JP2015196312A - Sliding member and method for manufacturing sliding member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sliding member that has high heat resistance, is easily manufactured and thinned, and hardly causes the deterioration in sliding characteristics and to provide a method for manufacturing the sliding member.SOLUTION: The sliding member has a metal layer, a resin layer laminated on the front side of the metal layer and an adhesion layer laminated between the metal layer and the resin layer. The resin layer is composed mainly of a phenolic resin. The adhesion layer is laminated on the surface of the metal layer and has a first adhesion layer comprising a porous metal film and a resin material filled in voids of the metal film in which the resin material is composed mainly of a phenolic resin and a second adhesion layer laminated between the first adhesion layer and the resin layer and composed mainly of a phenolic resin. Preferably, the content of the phenolic resin in the second adhesion layer is larger than that of the phenolic resin in the resin layer. The porous metal film of the first adhesion layer is preferably a sintered body of metal particles.

Description

  The present invention relates to a sliding member and a method for manufacturing the sliding member.

  In recent years, in industrial equipment, office equipment, transportation equipment, etc., in order to meet the demands for downsizing, cost reduction, weight reduction, etc., a sliding member combining a metal having excellent wear resistance and strength and a light weight resin has been used. Various proposals have been made. Such a sliding member has a structure in which a resin layer is laminated on a metal base material, and this resin layer slides with a counterpart material.

In the above sliding member, in order to obtain a high bonding strength between a metal and a resin, a technique of sintering a metal powder in a metal layer and filling a void of the sintered metal with a fluororesin or the like (Japanese Patent Laid-Open No. 2003-254330) See), a technique for forming a layer made of a mixture of fluororesin and metal powder on the surface of the metal layer (see JP 2010-121692 A), and between the metal layer and the phenol resin layer, facing the phenol resin layer. For example, a technique of providing three or more mixed layers in which the metal content gradually decreases (see Japanese Patent Application Laid-Open No. 2012-86529) has been developed.

  However, the sliding member using the above-described fluororesin is not suitable for use because the resin softens in an environment where it is instantaneously exposed to a high temperature of about 300 ° C. On the other hand, the sliding member using the above-mentioned phenol resin is suitable for use in the above environment, but has a disadvantage that the formation cost of the mixed layer becomes high. Furthermore, since the number of mixed layers is large, the sliding member is increased in thickness.

  Further, in the above conventional sliding member, when the resin layer is worn out, the metal is exposed on the sliding surface, which causes the surface of the sliding counterpart material to be damaged, and the friction coefficient is likely to increase, that is, the sliding characteristics are lowered. There is also the inconvenience that it is easy.

JP 2003-254330 A JP 2010-121692 A JP 2012-86529 A

  The present invention has been made based on the above circumstances, and provides a sliding member and a manufacturing method of the sliding member that have high heat resistance, that are easy to manufacture and thin, and that do not easily deteriorate sliding characteristics. With the goal.

  The invention made to solve the above problems comprises a metal layer, a resin layer laminated on the surface side of the metal layer, and an adhesive layer laminated between the metal layer and the resin layer. A sliding member comprising a phenol resin as a main component, wherein the adhesive layer is made of a resin material laminated on the surface of the metal layer and filled in a porous metal film and a gap in the metal film. A sliding member comprising: a first adhesive layer mainly composed of a phenol resin; and a second adhesive layer laminated mainly between the first adhesive layer and the resin layer and mainly composed of the phenol resin. .

  The sliding member of the present invention has high heat resistance because the resin layer that slides with the counterpart material contains phenol resin as a main component. Moreover, since the adhesive layer includes a first adhesive layer made of a metal film and a resin material and a second adhesive layer mainly composed of a phenol resin, the bonding strength is excellent. Further, since the sliding member has a relatively small number of layers and each layer can be easily formed, manufacturing and thinning are easy. Furthermore, since the second adhesive layer containing phenol resin as a main component is laminated between the first adhesive layer and the resin layer, even when the resin layer is worn away by sliding, metal powder or the like is not exposed on the sliding surface. Therefore, the sliding member is unlikely to damage the surface of the sliding counterpart material, and the sliding characteristics are unlikely to deteriorate.

  The content of the phenol resin in the second adhesive layer is preferably larger than the content of the phenol resin in the resin layer. Thus, since the second adhesive layer contains a relatively large amount of phenol resin, the second adhesive layer is more easily worn than the resin layer. For this reason, when the resin layer wears and slides on the second resin layer, the wear powder increases, whereby the replacement time of the sliding member can be estimated. Therefore, it is possible to replace the sliding member at an appropriate time, and it is possible to further reduce the breakage of the counterpart material and increase in the friction coefficient, and to exhibit excellent sliding characteristics.

  The porous metal film of the first adhesive layer may be a sintered body of metal particles. Thus, since the porous metal film is a sintered body of metal particles, the metal particles are bonded to the metal layer, and a porous metal film is formed. Further, the voids of the metal film are easily filled with the resin material, and as a result, the anchor effect of the metal film and the resin material of the first adhesive layer is improved. Therefore, the metal layer and the second adhesive layer are firmly bonded via the first adhesive layer, and the strength is improved.

  The average particle size of the metal particles is preferably 100 μm or more and 500 μm or less. By making the average particle diameter of the metal particles in the above range, the anchor effect is further improved and the strength is further increased.

  The phenol resin of the first adhesive layer or the second adhesive layer may be a novolac type phenol resin, a resol type phenol resin, or a combination thereof. When the phenol resin of the first adhesive layer or the second adhesive layer is a novolac type phenol resin, the strength of these layers is improved due to the high crosslink density. On the other hand, when these layers are resol type phenol resins, the thermal shock resistance is improved, so that they are more suitable for use in a high temperature environment. Furthermore, when it is a combination of a novolac type phenol resin and a resol type phenol resin, it can have the said characteristic, and can adjust the intensity | strength etc. of each layer as needed.

  The phenol resin of the resin layer may be a novolac type phenol resin. Thus, since the main component of the resin layer is a novolac type phenol resin, the amount of wear of the resin layer, which is the first sliding surface, can be reduced.

  The resin layer or the second adhesive layer may further contain a filler, a boron compound, or an elastomer. When the resin layer or the second adhesive layer further contains these components, the friction coefficient of these layers is reduced, the sliding characteristics are improved, and the wear resistance, strength, and the like are also improved.

  The filler may include carbon fiber. Thus, when a filler contains carbon fiber, the intensity | strength of a resin layer or a 2nd contact bonding layer improves, and also it becomes difficult to reduce an intensity | strength also in high temperature environment. Moreover, since the carbon fiber is less likely to damage the counterpart material than other fibers used for the filler, it is possible to further reduce the deterioration of the sliding characteristics of the thermosetting resin or the like.

  The elastomer forming material may include acrylonitrile butadiene rubber, urethane rubber, silicone rubber, or a combination thereof. By using the elastomer as described above, the elastic modulus of the resin layer or the second adhesive layer can be reduced, and the wear amount of these layers can be reduced.

  The sliding member includes a metal layer, a resin layer laminated on the surface side of the metal layer, and an adhesive layer laminated between the metal layer and the resin layer, and the resin layer is mainly composed of a phenol resin. The method includes the steps of forming a porous metal film by sintering metal particles on the surface of the metal layer, and filling the voids of the metal film with a resin material mainly composed of a phenol resin. The present invention also provides a method for manufacturing a sliding member comprising: a step of forming one adhesive layer; and a step of laminating a second adhesive layer mainly composed of a phenol resin between the first adhesive layer and the resin layer. Included in the invention. In the manufacturing method, since the porous metal film is formed by sintering metal particles and then the resin material is filled in the voids of the metal film, the first adhesive layer can be easily formed. For this reason, the said manufacturing method can manufacture the said sliding member efficiently.

  Here, the “main component” refers to a component (for example, 50% by mass) that is the largest on a mass basis among the resin components constituting the resin layer, the first adhesive layer, and the second adhesive layer.

  As described above, the sliding member of the present invention has high heat resistance, is easy to manufacture and thin, and does not easily deteriorate the sliding characteristics. Therefore, the said sliding member can be used suitably as a sliding member used in high temperature environments, such as components for motor vehicles. Moreover, the said manufacturing method can manufacture the said sliding member efficiently.

It is typical sectional drawing which shows the sliding member of one Embodiment of this invention. It is typical sectional drawing which shows the slide bearing using the sliding member of this invention.

  Hereinafter, the sliding member of the present invention will be described in detail.

[Sliding member]
The sliding member 1 of the present invention mainly includes a metal layer 2, a resin layer 3 laminated on the surface side of the metal layer 2, and an adhesive layer 4 laminated on the metal layer 2 and the resin layer 3. The adhesive layer 4 is laminated on the surface of the metal layer 2, and the first adhesive layer 5 made of the porous metal film 5a and the resin material 5b filled in the gap of the metal film 5a, the first adhesive layer 5 and And a second adhesive layer 6 laminated between the resin layers 3.

<Metal layer>
The metal layer 2 is plate-shaped, and the first adhesive layer 5, the second adhesive layer 6, and the resin layer 3 are laminated on the surface side. The shape of the metal layer 2 can be appropriately changed according to the usage mode of the sliding member 1, and the shape, thickness, and the like are not particularly limited. Examples of the material of the metal layer 2 include iron, copper, aluminum, indium, bismuth, tin, alloys of these metals, and stainless steel. Among these, iron, copper, or an alloy thereof is preferable. Furthermore, the surface of the metal layer may be plated. As this plating, known ones such as copper plating can be used.

<Resin layer>
The resin layer 3 has a phenol resin as a main component and is laminated on the surface side of the metal layer 2. The resin layer 3 preferably further contains a boron compound, a filler, or an elastomer, and may further contain other optional components as long as the effects of the present invention are not hindered.

(Phenolic resin)
As the phenol resin, any phenol resin commonly used as a material for a sliding member can be used without any particular limitation. Examples of such phenol resins include novolac type phenol resins and resol type phenol resins. Among these, as the phenol resin which is the main component of the resin layer 3, a novolac type phenol resin is preferable. Since the novolac type phenol resin has a higher crosslinking density than the resol type phenol resin, the amount of wear of the resin layer 3 can be further reduced.

(Novolac type phenolic resin)
As a minimum of the number average molecular weight (Mn) of a novolak-type phenol resin, 400 is preferable and 600 is more preferable. On the other hand, the upper limit of Mn of the novolac type phenol resin is preferably 1200, more preferably 1000. By making Mn of the novolak type phenol resin within the above range, the strength reduction of the resin layer 3 due to temperature change can be reduced.

  As a minimum of the weight average molecular weight (Mw) of a novolak-type phenol resin, 400 is preferable and 1000 is more preferable. On the other hand, the upper limit of Mw of the novolak type phenol resin is preferably 5000, and more preferably 4000. The stability and moldability of the resin layer 3 can be improved by setting the Mw of the novolac type phenol resin within the above range.

  The lower limit of the dispersion ratio (Mw / Mn) of Mw and Mn of the novolak type phenol resin is preferably 1.1. On the other hand, the upper limit of Mw / Mn of the novolac type phenol resin is preferably 3.0, and more preferably 2.8. By making Mw / Mn of the novolac type phenol resin within the above range, the stability and moldability of the resin layer 3 can be improved, and the heat resistance and dimensional accuracy can be improved. Mw, Mn, and Mw / Mn are measured values by gel filtration chromatography.

  In the novolac type phenol resin, the upper limit of the total content of the phenolic monomer and the phenolic dimer is preferably 10% by mass, and more preferably 5% by mass. By making the total content of phenolic monomers and phenolic dimers in the novolak-type phenolic resin within the above range, the friction coefficient of the resin layer 3 can be reduced, the amount of wear can be reduced, and heat resistance and dimensional accuracy can be reduced. Can be improved. The total content of the phenolic monomer and the phenolic dimer in the novolak type phenolic resin may be 0% by mass. Moreover, the said total content is a measured value by the area method of a gel filtration chromatograph.

  The novolac type phenolic resin preferably has a total content of phenolic monomers and phenolic dimers of 10% by mass or less and Mw / Mn of 1.1 or more and 3.0 or less. Thus, by making both the total content of the phenolic monomer and phenolic dimer of the novolak-type phenolic resin and the above Mw / Mn within the above range, the friction coefficient of the resin layer 3 is further reduced, and the wear amount is further increased. Can be reduced.

(Resol type phenol resin)
Examples of the resol type phenol resin include methylol type and dimethylene ether type. Of these, dimethylene ether type phenol resins are preferred because they are less likely to chip during processing and are excellent in wear resistance.

  As a minimum of the number average molecular weight (Mn) of a resol type phenol resin, 400 is preferable and 600 is more preferable. On the other hand, the upper limit of Mn of the resol type phenol resin is preferably 1000, and more preferably 800. By setting the Mn of the resol type phenol resin within the above range, the strength reduction of the resin layer 3 due to the temperature change can be reduced.

  As a minimum of the weight average molecular weight (Mw) of a resol type phenol resin, 4000 are preferable and 5000 are more preferable. On the other hand, the upper limit of Mw of the resol type phenol resin is preferably 10,000, and more preferably 9000. By setting the Mw of the resol type phenolic resin within the above range, the stability and moldability of the resin layer 3 can be improved.

  As a minimum of dispersion ratio (Mw / Mn) of Mw and Mn of a resol type phenol resin, 6 is preferred and 7 is more preferred. On the other hand, the upper limit of Mw / Mn of the resol type phenol resin is preferably 12, and more preferably 10. By setting Mw / Mn of the phenol resin within the above range, the stability and moldability of the resin layer 3 can be improved, and the heat resistance and dimensional accuracy can be improved.

  The resin layer 3 may contain a novolac type phenol resin as a main component or a resol type phenol resin as a main component, but it is preferable from the viewpoint of strength or the like that the novolac type phenol resin is a main component. The upper limit of the content of the resol type phenol resin when the resin layer 3 is mainly composed of a novolak type phenol resin is preferably 10% by mass, and more preferably 5% by mass. On the other hand, the lower limit of the content is preferably 0.05% by mass. By setting the content of the resol type phenol resin in the above range, the abrasion resistance of the resin layer 3 can be made high, and the thermal shock resistance is also improved.

(Filler)
When the resin layer 3 contains the filler, the friction coefficient is reduced and the sliding characteristics are improved. In addition, friction resistance, strength, etc. are improved.

  Examples of the filler include carbon materials such as graphite (graphite) and carbon fibers, calcium carbonate, clay, talc, silica, alumina, glass fibers, and aramid fibers. Among these, carbon materials or aramid fibers are used. Preferably, carbon fiber is more preferable. These fillers may be used individually by 1 type, and may use 2 or more types together.

  Since the filler contains carbon fibers, the resin layer 3 is excellent in strength, and the strength is not easily lowered in a high temperature environment. Furthermore, since the carbon fiber is less likely to damage the counterpart material than other fibers, the slidability of the resin layer 3 is also improved. Examples of such carbon fibers include PAN-based and pitch-based, and PAN-based carbon fibers are preferable. By using PAN-based carbon fiber, gas generation during sliding can be suppressed.

  Although it does not specifically limit as an upper limit of the average length of carbon fiber, 1 mm is preferable, 0.75 mm is more preferable, 0.5 mm is further more preferable. On the other hand, as a minimum of average length of carbon fiber, 0.01 mm is preferred, 0.05 mm is more preferred, and 0.1 mm is still more preferred. If the average length of the carbon fibers exceeds the above upper limit, the carbon fibers are easily peeled off during sliding, and the sliding characteristics of the resin layer 3 may be deteriorated. Conversely, if the average length is less than the lower limit, the mechanical strength of the resin layer 3 may be reduced. Here, the average length refers to the average value of the major axis in the carbon fiber.

  More preferably, the filler contains graphite (graphite) in addition to the carbon fiber. When the resin layer 3 contains carbon fiber and graphite (graphite), the amount of wear can be reduced, and sliding characteristics such as a friction coefficient can be improved.

  The aramid fiber is a fiber made of polyamide composed only of an aromatic skeleton. Aramid fibers have excellent tensile strength and self-extinguishing properties, and are excellent in flame retardancy. Examples of aramid fibers include meta-aramid fibers and para-aramid fibers, and among these, para-aramid fibers are preferred. Para-aramid fibers have a rigid molecular structure and are therefore excellent in strength and elastic modulus, and can provide sufficient strength with a small content.

  As an upper limit of the average length of an aramid fiber, 8 mm is preferable and 3 mm is more preferable. On the other hand, the lower limit of the average length is preferably 0.5 mm, and more preferably 1 mm. If the average length exceeds the upper limit, the moldability of the resin layer 3 may be deteriorated. On the other hand, when the average length is less than the lower limit, the impact resistance of the resin layer 3 is lowered, and the wear powder on the sliding surface may increase.

  The upper limit of the average diameter of the aramid fibers is preferably 18 μm, and more preferably 12 μm. On the other hand, the lower limit of the average diameter is preferably 8 μm. If the average diameter exceeds the upper limit, the strength of the resin layer 3 may be reduced. Conversely, if the average diameter is less than the lower limit, the wear resistance of the resin layer 3 may be reduced.

  As an upper limit of content of the filler with respect to 100 mass parts of phenol resins, 400 mass parts is preferable, 250 mass parts is more preferable, and 200 mass parts is further more preferable. On the other hand, as a minimum of the above-mentioned content, 50 mass parts are preferred, 80 mass parts are more preferred, and 100 mass parts are still more preferred. If the content exceeds the upper limit, the moldability of the resin layer 3 may be deteriorated. On the contrary, when the content is less than the lower limit, the friction coefficient of the resin layer 3 is not sufficiently decreased, and the wear amount may be increased.

(Boron compound)
By containing the boron compound, the resin layer 3 can suppress a temperature increase during sliding while maintaining mechanical strength, and can maintain a stable friction coefficient.

  Examples of the boron compound include boric acid, borate, boric acid ester, boron oxide, and borax. Examples of the borate include metal salts such as metaboric acid and tetraboric acid, and specific examples include zinc borate. Among these, boric acid, borate and boron oxide are preferable, and boric acid, zinc borate and boron oxide are more preferable. These boron compounds may be used alone or in combination of two or more.

  As an upper limit of content of the boron compound with respect to 100 mass parts of phenol resins, 10 mass parts is preferable and 7 mass parts is more preferable. On the other hand, as a minimum of the above-mentioned content, 0.5 mass part is preferred and 1 mass part is more preferred. If the boron compound content exceeds the upper limit, the mechanical strength and moldability of the resin layer 3 may be reduced. On the contrary, when the content is less than the lower limit, the wear amount of the thermoplastic resin layer 3 may increase.

(Elastomer)
The resin layer 3 contains the above elastomer, so that processability and sliding characteristics are improved. Moreover, since the elasticity modulus of the resin layer 3 falls, the abrasion amount at the time of sliding can be reduced.

  Examples of the elastomer include acrylonitrile butadiene rubber (NBR), urethane rubber, styrene-butadiene rubber (SBR), acrylic rubber, silicone rubber, and polybutadiene. Among these, NBR, urethane rubber, and silicone rubber are preferable in that the elastic modulus of the resin layer 3 can be effectively reduced. preferable. These elastomers may be used individually by 1 type, and may use 2 or more types together.

  As an upper limit of content of the elastomer with respect to 100 mass parts of phenol resins, 30 mass parts is preferable and 20 mass parts is more preferable. On the other hand, the lower limit of the content is preferably 2 parts by mass and more preferably 5 parts by mass. When the said content exceeds the said upper limit, the elasticity modulus of the resin layer 3 may fall too much and there exists a possibility that creep resistance may fall. On the other hand, when the content is less than the lower limit, the elastic modulus of the resin layer 3 is not sufficiently lowered, and there is a possibility that the wear amount during sliding increases.

(Other ingredients)
Examples of other components that may be contained in the resin layer 3 include a curing agent (for example, hexamethylenetetramine), a mold release agent (for example, calcium stearate, zinc stearate), and a curing accelerator (magnesium oxide, slaked lime, etc.). , Coupling agents, solvents and the like. These may be used alone or in combination of two or more.

  It does not specifically limit as average thickness of the resin layer 3, It can change suitably as needed. The upper limit of this average thickness is preferably 10 mm, more preferably 8 mm. On the other hand, the lower limit of the average thickness is preferably 1 mm, and more preferably 1.2 mm. If the average thickness of the resin layer 3 exceeds the above upper limit, the resin layer 3 contracts significantly, and the resin layer 3 may be peeled off from the sliding member 1. Conversely, when the average thickness is less than the lower limit, the life of the sliding member 1 may be shortened.

<Adhesive layer>
The adhesive layer 4 is a layer that is laminated between the metal layer 2 and the resin layer 3 and contributes to the adhesion of these layers. The adhesive layer 4 includes a first adhesive layer 5 laminated on the surface of the metal layer 2 and a second adhesive layer 6 laminated between the first adhesive layer 5 and the resin layer 3.

<First adhesive layer>
The first adhesive layer 5 includes a porous metal film 5a and a resin material 5b filled in the gap. The porous metal film 5 a is bonded to the metal layer 2, and the resin material 5 b is bonded to the second adhesive layer 6.

(Metal film)
The metal film 5a is porous and includes, for example, a spongy metal and a sintered body of metal powder. Among these, a sintered body of metal particles is preferable. Examples of the material of the metal film 5a include the same materials as those exemplified in the metal layer 2.

  A known metal powder can be used as the metal particles. Examples of the metal particles include spherical particles, non-spherical particles, and a mixture of spherical and non-spherical particles. Of these, spherical particles are preferred.

  The upper limit of the particle size of the metal particles is preferably 500 μm, and more preferably 450 μm. On the other hand, the lower limit of the particle size of the metal particles is preferably 50 μm, more preferably 100 μm, and even more preferably 180 μm. When the particle size of the metal particles exceeds the upper limit, the gap of the metal film 5a is increased, and the contact area between the metal and the resin in the first adhesive layer 5 is decreased, which may reduce the anchor effect. . On the contrary, when the particle size of the metal particles is less than the lower limit, the total volume of voids in the metal film 5a is reduced, and the content of the phenol resin in the first adhesive layer 5 is reduced. May decrease. Here, the “particle size of the metal particles” means an average value of diameters measured with a scanning electron microscope for 100 metal particles fixed to the metal layer 2. It shall refer to the diameter at the periphery that is not adjacent to the metal particles.

  Further, the metal film 5a preferably has a structure in which metal particles are sintered in two or three stages. As described above, by stacking a plurality of metal particles, the degree of penetration of the resin layer 5b in the thickness direction of the metal film 5a is increased, and the anchor effect is further improved.

(Resin material)
The resin material 5b contains phenol resin as a main component and fills the gaps in the metal film 5a. As this phenol resin, the thing similar to what was illustrated in the said resin layer 3 is mentioned. When the main component of the resin material 5b is a novolac type phenol resin, the strength of the first adhesive layer 5 is improved. When the main component of the resin material 5b is a resol type phenol resin, the thermal shock resistance of the first adhesive layer 5 is improved. Moreover, the resin material 5b may contain both a novolac type phenol resin and a resol type phenol resin.

  It is preferable that the resin material 5b does not contain other components such as the filler. Since the resin material 5b does not contain a filler or the like, the metal film 5a can be efficiently filled with the resin material 5b. As a content rate of the phenol resin in the resin material 5b, 85 mass% or more is preferable, 95 mass% or more is more preferable, 98 mass% is more preferable.

  Further, the resin material 5b may be filled in all the gaps of the metal film 5a, or may be filled only in a part thereof. When the resin material 5b impregnates only a part of the metal film 5a, the average thickness is preferably 60% or more and more preferably 70% or more with respect to the average thickness of the metal film 5a. When the said average thickness is less than the said minimum, there exists a possibility that joining strength with the other layer of the 1st contact bonding layer 5 may fall.

  As an upper limit of the average thickness of the 1st contact bonding layer 5, 1000 micrometers is preferable and 700 micrometers is more preferable. On the other hand, the lower limit of the average thickness of the first adhesive layer 5 is preferably 200 μm, and more preferably 250 μm. If the average thickness exceeds the upper limit, the weight of the sliding member 1 may increase. On the contrary, when the average thickness is less than the lower limit, the adhesive strength between the first adhesive layer 5 and the metal layer 2 or the second adhesive layer 6 may be reduced.

<Second adhesive layer>
The second adhesive layer 6 has a phenol resin as a main component and is laminated between the first adhesive layer 5 and the resin layer 3. As this phenol resin, the thing similar to what was illustrated in the said resin layer 3 is mentioned. When the main component of the second adhesive layer 6 is a novolac type phenol resin, the wear resistance of the second adhesive layer 6 is improved. On the other hand, when the main component of the second adhesive layer 6 is a resol type phenol resin, hexamethylenetetramine as a curing agent is not required, and therefore corrosion of peripheral devices due to ammonia liberated from hexamethylenetetramine can be prevented. Moreover, when the 2nd contact bonding layer 6 contains a novolak-type phenol resin and a resole type resin, the abrasion resistance and thermal shock property of the 2nd contact bonding layer 6 improve, and also the resin layer 3 and the 1st contact bonding layer 5 become a novolak. High bonding strength can be obtained in any case of a type phenol resin, a resol type phenol resin, or a combination thereof.

  The content of the phenol resin in the second adhesive layer 6 is preferably larger than the content of the phenol resin in the resin layer 3. That is, it is preferable that the total content of the filler, boron compound, elastomer, and other optional components contained in the second adhesive layer 6 is less than the total content in the resin layer 3.

  The phenol resin of the first adhesive layer 5 and the second adhesive layer 6 is preferably the same property as the phenol resin of the adjacent layer. Thus, the phenol resin of an adjacent layer is what has the same property, and the phenol resin of an adjacent layer fuse | melts and the joint strength of layers improves.

  Moreover, when any of the resin layer 3, the 1st contact bonding layer 5, or the 2nd contact bonding layer 6 contains a novolak type phenol resin and a resol type phenol resin, it is preferable that the adjacent layer contains a novolak type phenol resin. Thus, one of the adjacent layers contains a novolac-type phenol resin and a resol-type phenol resin, and the other contains a novolac-type phenol resin, so that the two layers are fused by the novolak-type phenol resin contained together, and Since the resol type phenolic resin bonds the two layers relatively firmly, the bonding strength between the layers is further improved.

  The upper limit of the content of the filler with respect to 100 parts by mass of the phenol resin in the second adhesive layer 6 is preferably 220 parts by mass, more preferably 175 parts by mass, and further preferably 135 parts by mass. On the other hand, as a minimum of the above-mentioned content, 25 mass parts are preferred, 35 mass parts are more preferred, and 45 mass parts are still more preferred.

  The upper limit of the content of the boron compound with respect to 100 parts by mass of the phenol resin in the second adhesive layer 6 is preferably 5 parts by mass, and more preferably 3.5 parts by mass. On the other hand, as a minimum of the above-mentioned content, 0.25 mass part is preferred and 2.5 mass parts is more preferred.

  The upper limit of the elastomer content relative to 100 parts by mass of the phenol resin in the second adhesive layer 6 is preferably 15 parts by mass, and more preferably 10 parts by mass. On the other hand, as a minimum of the above-mentioned content, 1 mass part is preferred and 2.5 mass parts is more preferred.

  When the content of the filler or the like in the second adhesive layer 6 is in the above range, properties such as wear resistance can be imparted to the second adhesive layer 6 at a level lower than that of the resin layer 3. Thereby, when the 2nd contact bonding layer 6 is exposed to a sliding surface, the quantity of wear powder can be increased, reducing the wear rate of the 2nd contact bonding layer 6. FIG.

  The upper limit of the average thickness of the second adhesive layer 6 is preferably 2 mm, and more preferably 1.8 mm. Conversely, the lower limit of the average thickness is preferably 0.5 mm, and more preferably 0.8 mm. When the average thickness exceeds the upper limit, the shrinkage of the second adhesive layer 6 increases, and the second adhesive layer 6 may be peeled from the sliding member 1. There is a risk that the sliding member is thinned. On the other hand, when the average thickness is less than the lower limit, the time required from the exposure of the second adhesive layer 6 to the sliding surface until the wear is shortened, and the first adhesive layer 5 may be easily exposed to the sliding surface. There is.

  The second adhesive layer 6 may be colored. Examples of the coloring method include a method of mixing a pigment, a dye, and the like with the second adhesive layer 6. Thus, when the 2nd contact bonding layer 6 is colored, when the resin layer 3 is worn out and the 2nd contact bonding layer 6 is exposed to a sliding surface, the surface of the said sliding member 1 and the color of abrasion powder change. In addition, the replacement time of the sliding member 1 can be estimated more easily.

[Sliding member manufacturing method]
The manufacturing method of the sliding member 1 includes a step of forming a porous metal film 5a on the surface of the metal layer 2 by sintering metal particles (hereinafter, also referred to as “metal film forming step”), and the metal film. A step of forming the first adhesive layer 5 by filling the gap 5a with a resin material 5b containing phenol resin as a main component (hereinafter also referred to as “resin material filling step”), and the first adhesive layer 5 and the resin A step of laminating the second adhesive layer 6 mainly composed of a phenol resin between the layers 3 (hereinafter, also referred to as “second adhesive layer laminating step”) is mainly provided.

<Metal film formation process>
In the metal film forming step, the metal particles are sintered on the surface of the metal layer 2 to form the porous metal film 5a. The sintering temperature and time are appropriately adjusted depending on the material of the metal particles, the average thickness of the metal film 5a to be formed, and the like.

  As an upper limit of sintering temperature, 900 degreeC is preferable and 850 degreeC is more preferable. On the other hand, as a minimum of sintering temperature, 700 degreeC is preferable and 750 degreeC is more preferable. Moreover, as an upper limit of sintering time, 30 minutes are preferable and 15 minutes are more preferable. On the other hand, the lower limit of the sintering time is preferably 5 minutes, and more preferably 10 minutes. If the sintering temperature or time exceeds the upper limit, the metal particles or the like may be melted or deformed. Conversely, when the sintering temperature or time is less than the lower limit, the metal particles may not be sufficiently bonded to the metal layer 2.

<Resin filling process>
In the resin material filling step, the first adhesive layer 5 is formed by filling the voids of the metal film 5a with the resin material 5b. As this filling method, a liquid resin material 5b is applied to the metal film 5a and solidified by heating or the like, and a solid resin material 5b is laminated on the metal film 5a and solidified by heating or the like. And the like.

<Second adhesive layer lamination step>
In the second adhesive layer laminating step, the second adhesive layer 6 is laminated on the surface of the first adhesive layer 5. Examples of the laminating method include a method in which a powdery resin composition containing a phenol resin, a filler, and the like is laminated on the surface of the first adhesive layer 5 and pressure-molded.

  In the method of laminating the powdery resin composition on the surface of the first adhesive layer 5, all of the powdery resin compositions may have the same composition, or powders of different compositions may be mixed. By mixing powders having different compositions, the second adhesive layer 6 having a desired composition can be obtained.

  Particularly, a phenol resin powder containing a filler (hereinafter also referred to as “powder (A)”) as in the case of the resin layer 3 and a phenol that does not contain a filler as in the case of the resin material 5 b of the first adhesive layer 5. It is preferable to mix resin powder (hereinafter also referred to as “powder (B)”). Thus, by mixing the powder (A) and the powder (B), it is easy to adjust the content of the filler and the like of the second adhesive layer 6 as appropriate, and the portion derived from the powder (A) is the resin layer 3. Since the portion derived from the powder (B) is firmly bonded to the first adhesive layer 5, the bonding strength between the second adhesive layer 6, the resin layer 3, and the first adhesive layer 5 is improved.

  As a minimum of mass ratio of powder (B) on the basis of mass of powder (A), 0.11 is preferred and 0.15 is more preferred. On the other hand, the upper limit of the mass ratio is preferably 1.2, and more preferably 1.15. Moreover, it is more preferable that the mixing ratio of the powder (A) and the powder (B) is 1: 1. If the mass ratio exceeds the upper limit, the wear resistance and the like of the second adhesive layer 6 may be reduced. Conversely, when the mass ratio is less than the lower limit, the bonding strength between the second adhesive layer 6 and the first adhesive layer 5 may be reduced.

  After the second adhesive layer laminating step, the resin layer 3 is laminated on the surface side of the second adhesive layer 6. As this lamination method, the same methods as those exemplified in the second adhesive layer lamination step can be used.

  Moreover, the 1st contact bonding layer 5, the 2nd contact bonding layer 6, and the resin layer 3 can also be formed simultaneously. Specifically, the above-mentioned three layers can be formed simultaneously by a single press by sequentially laminating a powdery resin compound having the composition of each layer, pressing the laminate, and press-molding.

  Further, after forming the first adhesive layer 5, the second adhesive layer 6 and the resin layer 3 may be formed simultaneously. Specifically, the first adhesive layer 5 is formed on the surface of the metal layer 2 by the above-described procedure, and then the resin constituting the second adhesive layer 6 and the resin layer 3 is sequentially laminated on the surface of the first adhesive layer 5. The second adhesive layer 6 and the resin layer 3 can be formed simultaneously by pressing.

  The sliding member of the present invention can be suitably used as a slide bearing, a washer, a linear motion guide or the like. Moreover, the said slide bearing etc. can be used suitably for sliding parts, such as industrial equipment, a machine tool, a motor vehicle, and foodstuff equipment.

  Examples of the shape of the slide bearing using the sliding member include a thrust type, a radial type, a thrust and a radial mixed type, and the like. These shapes are shown in FIG. 2A is a thrust type bearing, FIG. 2B is a radial type bearing, and FIG. 2C is a thrust and radial mixed type bearing. In FIG. 2, the adhesive layer 4 is omitted. In FIG. 2 (a), a sliding mating member is disposed above the figure, and in FIG. 2 (b), a sliding mating material is disposed in the center of the figure. Moreover, in FIG.3 (c), the other party material of sliding is arrange | positioned in the center and upper direction. Further, the shape of the slide bearing can be appropriately changed as necessary, such as providing a groove on the sliding surface.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples. In the examples, “parts” and “%” indicate “parts by mass” and “% by mass” unless otherwise specified. Moreover, when describing a compounding quantity using a mass part in this specification, it describes as a mass part with respect to 100 mass parts of phenol resins.

  In this example, Mw and Mn are standard polystyrene using “SC-8020 series build-up system (column: G2000Hxl + G4000Hxl, detector: UV254 nm, carrier: 1 ml / min of tetrahydrofuran, column temperature: 38 ° C.) manufactured by Tosoh Corporation. It is a value obtained by conversion.

[Production of phenolic resin]
<Manufacture of novolac-type phenolic resin>
In a reaction vessel equipped with a thermometer, a stirrer and a condenser, 193 parts of phenol (P), 57 parts of 92% paraformaldehyde (F) (F / P (molar ratio) = 0.85), 89% phosphoric acid 116 Part (60% / P) and 96.5 parts (50% / P) of ethylene glycol were charged, respectively, and stirred and mixed. Next, under a cloudy state (two-phase mixture) formed by stirring and mixing, the temperature was gradually raised to the reflux temperature, and a condensation reaction was further performed at the same temperature for 10 hours. After the reaction was stopped, methyl isobutyl ketone was added to the reaction mixture with stirring and mixing to dissolve the condensation product. Thereafter, stirring and mixing were stopped, and the contents were transferred to a separation flask and allowed to stand, and separated into a methyl isobutyl ketone solution layer (upper layer) and a phosphoric acid aqueous solution layer (lower layer). Next, after removing the phosphoric acid aqueous solution layer and washing the methyl isobutyl ketone solution with water several times to remove phosphoric acid, the contents are returned again into the reaction vessel, and methyl isobutyl ketone is completely removed by distillation under reduced pressure. 213.5 parts of type phenol resin was obtained. This novolak type phenol resin had Mn of 755, Mw of 1227, and Mw / Mn of 1.63. Moreover, it was 0.3% and 3.3% when it measured by the area method which displays the area of the phenolic monomer and phenolic dimer with respect to the whole area of molecular weight distribution by a percentage. Moreover, 14 parts of hexamethylenetetramine was added to 100 parts of the novolak type phenol resin and co-ground to obtain a curing agent-containing novolac type phenol resin (n).

<Manufacture of resol type phenolic resin>
In a reaction vessel equipped with a thermometer, a stirrer and a reflux condenser, 100 parts of phenol (P), 52 parts of 92% paraformaldehyde (F) (F / P (molar ratio) = 1.50), zinc chloride 0 .12 parts (0.12% / P), manganese acetate 0.28 parts (0.28% / P) and water 8 parts (8% / P) were charged, and the mixture was stirred and mixed. Next, the temperature was gradually raised to the reflux temperature, and the reaction was further performed at the same temperature for 3.5 hours. Thereafter, a dehydration condensation reaction was performed under reduced pressure for 3.5 hours, and cooling after the completion of the reaction yielded 108 parts of a solid resol type phenol resin (r-S). This resol type phenol resin had Mn of 648, Mw of 6099, and Mw / Mn of 5.99. Further, this solid resol type phenol resin was dissolved in acetone to obtain a liquid resol type phenol resin (r-L) having a resin concentration of 50%. Moreover, it was 3.2% when it measured by the area method which displays the area of the phenolic monomer with respect to the whole area of molecular weight distribution by a percentage.

[Production of resin composition]
<Production of novolak type phenol-containing resin composition>
100 parts by mass of the above-mentioned novolak type phenolic resin, 100 parts by mass of graphite (made by Nippon Graphite Industries Co., Ltd.), 5 parts by mass of boric acid (made by NIPPON DENKO), 50 parts by mass of carbon fiber (“TA008A” manufactured by Toray Industries, Inc.) Part, 15 parts by mass of a curing agent (hexamethylenetetramine) and 3 parts by mass of a release agent (calcium stearate) were mixed and mixed uniformly. Thereafter, the obtained mixture was uniformly heated and kneaded with a hot roll to form a sheet, cooled, and then pulverized with a power mill to obtain a granular novolak-type phenol-containing resin composition (NR).

<Production of resol type phenol-containing resin composition>
100 parts by mass of the above-mentioned resol type phenol resin, 100 parts by mass of graphite (made by Nippon Graphite Industries Co., Ltd.), 5 parts by mass of boric acid (made by NIPPON Denko), 50 parts by mass of carbon fiber (“TA008A” manufactured by Toray Industries, Inc.) Part, 4 parts by mass of slaked lime and 3 parts by mass of a release agent (calcium stearate) were mixed and mixed uniformly. Thereafter, the obtained mixture was uniformly heated and kneaded with a hot roll to form a sheet, cooled, and then pulverized with a power mill to obtain a granular resol type phenol-containing resin composition (RR).

[Manufacture of sliding members]
<Example 1>
Copper plating was performed on the surface of an iron plate having an average thickness of 2 mm, and copper alloy powder having an average particle diameter of 400 μm was sintered on the copper plating to form a porous metal film having an average thickness of 700 μm. This metal film was placed in a mold and impregnated with a liquid resol type phenol resin (r-L). The average thickness impregnated with this liquid resol type phenolic resin (r-L) was 500 μm. On top of this, a mixture of a powdered novolac type phenol-containing resin composition (NR) (powder (A)) and a powdered resol type phenolic resin (r-S) (powder (B)), and a novolac type phenol The containing resin composition (NR) was laminated in order. The mixing ratio based on mass of the powder (A) and the powder (B) was 1: 1. Then, this laminated body was pressed in the laminating direction with a press machine to form the first adhesive layer, the second adhesive layer, and the resin layer at the same time, thereby obtaining a sliding member. The pressure at the time of pressing was 56 MPa, and the pressing time was 840 seconds. The average thickness of the first adhesive layer after pressing was 700 μm, the average thickness of the second adhesive layer was 1 mm, and the average thickness of the resin layer was 4 mm.

<Examples 2 to 6 and Comparative Examples 5 and 6>
A sliding member was produced by the same procedure as in Example 1 except that the types of phenol resin, resin composition and metal particles used, and the average thickness of each layer were as described in Table 1. In Comparative Example 6, an epoxy adhesive (“MOS8” manufactured by Konishi Co., Ltd.) was used in the first adhesive layer instead of the phenol resin.

<Comparative Example 1 and Comparative Example 2>
A sliding member was manufactured by the same procedure as in Example 1 except that the metal film was not formed and only the resin material was laminated on the surface of the metal layer.

<Comparative Example 3>
Except that a metal film was not formed and a copper alloy powder having an average particle diameter of 100 μm and a liquid resol type phenol resin (r-L) mixed at 1: 9 (mass ratio) were laminated on the surface of the metal layer. A sliding member was produced by the same procedure as in Example 1.

<Comparative Example 4>
After forming the metal film, the novolac type phenol-containing resin composition (NR) is filled into the metal film, laminated on the surface of the metal film, and pressed under the same conditions as in Example 1 to thereby form the first adhesive layer and the resin layer. And a sliding member was manufactured.

[Evaluation]
The sliding members of Examples and Comparative Examples were evaluated by the following methods.

<Joint strength>
About the joint strength of each sliding member immediately after manufacture, based on JIS-D4415: 1998, shear strength was measured on condition of the following.
Test piece: length 20 mm, width 20 mm, thickness 3-7 mm
Shear rate: 0.5 mm / min

  Further, using a thermal shock device (“TSA-42EL” manufactured by ESPEC), each sliding member was heated at 120 ° C. for 30 minutes and then cooled at −30 ° C. for 30 minutes. This was defined as one cycle, and the bonding strength of each sliding member after 300 cycles was measured in the same manner as the bonding strength immediately after the production.

  Table 2 shows the measurement results of these shear strengths. In Table 2, “−” indicates that the value of the shear strength was small and could not be detected.

  As shown in Table 2, the sliding member of the example is excellent in both the shear strength immediately after production and after heating and cooling, and therefore can be suitably used even in an environment where the temperature changes drastically.

  In addition, Examples 4 and 5 in which the resin layer, the first adhesive layer, and the second adhesive layer all contain a novolak type phenol resin are more excellent, and the second adhesive layer is made of novolac type phenol resin and resol type phenol resin. Example 4, which was a mixture, was particularly excellent.

  As described above, the sliding member of the present invention has high heat resistance, is easy to manufacture and thin, and does not easily deteriorate sliding characteristics. Therefore, the said sliding member can be used suitably as a sliding member used in high temperature environments, such as components for motor vehicles. Moreover, the said manufacturing method can manufacture the said sliding member efficiently.

DESCRIPTION OF SYMBOLS 1 Sliding member 2 Metal layer 3 Resin layer 4 Adhesive layer 5 1st adhesive layer 5a Metal film 5b Resin material 6 2nd adhesive layer

Claims (10)

A sliding member mainly comprising a phenol resin, comprising a metal layer, a resin layer laminated on the surface side of the metal layer, and an adhesive layer laminated between the metal layer and the resin layer. And
The adhesive layer is
A first adhesive layer comprising a resin material that is laminated on the surface of the metal layer and is filled in a porous metal film and a gap in the metal film, the resin material being a phenol resin as a main component,
A sliding member comprising: a second adhesive layer which is laminated between the first adhesive layer and the resin layer and mainly contains a phenol resin.   The sliding member according to claim 1, wherein the content of the phenol resin in the second adhesive layer is larger than the content of the phenol resin in the resin layer.   The sliding member according to claim 1 or 2, wherein the porous metal film of the first adhesive layer is a sintered body of metal particles.   The sliding member according to claim 3, wherein the average particle diameter of the metal particles is 100 μm or more and 500 μm or less.   The sliding member according to any one of claims 1 to 4, wherein the phenol resin of the first adhesive layer or the second adhesive layer is a novolac type phenol resin, a resol type phenol resin, or a combination thereof.   The sliding member according to any one of claims 1 to 5, wherein the phenol resin of the resin layer is a novolac type phenol resin.   The sliding member according to any one of claims 1 to 6, wherein the resin layer or the second adhesive layer further contains a filler, a boron compound, or an elastomer.   The sliding member according to claim 7, wherein the filler includes carbon fiber.   The sliding member according to claim 7, wherein the elastomer forming material includes acrylonitrile butadiene rubber, urethane rubber, silicone rubber, or a combination thereof. Production of a sliding member comprising a metal layer, a resin layer laminated on the surface side of the metal layer, and an adhesive layer laminated between the metal layer and the resin layer, the resin layer being a phenol resin as a main component A method,
Forming a porous metal film on the surface of the metal layer by sintering metal particles;
Forming a first adhesive layer by filling a resin material containing phenol resin as a main component into the voids of the metal film;
And a step of laminating a second adhesive layer containing phenol resin as a main component between the first adhesive layer and the resin layer.

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