JPH09286916A - Underwater slidable resin composition and disk valve for faucet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition incorporated with vitreous carbon of specified particle size, high in dimensional accuracy with no shrinkage anisotropy when molded, good in self-lubricity and abrasion resistance, and useful for e.g. switch cocks. SOLUTION: This underwater slidable resin composition is obtained by incorporating (A) 100 pts.wt. of a polyarylene sulfide-based resin [pref. e.g. composed of recurring unit of formula I (Ph is formula II, etc.; (m) is 1-4)] with (B) 55-165 pts.wt. of vitreous carbon 1-30μm in average particle size, and pref. furthermore, (C) 1-30 pts.wt. of fluororesin powder (pref. perfluororesin powder or tetrafluoroethylene resin powder, esp. reclaimed tetrafluoroethylene resin powder).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an underwater slidable resin composition which is used as a material for parts that slide in water, and further uses the composition to wash hot and cold water and the like, and to wash hot water for toilet bowls. The present invention relates to a slide-type water faucet disk valve such as a flow path switching stopper for an ionizer and an ion water purifier.

[0002]

2. Description of the Related Art As a sliding member which exhibits slidability in water, a water valve disk valve for mixing hot and cold water is known. A general disc valve is composed of a valve seat having a plurality of valve holes of about 2 to 5 called a fixed disc, and a valve body having one or a plurality of flow passages leading to the valve holes called a sliding disc valve. This valve element operates in a state of slidingly contacting the valve seat in a liquid-tight manner.

As a conventional example of such a disc valve, one of the valve body and the valve seat is formed of ceramics having excellent wear resistance, and the other is made of a self-lubricating material such as fluororesin or ultra high molecular weight polyethylene. A resin formed with the resin or a resin filled with a lubricating filler such as molybdenum disulfide or carbon is described in JP-A-63-36765.

The resin composition for molding the valve body or valve seat of such a valve device is required to have creep resistance in order to prevent water leakage, but a valve body or valve seat molded of a self-lubricating resin is used. When attempting to improve creep resistance by reinforcing with fibers, the wettability between the resin and the fibers was not sufficient, and the reinforcing effect could not be obtained to the desired degree.

When a general resin having no self-lubricating property is filled with a self-lubricating filler, a large amount of filler is required in order to exhibit the required lubricity. With a resin disc filled with such a large amount of filler,
The impact strength and creep resistance were remarkably reduced, and the problem of cracking occurred.

Further, Japanese Patent Laid-Open No. 6-213341 discloses that at least one of a valve seat and a valve body is a molded product of a resin composition in which carbon fibers are mixed with a polycyanoaryl ether resin.

[0007]

However, there is a problem that the resin composition obtained by blending the polycyanoaryl ether resin with the carbon fiber has anisotropy in the shrinkage rate at the time of molding and the self-lubricating property is not sufficient.

As a slidable material having improved creep resistance and lubricity, polyphenylene sulfide resin (hereinafter abbreviated as PPS resin) 25 to 80% by weight and carbon fibers 20 to 75 having an average fiber diameter of 8 μm or less. A resin composition containing 100% by weight and further containing an inorganic powder filler such as natural mica is disclosed in JP-A-2-190677.

However, this resin composition has a large change in surface shape when it absorbs water, and it cannot be said that the resin composition is sufficiently satisfactory in waterproofness and durability when used as an underwater sliding material such as a disk valve. .

The properties required of a resin composition that slides in water include that it is not easily scratched even when foreign matter enters the sliding surface, and that it is excellent in non-water absorption and abrasion resistance.

Therefore, the first object of the present invention is to solve the above-mentioned problems and to provide an underwater sliding resin composition by
The shrinkage rate during molding has no anisotropy, good dimensional accuracy, good self-lubricating property and wear resistance, and is hard to be damaged even if a hard foreign substance enters the sliding surface, and also absorbs water. Is to make the surface shape unchanged.

A second object of the present invention is to solve the above-mentioned first problem.
SUMMARY OF THE INVENTION It is an object of the present invention to provide a disk valve for faucet which has a good performance of being molded in a precise shape, having self-lubricating properties and wear resistance, being hard to be scratched and not deformed during use.

[0013]

In order to solve the above-mentioned first problem, in the present invention, the average particle size is 1 to 3 relative to 100 parts by weight of the polyarylene sulfide resin.
This was the underwater slidable resin composition containing 55 to 165 parts by weight of 0 μm glassy carbon.

Further, polyarylene sulfide resin 1
To 100 parts by weight, 55 to 165 parts by weight of glassy carbon having an average particle size of 1 to 30 μm, and 1 to 1 of fluororesin powder
That is, an underwater slidable resin composition containing 30 parts by weight was prepared.

In order to solve the above-mentioned second problem, in the present invention, the valve body is superposed on the valve seat having the valve hole, and the valve body is slid with respect to the valve seat to form the valve hole. In a disc valve for a water faucet that is opened and closed, at least one of the valve seat and the valve body has an average particle size of 1 with respect to 100 parts by weight of a polyarylene sulfide resin.
A disk valve for a faucet, which is a molded product of a resin composition containing 55 to 165 parts by weight of glassy carbon of 30 μm.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION First, a polyarylene sulfide resin (hereinafter abbreviated as PAS) in the present invention.
Is a compound consisting of a repeating unit represented by the following chemical formula 1, and all have a water absorption rate of 0.1% or less and a specific structural formula of 0.05% or less. It is considered that this is unlikely to occur, and is suitable as a material for underwater use.

[0017]

Embedded image

PPS as a typical example of PAS
Is a well-known polymer composed of repeating units represented by the following chemical formula 2, and in order to impart preferable characteristics to the molded article, 70% by mole or more, preferably 90 to 100% by mole or more of such repeating units is used. It is a polymer containing.

[0019]

Embedded image

In order not to affect the crystallinity of such a polymer, the copolymerization component represented by the following chemical formula 3 is used in an amount of less than 30 mol%, preferably 1 to 10 mol%. May be included.

[0021]

Embedded image

Although PPS is synthesized by a well-known condensation reaction, it is an uncrosslinked product having a color close to white immediately after the reaction, and since it has a low molecular weight and a low viscosity as it is, it is used for extrusion molding, injection molding, etc. For example, it is heated in air to a temperature below its melting point, and oxidatively crosslinked to increase its molecular weight to a melt viscosity suitable for molding. The melt viscosity (orifice: diameter 1 mm, length 2 mm, load 10 kg) at a measurement temperature of Ryton P-4 (manufactured by Philippe Petroleum Co., Ltd.) commercially available for melt molding after such treatment is 300 ° C., 15
It is more than 00 and 5000 poise or less.

The melt viscosity of the crosslinkable PPS resin produced as described above is more than 1500 and not more than 20000 poise, preferably 1600 to 5000 poise, more preferably 2000 to 4000 poise. In that case, the crosslinkable PP having a melt viscosity of less than 1500 poise
The S resin is not preferable, because mechanical properties such as creep resistance are deteriorated in hot water of 80 ° C. or higher or in a high temperature range of 150 ° C. or higher, and the S resin is easily deformed. A crosslinkable PPS resin having a porosity of more than 20,000 poise has poor moldability and flexibility. The crosslinked PPS is superior to the linear PPS in heat resistance, creep resistance, burr generation state, cost, and the like.

However, since such a PPS is obtained by oxidatively cross-linking a low molecular weight one as described above, it becomes brittle depending on the composition and has a low impact strength, and even when foreign matter is mixed in the sliding portion. There is a possibility that a part of the sliding surface may be lost to promote wear of the sliding surface.

In order to improve these fragility, it is preferable to use linear PPS. Such linear PPS is disclosed in JP-A-617332 and JP-A-61732.
Manufactured by a well-known method described in JP-A-66720, etc., the molecular chain is linearly grown to a high molecular weight in the polymerization step without heat treatment at high temperature after polymerization and addition of a crosslinking agent. As a commercially available product, KPS-W214 manufactured by Kureha Chemical Industry Co., Ltd. may be mentioned.

The melt viscosity of the linear PPS resin thus produced is 200 to 10,000 poise, preferably 300 to 3,000 poise, more preferably 300.
It may be ˜1500 poise. In that case, a linear PPS resin having a melt viscosity of less than 300 poise has a viscosity of, for example, 8
Mechanical properties such as creep resistance are deteriorated under hot water of 0 ° C. or higher or in a high temperature range of 150 ° C. or higher, and are easily deformed, which is not preferable. If the linear PPS resin having a porosity of more than 3000 poise is added with a filler, the moldability is deteriorated and the flexibility is deteriorated. The measurement conditions for the melt viscosity in this case are the measurement temperature 3
00 ° C, orifice: hole diameter 1mm, length 10mm,
Load 20 kg / cm ² , measuring machine: Koka type flow tester,
The preheating time is 6 minutes. The shear rate of melt viscosity is
The evaluation is generally performed under the condition of 10 ² to 10 ⁴ (sec ⁻¹ ).

The straight-chain type PPS is white and has a tensile strength in a specific direction, a bending strength, a bending elastic modulus, an elongation, etc., as compared with the characteristic that the crosslinking type PPS is hard and slightly brittle. Are better.

As the PPS used in the invention relating to the disc valve of the present application, a linear PPS having excellent moldability and little deformation is preferred in order to prevent water leakage when sliding in water. Further, since the straight-chain type PPS has less "sinking" after molding, it is also preferable that the polishing allowance required for polishing the sliding surface is reduced.

The glassy carbon used in the present invention is a glassy carbon (amorphous, that is, non-crystalline) having no specific crystal structure obtained by carbonizing and firing a thermosetting synthetic resin such as phenol resin or furan resin. It is crystalline and has the same hardness (viscosity) as that of solid carbon), and usually powdery one is used.

The higher the firing temperature of the raw material for obtaining the glassy carbon, the more excellent the scratch resistance and sliding characteristics are. Therefore, the maximum temperature is 500 to 2800 ° C., preferably 800 to 2800 ° C. It is a thing.

The size of the glassy carbon after firing may be powder having a diameter of about 1 mm or less, but preferably an average particle size of 100 μm or less (preferably an average particle size of 1 to 50 μm).
m, more preferably 5 to 25 μm) is uniformly dispersed in the composition and has a high effect of reducing the dimensional change and the coefficient of thermal expansion when absorbing water.

Since such glassy carbon has a spherical shape, it is not oriented in a specific direction during injection molding.
Further, when it is exposed on the surface of the molded product, it comes into point contact with the mating material, so that the composition tends to have a low coefficient of friction.

As a commercially available product of glassy carbon made from phenol resin powder as a raw material, a weight average molecular weight having a methylol group in the molecule is 3,000 or more, preferably 5,000.
As described above, more preferably 10 ⁴ to 10 ⁷ phenol-formaldehyde resin is baked (heat-treated) at 500 to 3000 ° C., preferably 800 to 2000 ° C. (Kanebo Co., Ltd .: Bell Pearl C-800, manufactured by the same company). : Bellpearl C-2000), and these have an average particle size of 1 to 30.
μm, preferably 3 to 20 μm, more preferably 5 to 1
It is possible to use a fine particle adjusted to 5 μm. The glassy carbon has a high molecular weight and is carbonized, and the higher the heat treatment temperature, the closer the structure to that of graphite.

Concretely, glassy carbon has a disordered structure having an extremely small crystal size as a basic structure and has a non-oriented structure as a fine structure. Phenolic resin, furan resin, epoxy resin, It is obtained by carbonizing a thermosetting resin such as an unsaturated polyester resin, a urea resin, a melamine resin, an alkyd resin or a xylene resin at a high temperature.

This glassy carbon is characterized in that its fracture surface has a glassy luster, but in addition to this, a wide peak is observed in the vicinity of a diffraction angle (2θ) of 23 to 25 degrees in the spectrum in a usual X-ray diffraction method. It is also confirmed by having. In addition, the X-ray diffraction method is measured by Cu-Kα ray (double line) according to a conventional method.

Conventional carbon materials, such as graphite, do not have a broad peak like glassy carbon, and at other diffraction angles (2θ = 26.4 ° C.), sharp d ₀₀₂ peaks due to crystallinity are present. Indicates.

The glassy carbon used in the present invention may have substantially no peak characteristic of graphite. Further, a mere organic carbonized product does not have a glassy luster in its fracture surface, and of course, in its X-ray diffraction spectrum, it does not have the peak of a specific diffraction angle characteristic of graphite as well as glassy carbon.

By the way, such glassy carbon may contain an incomplete carbonized product or an uncarbonized product due to being produced by carbonizing a thermosetting resin such as a phenol resin as described above. is there.

That is, even if the glassy carbon is confirmed by the fact that the fracture surface has a glassy luster or has a wide peak at a specific diffraction angle in the X-ray diffraction spectrum, this glassy carbon is not May include fully carbonized or uncarbonized.

When glassy carbon is blended with a thermoplastic resin, the presence of the incomplete carbonized product or uncarbonized product as described above does not cause a problem in the thermoplastic resin molding process or the molded product itself. Often. This is because these incompletely carbonized materials or uncarbonized materials are considered to be the thermosetting resin itself which is the raw material resin for glassy carbon, or the thermally decomposed low polymer thereof.

The commercially available spherical glassy carbon powders that can be used in the present invention are listed below. Note that the weight loss referred to below means weight loss when the temperature is raised from room temperature to 350 ° C. at a rate of 10 ° C./min and is held at this temperature for 30 minutes, and measurement can be performed using a commercially available thermobalance. It is possible. The reduction value of the spherical glassy carbon powder that can be used in the present invention is preferably 8% or less, more preferably 0.01 to 5%.

(A) Kanebo Co., Ltd .: Bell Pearl, C-80
0, weight loss 1.2%, average particle size 10 μm (b) Belle Pearl Co., Ltd .: Bell Pearl, C-2000, weight loss 0.
2%, average particle size 10 μm (c) Unitika Ltd .: Univex, GCP-50
(H), weight loss 0.5%, average particle size 30 μm (d) Unitika Ltd .: Univex, GCP-50
(L), weight loss 5.1%, average particle diameter 30 μm It was confirmed that each of the above-mentioned glassy carbons had a glassy gloss in the particle cross section, and Cu-Kα
X-ray diffraction angle (2θ) 23 measured by X-ray (double line)
It may also have a distinctly broad peak around -25 degrees. Further, in the glassy carbons of (a), (c) and (d), the sharp peak peculiar to graphite was hardly recognized, but in the carbon of (b), the diffraction angle 2θ = 2.
The d ₀₀₂ peak may be recognized as a shoulder at 6.4 degrees.

The glassy carbon used in the present invention has an average particle size of 1 to 30 μm, preferably 3 to 25 μm. The reason is that if the particle diameter is less than the above-mentioned predetermined particle size range, the particles tend to agglomerate and it is difficult to uniformly disperse in the matrix, and the desired sliding characteristics cannot be obtained. This is because the aggressiveness increases.

The blending ratio (parts by weight) of glassy carbon to PPS is 55 to 165 parts by weight of glassy carbon to 100 parts by weight of PPS. Because, when the amount of glassy carbon is less than the above predetermined range, the scratch resistance is poor, and the elastic modulus is too small to sufficiently stop the water of the valve body, and when the amount exceeds the predetermined range, the moldability becomes poor. In addition, the impact strength of the molded product is significantly reduced.

Further, 55 to 165 parts by weight of glassy carbon may be added to 100 parts by weight of PPS, and if necessary, fluorine resin powder may be added. Addition of fluororesin powder improves the slidability of the composition, reduces the operability (rotation torque) when used in the valve body or valve seat of a valve device, and tends to occur during operation. This is because it is considered that sliding noise (abnormal noise) can be eliminated.

As typical examples of the above-mentioned fluorine-based resin, the resins listed below can be mentioned. In addition, [] shows the thermal decomposition temperature. Polytetrafluoroethylene (PTFE) [about 50
8 to 538 ° C] Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) [about 464 ° C or more] Tetrafluoroethylene-hexafluoropropylene copolymer (FEP) [about 419 ° C or more] Polychlorotrifluoroethylene ( PCTFE)
[About 347 to 418 ° C] Tetrafluoroethylene-ethylene copolymer (ET
FE) [about 347 ° C. or higher] Chlorotrifluoroethylene-ethylene copolymer (ECTFE) [about 330 ° C. or higher] Polyvinylidene fluoride (PVDF) [about 40
0-475 ° C] Polyvinyl fluoride (PVF) [about 372-4
80 ° C.] Tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer (E
PE) [about 440 ° C. or higher].

The fluororesin is, for example, a fluorinated polyolefin such as a copolymer of two or more kinds or a terpolymer with a polymerization amount of about 1:10 to 10: 1 of the above-mentioned fluororesin monomer. , Which exhibit properties as solid lubricants. Among them, PTFE is
It has excellent properties such as heat resistance, chemical resistance, non-adhesion, and low friction coefficient, and can be said to be preferable.

These fluororesin groups are also preferable because they have a relatively high differential thermal decomposition initiation temperature. For example, PTFE, P
The decomposition points of VDF are about 490 ° C. and about 350 ° C., respectively.
It also shows 5 ° C. and about 460 ° C., and among fluororesins, perfluoro-based PTFE, PFA, FEP and the like are preferable because of their excellent high-temperature properties. Therefore, it can relatively withstand various thermal history as described above in the process of manufacturing the valve body made of PPS by melting or the like. Especially, the decomposition point of PTFE is
The melting point of PPS (about 280
˜290 ° C.) and is about 100-200 ° C. higher, which is preferable. By adding 1 to 30 parts by weight, preferably 5 to 15 parts by weight of these fluorine-based resins, excellent mechanical properties,
Compressive strength of standard products is 500-2000kgf / cm
It is possible to improve impact resistance, fatigue resistance, wear resistance and the like in addition to good creep resistance and PPS characteristics which are excellent in heat insulation and hot water resistance around ² .

If the amount added is less than 1 part by weight, these effects cannot be expected. If the amount added exceeds 30 parts by weight, the melt viscosity of these causes the melt molding machine to be used at the time of granulation or injection molding. The load on the cylinder of
In some cases, stable granulation properties, injection moldability, and dimensional accuracy cannot be expected.

Incidentally, the melt viscosities of PFA and FEP are about 10 ⁴ to 10 ⁵ poises and about 4 × at about 380 ° C., respectively.
10 ⁴ to 10 ⁵ poise, especially about 34 in PTFE
Since a fluororesin having a viscosity characteristic of about 10 ¹¹ to 10 ¹² poises at 0 to 380 ° C. and about 10 ⁴ to 10 ¹² poises even at such a high temperature has high viscosity characteristics, It is preferable because it has excellent heat resistance.

Even when PTFE is blended, PPS10
The ratio is 1 to 30 parts by weight with respect to 0 parts by weight. This is because if the amount exceeds 30 parts by weight, the mechanical properties of PPS are significantly impaired and the valve seat or the valve body is easily scratched. If the amount is less than 1 part by weight, the effect of improving slidability by adding PTFE cannot be obtained.

The PTFE powder can be used without any particular limitation on its shape and size, but a granular one having a particle size of 70 μm or less, preferably 1 to 50 μm, makes the resin composition uniform. Preferred for.

Further, it is preferable to use recycled PTFE powder in place of the virgin PTFE powder in order to prevent the mechanical properties of PEN from being hindered. Regenerated PTFE
The powder is a powder obtained by firing the virgin material once and then pulverizing it, and this powder has a property that it is difficult to be fibrous, so that the blended resin composition maintains a good melt viscosity. , Is an excellent additive that improves moldability.

In the respective inventions of the present application, it is possible to maintain good water-stopping property and abrasion resistance even if the disk valves slide with each other and the disk valves are made of the same material. Usually, it is conceivable that cohesive wear may occur due to sliding between the same materials, but such abnormal wear does not occur in each invention of the present application.

Further, either the valve seat or the valve body of the disk valve for a water faucet is formed from the underwater slidable resin composition as described above, and the corresponding valve body or the valve seat is formed of a ceramic material. In this case, it is preferable to mold using a ceramic material such as new ceramics shown in Table 1 below. It is more preferable that these have appropriate strength and hardness, and that the valve body is made of a ceramic material within the range of the following numerical values.

In order to modify the strength and thermal characteristics of these materials, about 1 to 10% by weight of SiO ₂ and Y ₂ are added.
O ₃ , Al ₂ O ₇ , AlN, TaN, TiC, Co, etc.,
In addition, one or more kinds of harmless substances such as rare earths may be added.

[0057]

[Table 1]

The above-mentioned ceramic materials are super heat resistant, and the resin material is relatively excellent in heat insulating property, but since the linear expansion coefficient is about 1/10 smaller than that of the resin material, the gap between the valve bodies is small. It is possible to provide a valve device with a high clearance accuracy that is relatively small.

As described above, the coefficient of linear expansion is relatively small, the material has a heat insulating property, and, for example, the thermal shock resistance is at least about 1.
The accuracy of the clearance between the valve body and the valve seat is increased by applying a material of 00 ℃ or more, about 150 ℃ or more considering safety, and about 200 ℃ or more considering safety to the valve body. Even if it is applied to a valve device having a large operating temperature difference in which water and hot water are mixed, it is possible to provide a valve device with less backlash and a low torque and a long life.

Alumina (aluminum oxide, which is a typical fine ceramic among ceramic materials,
Al ₂ O ₃ ), depending on the crystal form, the use of additives, etc., may have the above-mentioned properties and the properties shown in Table 2 below, such as mechanical strength, heat resistance, dimensional stability, etc. , It can be used as a valve device without excessive specifications and is relatively average in terms of price.
Excellent overall.

[0061]

[Table 2]

If the valve body is made of a ceramic material having a compression strength, a bending strength, a hardness, a linear expansion coefficient, a thermal conductivity, a thermal shock resistance and the like, for example, about 17.5 kgf.
Even if a water pressure of about / cm ² is applied to the valve body or seat, the bending strength and hardness of the valve body or seat are sufficient, so the valve body and seat do not deform, and the heat insulation and heat resistance Since it has excellent impact resistance and the like, it is difficult for heat to escape and a stable hot water temperature can be maintained. Even if it is exposed to boiling water of about 100 ° C and low-temperature water at the same time, it is sufficient as a valve body or valve seat. A valve device having thermal shock resistance and corrosion resistance can be provided.

The underwater lubricating resin composition of the present invention comprises the above-mentioned PPS, glassy carbon and, if necessary, PT.
The FE powder is mixed and melt-molded, and the mixing / molding method is not particularly limited.

For example, these raw materials are dry-mixed by using a mixer such as a Henschel mixer, a ball mill or a tumbler mixer, or two or more kinds of them are simultaneously mixed, and then a hot roll, a kneader, a Banbury mixer, a melt extruder. It may be melt-mixed by, for example, and melt-molded into a predetermined shape. The melt molding temperature is not lower than the melting temperature of PPS and is 290 to 350 ° C., preferably 300 to 3
30 ° C. The melt molding method is preferable because injection molding has good mass productivity and can reduce cost.

Further, the sliding surface of at least one of the molded body such as the valve body and the valve seat and the mating member is Ra defined by JIS.
The surface roughness (arithmetic mean roughness) is 25 μm or less, preferably 8 μm or less, and more preferably 3 μm or less.
This is because when the surface roughness exceeds the above-mentioned predetermined range, the waterproofness is lowered and the sliding surface is often scratched, which is a cause of abrasion.
Water pressure of 50 kgf / cm ² , more specifically 2 to 20 k
Water pressure of gf / cm ² and specific evaluation criteria 1
This is because it may be difficult to stop water under a water pressure of 7.5 kgf / cm ² . The lower limit value of the surface roughness Ra is considered to be 0.01 μm or more, and 0.1 μm or more in consideration of the practicality of polishing.

The surface roughness may be in the range of 0.1 to 1 μm as long as the specifications and conditions are not affected by wear. This is because a process such as finishing of the surface of the mating material requires a long time, which may be inefficient and may be affected by the formation of the transition film of the resin material. Also, by finishing the sliding parts such as polishing, the sliding surface becomes a very good flat surface, so there is no water leakage.
Although the disk valve has excellent water blocking properties, the polishing step may be omitted depending on the required properties of water blocking properties.

Although the mechanism of action of the underwater-lubricating resin composition of the present invention has not been clearly elucidated, it exhibits good sliding properties when used in water.
In addition, the wear resistance is improved in combination with the characteristics of PPS, and it can withstand mechanical and thermal shocks well.

Further, in the invention relating to the disk valve, the properties of PPS and glassy carbon are synergistically exerted to improve the lubricity and wear resistance of the valve seat or the valve body, and the mechanical and thermal properties are improved. Strong against shocks. Also, since the glassy carbon to be blended has no anisotropy,
The flatness and dimensional accuracy of the sliding contact surface of the valve seat or the valve body becomes extremely high. Therefore, the disc valve of the present invention can maintain good water-stopping property and operability for a long time even if it is continuously used for a long time.

Further, by adopting a resin composition obtained by adding PTFE powder to the resin composition to the valve body or valve seat of such a valve device, the slidability is further improved,
The rotational torque of the valve device is reduced, and sliding noise (abnormal noise) during operation is eliminated.

Such a disc valve has a water temperature of -20 to 1 depending on the specifications and conditions (for example, atmospheric pressure).
It can also be used under a temperature condition of 20 ° C. Specifically, even under a normal temperature condition of 0 to 100 ° C. under atmospheric pressure, warp or the like does not occur in the disk valve, and good dimensional accuracy can be maintained, which is preferable.

The glass transition point of the PAS resin (80-
When used in hot water of 90 ° C. or higher, annealing heat treatment is required to be performed at 90 to 230 ° C. for 1 to 24 hours in order to improve dimensional stability and heat resistance. When using under the following temperature conditions,
The heat treatment may be omitted. The skin layer formed by the above heat treatment may be removed by polishing to improve the sliding characteristics of the sliding surface.

[0072]

【Example】

[Examples 1 to 9 and Comparative Examples 1 to 8] The raw materials used in Examples 1 to 9 and Comparative Examples 1 to 8 are summarized below. Note that the abbreviations used in the table are shown in parentheses, and all the mixing ratios are shown by weight%. (1) Polyphenylene sulfide resin (PPS-1) manufactured by Toray Industries: M2888 (linear type, resin melt viscosity 300 to
600 Poise) (2) Polyphenylene sulfide resin (PPS-2) made by Topren: K4 (crosslinking type, resin melt viscosity 1800)
〜2400 Poise) (3) Glassy carbon (GC-1) Kanebo Co., Ltd .: Bell Pearl C-2000 (2000 ° C. baked product) (4) Glassy carbon (GC-2) Kanebo Co., Ltd .: Bell Pearl C-600 (600) (° C fired product) (5) Recycled tetrafluoroethylene resin (PTFE) Kitamura: KT400H (6) Polyoxymethylene resin (POM) Polyplastics: M90-44 (7) Ultra high molecular weight polyethylene (PE) Mitsui Petrochemical: Lubmer, injection molding grade (8) Carbon fiber (CF) Toray: Vesphite HTA, fiber diameter 7.2 μm (9) Glass fiber (GF) Asahi Fiberglass: Chopped strands, average Fiber diameter 13 μm, (10) Mica manufactured by Canadian Mica: Mica S-200, average particle diameter 60 μm
m.

The above raw materials were blended in the proportions shown in Table 3 or Table 4, preliminarily dry-mixed, and then fed to a twin-screw extruder (PCM-30 manufactured by Ikegai Tekko KK) for extrusion granulation. A test piece was prepared from the obtained pellet by injection molding using a predetermined mold, and the results are also shown in Table 3 or Table 4. In addition, about the thing which performs a 90 degreeC hot-water test, 120-200 degreeC performed the annealing heat processing of 8 hours.

<Friction test> Cylindrical test piece A (inner diameter 17 m
m, outer diameter 21 mm, length 10 mm) and a cylindrical test piece B (inner diameter 6 mm, outer diameter 35 mm, thickness 6 mm) were mounted in a thrust friction wear test, and the test condition was a sliding speed of 4 m /
As a condition of minute, load of 4 kgf / cm ² , and hot and cold water (60 ° C.) lubrication, the coefficient of friction was determined 1 hour after the start of the test (initial stage) and 50 hours after the test.

<Durability Test> Further, a valve seat (outer diameter 35 mm, height 5) which can be mounted on the valve device having the structure shown in FIGS.
mm) and a valve body (outer diameter 27 mm, height 9 mm) were prepared by the same manufacturing method as the test piece described above.

The valve device having the structure shown in FIGS. 1 and 2 for mounting the test piece is a slide type valve device for mixing hot water and water. Two valve devices are provided on the bottom plate 2 attached to the lower portion of the valve box 1. The annular packings 3 are attached and the inside of each is used as an inlet 4 for hot water or water, and the inlet 4 is provided on the valve seat 5 provided on the bottom plate 2.
Two valve holes 6 communicating with each of them are formed, a lever holder 8 is rotatably mounted on a valve body 7, and a lower end portion of a lever shaft 10 slidably supported by a pin 9 is attached to the valve holder 7. The valve body 7 is slidably contacted with the seat surface 13 of the valve seat 5 by connecting the valve body 7 with the rectangular recess 11 on the upper surface of the body 7 and swinging the lever 12 vertically and horizontally to form the two valve holes 6 respectively. Alternatively, the two are opened and closed at the same time.

When the valve body 7 is operated to open the valve hole 6,
The hot water and water respectively supplied to the two inlets 4 are provided in the valve holes 6
Flows into the flow path 14 formed by cutting out from the lower part of the valve body 7, flows into the mixing chamber 15, and is further discharged from the mixed water outlet 16 formed on the side wall of the valve box 1 toward the faucet tip. It will be.

In the above valve device, a ring-shaped seal member 17 is attached to the lower surface of the lever holder 8 to prevent water from leaking into the shaft insertion hole 18, and a ring-shaped seal member 19 is provided to prevent the leakage from both members. Prevents water leakage.

With respect to the valve seat 5 and the valve body 7 obtained as described above, the sliding contact surface (seat surface) is ground by a surface grinder to increase flatness, and further polished by a lapping machine to obtain surface roughness. Is sufficiently lowered (Ra 0.1 to 0.2 μm), and the valve seat 5 and the valve body 7 are integrally overlapped with each other and mounted on the valve device, and the following durability test is performed to check the waterproofness and operability. The evaluation was performed, and the results are shown in Table 3 or Table 4. A durability test was not performed on a test piece having a poor result of a scratch resistance test described below.

<Water stopping test and operability test> The valve seat and the valve body of the valve device (the internal structure is the same as that shown in FIGS. 1 and 2) are changed to a single lever type mixed faucet as shown in FIG. After being incorporated, the waterproofness and operability were investigated.

For water stopping, the lever is located in the lower center part (water stopping state).
Then, the water pressure was maintained at 17.5 kgf / cm ² by a pump for 30 seconds, and the pressure drop (kgf / cm ² ) due to water leakage after 30 seconds was measured. At this time, the amount of pressure drop was 0.3 kgf / cm ² or less at the initial stage and was less than 0.3 after the durability test.
It was judged to be good if it was 5 kgf / cm ² or less.

The operability was measured by using a torque measuring device (DFG-2K manufactured by Shinbo Kogyo Co., Ltd.) to measure the torque of the lever up and down (stopping water, water discharge, flow rate adjustment) and left and right (adjusting hot water temperature). The torque measurement value (operating force) at this time is 300 to 80.
If 0 gf, it was determined to be good. If the torque is less than 300 gf, the handle will drop due to its own weight during use, and if the torque exceeds 800 gf, smooth operability will not be obtained. From such a tendency, a more preferable range is 350 to 700 gf. Is. And it is good if the difference in torque from the initial test to the endurance test is within 200 gf.

Such water-stopping property and operability were confirmed by the following initial test and durability test. Initial test: The initial water stoppage and operability were measured before the durability test. Durability test: Using the valve element used in the initial test, connect the lever to a durability tester (NTN Precision Resins Co., Ltd.), and move the lever from the right end upper part Ru (water stop) to the right end as shown in FIG. Lower Rd (Cold water) → Lower left Ld (Hot water 90 ° C) →
Upper left end Lu (stop water) → Lower left end Ld (hot water 90 ° C) →
Central lower Cd (warm water 45 ° C) → central upper Cu (stop water) →
Lower center Cd (warm water 45 ° C) → Lower right end Rd (cold water) →
One cycle of the right upper Ru (water stop) (required time is about 25
Seconds) and the water-stopping property and operability after 50,000 cycles were confirmed.

<Scratchability Test> A super steel blade (contact angle 60 ° C., tip R2 μm) with a load of 200 g was applied to the sliding surface of the valve seat and the valve body of the test piece (a disc shape known as a disc valve). , At a speed of 100 m / min. afterwards,
A surface roughness meter (Dek, manufactured by Nippon Vacuum Co., Ltd.)
The results are shown in Table 1 below, and the results are as follows: ○ for scratches with a depth of less than 3 μm, Δ for 3 μm or more and less than 5 μm,
Those having a size of 5 μm or more were evaluated in three grades of X.

<Surface deformability before and after water absorption> Before water absorption (at room temperature,
A surface roughness meter (made by Nippon Vacuum Co., Ltd .: D)
Ektak), the change in surface shape is 3 μm
Less than ◯, 3 μm or more and less than 5 μm △, 5
Those having a size of μm or more were evaluated in three grades of x.

[0086]

[Table 3]

[0087]

[Table 4]

As is clear from the results of Table 3 or Table 4, Examples 1 to 9 are all excellent in the coefficient of friction and the stability thereof, and are hard to be scratched, and the surface shape is resistant to deformation due to water absorption. It was a good result. In Examples 7 and 8 in which the fluororesin was blended, the water blocking property after the durability test tended to slightly decrease (the pressure drop amount increased).

In Example 5 using the crosslinked PPS,
Compared to Example 2 using the same amount of linear PPS, it was found that the operability after the durability test decreased (the handle torque increased) and the wear was somewhat large, but depending on the degree of the required characteristics. Is usable.

Further, although Example 6 using the glassy carbon fired at 600 ° C. was found to be somewhat inferior in durability from the results of the other examples using the glassy carbon fired at 2000 ° C., It can be used depending on the degree of required characteristics.

On the other hand, Comparative Example 1 containing less than the predetermined amount of glassy carbon (20 parts by weight) per 100 parts by weight of PPS was inferior in scratch resistance and had a problem in practical use.

Further, in Comparative Example 2 in which the glassy carbon was blended in an amount larger than the predetermined amount (200 parts by weight) with respect to 100 parts by weight of PPS, there was a problem that the molded body was stuck to the cavity without being released during injection molding. However, the evaluation test was not conducted because there is a problem in molding. Further, in Comparative Example 3 in which the amount of the fluororesin was greater than the predetermined amount, a scratch of 5 μm or more was formed in the scratchability test, which was a problem in practical use.

In Comparative Examples 4 and 5 in which the fibrous reinforcing material was blended in place of the glassy carbon, the sliding contact surface was worn so that the pressure drop amount could not be measured after the durability test in the water stopping test.

Further, in Comparative Example 6 in which glassy carbon and mica were mixed with PPS, the sliding contact surface after water absorption was largely deformed, and the water stopping property after the durability test was poor.

Further, in Comparative Examples 7 and 8 in which glassy carbon was blended with a polyoxymethylene resin or a polyethylene resin, there were problems of scratch resistance and deformation of the sliding contact surface after absorbing water, and the disk valve It was not suitable for use as.

[0096]

As described above, the invention of an underwater slidable resin composition comprising a polyarylene sulfide-based resin and a predetermined amount of glassy carbon having a predetermined particle size has a shrinkage factor at the time of molding into glassy carbon. Has no anisotropy, has good dimensional accuracy, and has a merit that the self-lubricating property is sufficiently excellent in the case where a fluorine resin is blended if necessary.

In the invention in which at least one of the valve seat or the valve body is a disk valve which is a molded product of a resin composition comprising a polyarylene sulfide resin and a predetermined amount of glassy carbon having a predetermined particle size, the valve seat or The valve body is precisely molded without dimensional error, and they are excellent in wear resistance, and there is an advantage that the surface roughness of the sliding contact surface is increased during use and the foreign body is not easily scratched by foreign matter. Further, such a faucet disc valve has an advantage that it is excellent in operability of the valve body when continuously used for a long time.

[Brief description of drawings]

FIG. 1 is a vertical sectional view of an embodiment.

FIG. 2 is an exploded perspective view of parts of the embodiment.

FIG. 3 is a perspective view showing an external appearance of a mixing tap and an operation state of a lever.

[Explanation of symbols]

 1 valve box 2 bottom plate 3 annular packing 4 inlet 5 valve seat 6 valve hole 7 valve body 8 lever holder 9 pin 10 lever shaft 11 recess 12 lever 13 seat surface 14 flow path 15 mixing chamber 16 outlet 17, 19 sealing member 18 shaft Charging hole

Claims (6)

[Claims] 1. A polyarylene sulfide-based resin 100.
An underwater slidable resin composition containing 55 to 165 parts by weight of glassy carbon having an average particle size of 1 to 30 μm with respect to parts by weight. 2. A polyarylene sulfide-based resin 100.
55 to 165 parts by weight of glassy carbon having an average particle size of 1 to 30 μm, and fluorine-based resin powders 1 to 30 with respect to parts by weight.
An underwater slidable resin composition containing parts by weight. 3. The underwater slidable resin composition according to claim 2, wherein the fluororesin powder is a perfluoro fluororesin powder. 4. The underwater slidable resin composition according to claim 2, wherein the fluororesin powder is a tetrafluoroethylene resin powder. 5. The underwater slidable resin composition according to claim 4, wherein the tetrafluoroethylene resin powder is a regenerated tetrafluoroethylene resin powder. 6. A valve body is superposed on a valve seat having a valve hole,
In a faucet disc valve in which a valve body is slid relative to a valve seat to open and close the valve hole, at least one of the valve seat and the valve body is based on 100 parts by weight of a polyarylene sulfide resin. A disk valve for a water faucet, which is a molded product of a resin composition containing 55 to 165 parts by weight of glassy carbon having an average particle diameter of 1 to 30 μm.