When the wear ring inner diameter Ø 2 is changed to Ø 2 + ΔØ 2 by a change in Δt ° C., the thermal expansion coefficient is obtained by ΔØ 2 / (Ø 2 · Δt).

[Method of Manufacturing Cylindrical Sliding Member]

The continuous carbon fiber is wound one or more times in the circumferential direction of the cylindrical sliding member (or cylindrical circumferential direction if it is cylindrical) so that the properties of the carbon fiber can be effectively used, and the thermal expansion coefficient in the radial direction as the cylindrical sliding member can be set to a desired value. Can be. Thus, at least a part of the carbon fibers in the carbon fiber reinforced plastics constituting the cylindrical sliding member is preferably arranged substantially in the circumferential direction. Moreover, in order to prevent the cracks etc. by deformation, it is preferable that carbon fiber arrange | positioned in the cylindrical sliding member axial direction (direction of a rotating shaft) also exists.

In order to form a cylindrical sliding member of a predetermined shape, according to a molding method called, for example, a citro ring molding, first, a carbon resin is impregnated with a matrix resin by a known method, and a sheet-shaped one-way prepreg or a fabric prepreg is formed. After laminating it to the mandrel by a predetermined number of layers, and heat-curing the resin, if it is heat cured and then removed from the mandrel, a cylindrical molded body of carbon fiber reinforced plastic is obtained. Then, it cuts to predetermined length, and grinds and grinds with predetermined precision as needed in order to make a clearance correctly, and obtains a cylindrical cylindrical sliding member.

In addition, in the filament winding lamination method known as another lamination method, the toe prepreg in which carbon fibers are impregnated with a matrix resin can be wound while being oriented and laminated as many as necessary layers. In addition, the toe prepreg can be squeezed to form a cylindrical shape. Alternatively, the matrix resin may be impregnated after squeezing the carbon fiber into a cylindrical shape.

In one embodiment of the present invention, it is preferable that alternately laminating the circumferential directions 1 to 10 layers and the axial direction 1 to 10 layers using a one-way prepreg by forming by means of controlling molding. At that time, the sheet-shaped prepreg whose thickness becomes about 0.05 to 0.3 mm after hardening is used, and the lamination total number at that time changes suitably according to the thickness of one layer and the thickness of a cylindrical sliding member. For typical thicknesses it is, for example, about 20 to 300 layers. Moreover, it is preferable to laminate | stack about 1-10 layers of textile prepregs, especially about 1-5 layers as needed in the outermost layer (at least one of the outer side and the inner side of a cylinder) as needed. If the outermost layer is formed of a woven prepreg, there is an advantage that it is difficult to cause fluff during grinding and polishing.

[Use of Cylindrical Sliding Member]

Thus, the cylindrical sliding member processed into a cylindrical shape can be attached to the processed body so that the said cylindrical sliding member can be used. When an air is an impeller pump, a gas is a case main body or an impeller main body, for example.

The cylindrical sliding member is usually used for a pair of sliding members composed of an inner cylinder side sliding member (for example, a cylindrical sliding member on the impeller side) and an outer cylinder sliding member (for example, a cylindrical sliding member on the case side). The cylindrical sliding member can be used for one or both of the inner cylinder side sliding member and the outer cylinder side sliding member.

When only one of the inner cylinder side or the outer cylinder side is used, metal, ceramics, plastics, carbon, fiber-reinforced composite materials, etc. can be used as the counterpart sliding member, and metals are preferred for workability and cost merit, and wear resistance such as SUS304, SUS403, etc. This high and hard to rust stainless steel material is preferable. The inner cylinder side sliding member may be the shaft itself.

EMBODIMENT OF THE INVENTION Hereinafter, it demonstrates in detail using drawing. Specific use places of bearings, wear rings, bushes, sleeves and seal rings are as shown in, for example, FIGS. 2 to 6. 2 shows an example of a centrifugal pump, in which the sliding member of the present invention is a bushing (21: the sliding member of the present invention is the outer cylinder side of the sliding part), and the wear ring (22: the sliding member of the present invention is a pair). Inner cylinder side of the sliding member). The seal portion 23 is shown in detail in FIG. 3, and the sliding member of the present invention is used for the seal ring 31. FIG. 4 shows an example of an impeller pump, and details of the impeller portion 41 are shown in FIG. 5. Fig. 6 shows an example of a standing pump, in which the sliding member of the present invention is used for a sleeve 61 (in this case, the sliding member of the present invention is the outer cylinder side of the pair of sliding members).

5 shows an example of a pump structure using the cylindrical sliding member of the present invention as a wear ring, by rotating the impeller 1 housed in the cases 2a and 2b by a main shaft 3 connected to a motor (not shown) or the like. The fluid is introduced in the A direction, pressurized and discharged in the impeller circumferential direction, and then combined in the case and discharged at an outlet not shown. When attention is paid to the wear ring portion, the suction side impeller wear ring 5a and the suction side case wear ring 4a are paired, and the rear side impeller wear ring 5b and the rear side case wear ring 4b are configured in pairs. The wear ring of this example is all cylindrical having a predetermined thickness and length, and is attached to the impeller main body 7 and the case main body 8, for example, as shown in FIG.

In the pump of the present invention, in each pair of wear ring rings, that is, 4a and 5a, or 4b and 5b, the wear ring ring on one side of the pair may be formed of the cylindrical sliding member of the present invention. However, on the suction side, for example, in the case where the case wear ring 4a is made of metal by applying the wear ring of the present invention to the impeller wear ring 5a, the thermal conditions are also similar in consideration of the rear side. It is preferable to apply the wear ring of this invention to the impeller wear ring 5b, and to make the case wear ring 4b metal.

The pump shape is not limited to that illustrated in FIG. 5 but can be changed in accordance with the material used, the pump capacity, the type of fluid, and the like.

In the present invention, when the cylindrical sliding member is used as a wear ring for use in a pump, it can be used for both the case wear ring and the impeller wear ring.

When the sliding member of the present invention is used only on one side of the wear ring, as the wear ring material on the mating side, metal, ceramics, plastic, carbon, fiber reinforced composite material, and the like can be used. Metal is especially preferable at the point of workability and price, and stainless steel which is especially high in abrasion resistance, such as SUS304 and SUS403, and hard to rust is preferable.

The diameter, thickness, and axial length of the wear ring can also be changed as appropriate. Although the cylindrical shape and the shape of the inner cylinder side wear ring are generally cylindrical and easy to shape, the shape of the inner cylinder side or the outer cylinder side wear ring may be another shape known as a shape of a wear ring such as a cone (cone shape). In addition, in this specification, the terms of an outer cylinder side and an inner cylinder side are used in order to distinguish a sliding member of an outer side and a sliding member of a pair, and do not show only a cylindrical member of a "cylindrical shape."

When the cylindrical sliding member of the present invention is used for a wear ring, since the dimensional change due to moisture absorption and swelling is small, the clearance between the inner cylinder side and the outer cylinder side (inner diameter and inner cylinder side of the outer cylinder side) as long as the central accuracy of the rotating shaft is sufficiently ensured. Even if it sets the difference of the outer diameter of a side) to 0.4% or less of diameter (outer diameter of an inner cylinder side), and also to 0.2% or less, baking can be prevented without contacting. In general, since there is also a problem of the center accuracy of the rotating shaft, it is preferable to set it to 0.02% or more, preferably 0.05% or more, and more preferably 0.1% or more.

For example, in the case of a cylindrical sliding member having a diameter of 80 mm, it is most preferable to set the clearance to about 0.08 mm to 0.16 mm.

[Flat type sliding member]

One type of the sliding member of this invention is a plate-shaped sliding member. This is used, for example, as a vane of a vane pump having a rotor 72 having a radial groove and a vane 71 fitted in the groove, as shown in FIG. Although the detail is shown in FIG. 8, clearance 73 is the space | gap of the vane 71 and a main body case.

When the sliding member of the present invention is used as a vane for the vane, the clearance 73 can be set to 0.3 to 2.0 mm, more preferably 0.3 to 1.0 mm.

The plate-shaped sliding member can be manufactured by a well-known method as a manufacturing method of flat carbon fiber reinforced plastics.

For example, carbon fiber can be manufactured by impregnating the said epoxy resin composition into a prepreg, and laminating | stacking and hardening these again.

In particular, the prepreg sheet in which carbon fibers are oriented in one direction is laminated so that the fiber direction is in two directions of 0 ° and 90 ° with respect to the longitudinal direction of the plate-shaped sliding member, or 0 °, ± 45 ° and 90 °, Alternatively, it is preferable to obtain a plate-like sliding member having a desired elastic modulus by laminating in three directions of 0 °, ± 60 ° and 90 °.

Such a plate-like sliding member can maintain high strength by carbon fibers oriented longitudinally and horizontally. In addition, because of the excellent heat transfer characteristics and sliding heat can be removed well, the cooling effect is great. In addition, since the rate of dimensional change is small, vane voids (clearance) can be minimized, and whistling of vane in and out is suppressed, so that the vane slide is smoothly performed, thereby achieving low noise.

As a preferable example of the plate-like sliding member, it has an elongated plate-like structure, and has a skin layer located on both surfaces of the plate, and a core layer located between the skin layers, wherein the skin layer is carbon fiber with respect to the longitudinal direction of the sliding member. Is a layer orientated in parallel, and the core layer is composed of a layer in which the carbon fibers are perpendicular to the longitudinal direction of the sliding member, and if necessary, additionally oriented in an angular range of ± 60 ° or ± 45 ° relative to the longitudinal direction. Carbon fiber reinforced plastics are preferred. Although the prepreg of each layer can be laminated in multiple layers, the sheet type prepreg which becomes about 0.05-0.3 mm after hardening is used suitably for each layer, and the total number of laminated at that time depends on the thickness of one layer and the thickness of a sliding member. Make the appropriate changes. For typical thicknesses it is for example 20 to 300 layers.

The outermost surface may also be laminated with carbon fiber fabric prepregs, preferably 1 to 10 layers, more preferably 1 to 5 layers. In this case, it is preferable at the point which the post-processing of sliding members, such as grinding and grinding | polishing, for making clearance of the vane slide part becomes easy by the formed fabric layer.

Next, the present invention will be described in more detail with reference to Examples. The pump used for the evaluation is a cantilever centrifugal pump having a head of 55 m, a capacity of 14 m 3 / h, an output of 3.70 kW, and a rotational speed of 2900 rpm. The shape is almost the same as shown in FIGS. 4 and 5. In the pump shown in Fig. 5, the diameter and length of the wear ring pair on the suction side and the wear ring pair on the rear side are different, but in the pump used here, the suction side and the back side have the same shape.

In addition, the measurement of the performance of the pump in the Example uses about 20 degreeC water as a fluid, and the relationship of discharge amount and pump efficiency (simple efficiency = passive force / axial force x100), discharge amount, and voltage force by the method according to JIS. Relationship, discharge amount and axial force.

In the case of using various fluids such as petroleum, water and alkaline aqueous solution, the present invention provides a sliding member, in particular a cylindrical or plate-like sliding member, which has a small dimensional change due to the wetness of the fluid and can keep the clearance within a certain range. The present invention also provides a highly efficient pump having excellent sliding members, particularly a bearing using a cylindrical sliding member, a wear ring, a bush, a sleeve, a seal, and a vane using a plate-like sliding member. .

This invention is a sliding member which consists of carbon fiber reinforced plastics containing an epoxy resin composition and carbon fiber,

The dimensional change rate by swelling using the petroleum, pure water, and aqueous alkali solution at 25 degreeC of the hardened | cured material of the said epoxy resin composition is all 0.5% or less, It is a sliding member characterized by the above-mentioned.

The present invention also provides a sliding member made of a carbon fiber reinforced plastic containing an epoxy resin composition and carbon fibers and used in contact with a fluid.

The dimensional change rate by swelling using the said fluid at 25 degreeC of the hardened | cured material of the said epoxy resin composition is 0.5% or less, It is a sliding member characterized by the above-mentioned.

In this sliding member, the epoxy resin composition

(A) 100 mass parts of epoxy resins, and

(C) It is preferable to contain 20-45 mass parts of diamino diphenyl sulfones.

The epoxy resin composition

100 parts by mass in total (A) epoxy resin and (B) thermoplastic resin, and

(C) It is also preferable to contain 20-45 mass parts of diamino diphenyl sulfones.

The epoxy resin (A) is,

(a1) bisphenol A epoxy resin,

(a2) bisphenol F type epoxy resin,

(a3-1) phenol novolac type epoxy resin,

(a3-2) cresol novolac type epoxy resin, and

(a4) It is also preferable to contain 1 type (s) or 2 or more types of epoxy resins chosen from the group which consists of tetrafunctional glycidylamine type epoxy resins.

The thermoplastic resin,

(b1) phenoxy resins,

(b2) polyvinyl formal resin, and

(b3) It is also preferable to contain 1 type (s) or 2 or more types of thermoplastic resins chosen from the group which consists of a copolyester resin.

It is also preferable that the carbon fiber is a continuous carbon fiber having a tensile modulus of 45 GPa to 950 GPa.

The inner cylinder side has a clearance formed between one of the cylindrical sliding members for a pair of wearing rings for the inner cylinder side and the outer cylinder side, the clearance being formed between the other cylindrical sliding members. The sliding member is also preferably 0.4% or less of the outer diameter of the cylindrical sliding member.

For the plate-like sliding member used as a vane of a rotor having a radial groove and a vane pump having a vane fitted into the groove, the sliding member having a clearance between the rotor and 0.3 to 2.0 mm is also preferable.

The invention also includes a pump comprising the sliding member.

Although the Example is shown below, this invention is not limited to this at all.

Example 1

(i) Component (a2): 30 mass parts of bisphenol F-type epoxy resins (made by Toto Chemical Co., Ltd., brand name: Efototo YDF170)

(ii) Component (a3): 35 mass parts of phenol novolak-type epoxy resins (The Toto Chemical Co., Ltd. make, brand name: Efototo YDPN638)

(iii) Component (a4): 22 parts by mass of tetrafunctional glycidylamine-type epoxy resin (manufactured by Toto Chemical Co., Ltd., trade name: Efototo YH434L)

(iv) Component (bl): 13 parts by mass of phenoxy resin (manufactured by Toto Chemical Co., Ltd., product name: Phenototo YP-70)

(v) Component (C): 35 parts by mass of diaminodiphenylsulfone (manufactured by Wakayama Purification Industry Co., Ltd., product name: Seikakyua S ground product)

After mixing and dissolving (i), (ii) and (iv) above at 160 ° C for 2 hours, the temperature was lowered to 120 ° C and (iii) was added and mixed. After lowering the temperature of this mixture further, (v) which is a hardening | curing agent was added, and vacuum degassing was continued for 20 minutes, and the epoxy resin composition was obtained.

This epoxy resin composition was heated at 180 degreeC for 2 hours, and the resin hardened | cured material was obtained. The dimensional change rate at equilibrium when the cured resin was immersed in petroleum (crude oil, naphtha, diesel oil, kerosene), pure water, and 12 mass% sodium hydroxide aqueous solution was 0.5% or less at room temperature.

On the other hand, the epoxy resin composition was impregnated with carbon fiber (trade name: XN-60) manufactured by Nippon Graphite Fiber Co., Ltd., and a prepreg (I) having a thickness of about 0.25 mm having a volume content of carbon fiber of about 55%; Prepreg (II) having a thickness of about 0.25 mm (as thickness after lamination) in which Toray Co., Ltd. manufactured carbon fiber cross (trade name: CO6343) was impregnated with the epoxy resin to make the volume content of carbon fiber about 50%. Was prepared.

Using these, 5 layers of 0 degree alignment layers of prepreg (II) were laminated | stacked on a mandrel, 20 layers were laminated | stacked by alternately combining each of 0 degree alignment layers and 90 degree alignment layers of prepreg (I) one by one, Five layers of 0 ° alignment layers of prepreg (II) were laminated again, followed by thermosetting. As a result, a cylindrical molded body having an outer diameter of 102 mm and an inner diameter of 87 mm was obtained.

The carbon fiber-reinforced plastic cylinder was cut to a predetermined length, ground and ground, and processed into a shape having an outer diameter of 101.0 mm, an inner diameter of 88.5 mm, and a length of 22.5 mm. Again, the mounting screw hole was drilled to obtain a wear ring made of carbon fiber reinforced plastic. This was attached to both the suction side and the back side of the impeller.

On the other hand, as the case wearing ring, an inner diameter of 101.1 mm manufactured by SUS403 was used for both the suction side and the back side. That is, the clearance of the wear ring is 0.1 mm in diameter.

The performance of this pump, that is, the relationship between the discharge amount and the pump efficiency, the relationship between the discharge amount and the voltage force, and the relationship between the discharge amount and the axial force, are shown in Figs. 9, 10 and 11, respectively. In addition, despite this narrow clearance, baking did not occur.

Comparative Example 1

As the impeller wearing ring, a product made of SVUS403 having an outer diameter of 100.7 mm and a length of 22.5 mm was used. In addition, as a case wearing ring, the thing of inner diameter 101.1 mm made from SUS403 was used similarly to Example 1. That is, the clearance of the wear ring is 0.4 mm in diameter. In addition, in both the case wear ring and the impeller wear ring, the coefficient of thermal expansion was about 19 × 10 ⁻⁶ / ° C. in the radial direction. The performance of this pump is shown in FIG. 9, FIG. 10, and FIG. The performance of the pump was lower than that of Example 1, but no baking occurred.

Comparative Example 2

(ii ') 50 parts by mass of a phenol novolac-type epoxy resin (manufactured by Toto Chemical Co., Ltd .: Efototo YDPN638)

(iii ') 50 mass parts of 4-functional glycidylamine-type epoxy resins (Toto Kasei Co., Ltd. make: Efototo YH434)

(v ') 50 parts by mass of diaminodiphenylsulfone

(vi ') 2 parts by mass of diethylamine complex of boron chloride

After mixing said component (ii ') and component (iii') uniformly at 70 degreeC, (v ') is added as a hardening | curing agent, (F) is added again as a hardening accelerator, and it fully stirs and mixes an epoxy resin A composition was obtained.

This epoxy resin composition was heated at 180 ° C. for 2 h to obtain a resin cured product. The dimensional change rate at equilibrium when the resin cured product was immersed in petroleum (crude oil, naphtha, diesel oil, kerosene), pure water, and 12% sodium hydroxide solution at room temperature was 0.5% or less in petroleum, but pure, 12% sodium hydroxide. It was 0.8% in aqueous solution.

On the other hand, the wear ring was created and evaluated similarly to Example 1 except having used the said epoxy resin.

However, it was not possible to operate stably because baking was generated after a few minutes of starting to use the pump.

According to the present invention, even when various fluids such as petroleum, water, and alkaline aqueous solution are used, a sliding member having a small dimensional change or deterioration due to the wetness of the fluid is provided, and durability and clearance can be maintained in a constant range. In addition, a pump having excellent stability and efficiency is provided.

Claims (10)

A sliding member made of a carbon fiber reinforced plastic containing an epoxy resin composition and carbon fibers, The dimensional change rate by swelling by the petroleum, pure water, and aqueous alkali solution at 25 degreeC of the hardened | cured material of the said epoxy resin composition is 0.5% or less, The sliding member characterized by the above-mentioned. A sliding member made of a carbon fiber reinforced plastic containing an epoxy resin composition and carbon fibers and used in contact with a fluid, The dimensional change rate by swelling by the said fluid in 25 degreeC of the hardened | cured material of the said epoxy resin composition is 0.5% or less, The sliding member characterized by the above-mentioned. The method of claim 1 or 2, wherein the epoxy resin composition (A) 100 mass parts of epoxy resins, and (C) Sliding member containing 20-45 mass parts of diaminodiphenyl sulfones. The method of claim 1 or 2, wherein the epoxy resin composition 100 parts by mass in total (A) epoxy resin and (B) thermoplastic resin, and (C) Sliding member containing 20-45 mass parts of diaminodiphenyl sulfones. The epoxy resin (A) according to claim 3 or 4, (a1) bisphenol A epoxy resin, (a2) bisphenol F type epoxy resin, (a3-1) phenol novolac type epoxy resin, (a3-2) cresol novolac type epoxy resin, and (a4) Sliding member containing 1 type (s) or 2 or more types of epoxy resins chosen from the group which consists of a tetrafunctional glycidylamine type epoxy resin. The method of claim 4, wherein the thermoplastic resin, (b1) phenoxy resins, (b2) polyvinyl formal resin, and (b3) A sliding member containing at least one thermoplastic resin selected from the group consisting of copolyester resins. The sliding member according to any one of claims 1 to 6, wherein the carbon fiber is a continuous carbon fiber having a tensile modulus of 45 GPa to 950 GPa. The cylindrical sliding member according to any one of claims 1 to 7, for one cylindrical sliding member of a pair of cylindrical sliding members for wear rings, wherein the inner cylinder side and the outer cylinder side are used in pairs. And a clearance formed between the cylindrical sliding member and 0.4% or less of the outer diameter of the cylindrical sliding member on the inner cylinder side. 8. The plate-like sliding member and the rotor according to any one of claims 1 to 7, wherein the plate-like sliding member and the rotor are used for vane of a rotor having a radial groove and a vane pump having a vane fitted into the groove. The sliding member formed in between is 0.3-2.0 mm. The pump provided with the sliding member in any one of Claims 1-9.