JP4493022B2 - Umbrella valve, check valve device for air pump and air pump - Google Patents

Description

  The present invention relates to an umbrella valve, an air pump check valve device, and an air pump. More specifically, the present invention relates to an umbrella valve surface-treated with a specific treatment agent, an air pump check valve device including the umbrella valve, and an air pump.

  Conventionally, an air pump is known in which the inside of a housing is partitioned into an intake chamber, a pump chamber, and an exhaust chamber (see, for example, Patent Document 1).

  FIG. 1 is an explanatory view showing a configuration of a diaphragm pump which is such an air pump. In the diaphragm pump shown in the figure, the inside of a resin housing 1 is divided into an intake chamber 4, a pump chamber 5, and an exhaust chamber 6 by a resin partition 2.

  The intake chamber 4 is provided with an intake pipe 4p that forms a flow path hole communicating with the primary side. Further, the exhaust chamber 6 is provided with an exhaust pipe 6p that forms a channel hole communicating with the secondary side. In addition, a diaphragm 7 is provided in the pump chamber 5, whereby the pump chamber 5 is divided into a pump space 5A and a diaphragm drive chamber 5B.

  The outer periphery of the diaphragm 7 is fixed to the inner wall of the pump chamber 5, and the center thereof is fixed to one end surface (upper end surface in FIG. 1) of the piston 8. By reciprocating the piston 8 by appropriate means (up and down movement in FIG. 1), the volume of the pump space 5A surrounded by the diaphragm 7 and the partition wall 2 can be increased or decreased.

  The partition wall 2 (2a) that separates the intake chamber 4 and the pump chamber 5 is provided with a plurality of flow path holes 9a, and a rubber umbrella valve 3a is provided so as to close these holes. Yes. The umbrella-shaped portion of the umbrella valve 3a is located in the pump chamber 5, and only the gas flow from the intake chamber 4 to the pump space 5A is allowed by the umbrella valve 3a, and thereby the first check valve is provided. A valve device is constructed.

  On the other hand, the partition wall 2 (2b) separating the pump chamber 5 and the exhaust chamber 6 is formed with a plurality of flow passage holes 9b, and a rubber umbrella valve 3b is provided so as to be able to close the channel holes 9b. It has been. The umbrella-shaped portion of the umbrella valve 3b is located in the exhaust chamber 6, and only the gas flow from the pump space 5A to the exhaust chamber 6 is allowed by this umbrella valve 3b, and thereby the second check A valve device is constructed.

  In the diaphragm pump shown in FIG. 1, when the diaphragm 7 is deformed by lowering the piston 8, the volume of the pump space 5 </ b> A increases, the pressure decreases, and the pressure in the intake chamber 4 communicating with the primary side is reduced. As a result, the umbrella-shaped portion of the umbrella valve 3a is separated from the opening of the flow passage hole 9a and the first check valve device is opened (the pressure between the intake chamber 4 and the pump space 5A at this time). The difference corresponds to the operating pressure of the first check valve device.) The primary side gas flows through the intake pipe 4p and the intake chamber 4 into the pump chamber 5 (pump space 5A) ( Aspirated). At this time, the second check valve device maintains the closed state.

  Next, when the diaphragm 7 is deformed again by raising the piston 8, the volume of the pump space 5A decreases, the pressure rises, and becomes higher than the pressure in the exhaust chamber 6 communicating with the secondary side. The umbrella-shaped portion of the umbrella valve 3b is separated from the opening of the flow passage hole 9b, and the second check valve device is opened (the pressure difference between the pump space 5A and the exhaust chamber 6 at this time is the second The gas sucked into the pump chamber 5 (pump space 5A) flows to the secondary side through the exhaust chamber 6 and the exhaust pipe 6p (is discharged). ). At this time, the first check valve device maintains the closed state.

Here, the reciprocating motion of the piston 8 is performed at a very high speed (for example, 50 to 60 reciprocating motions per second).
JP 2003-278658 A

In the air pump configured as described above, if the operation is once stopped and then restarted, the first check valve device and / or the second check valve device may not operate.
That is, during the operation stop of the air pump in which both the first check valve device and the second check valve device are closed, the rubber umbrella valve (umbrella-shaped portion) constituting the check valve device is A positive flow (secondary to secondary from the primary side) that reaches the operating pressure (hereinafter referred to as “set pressure”) set in the check valve device as a result of sticking to the partition wall around the channel hole. Also, the umbrella valve cannot be separated (opened) from the opening of the flow path hole.

The above problems are unlikely to occur in a new air pump (check valve device). After using the air pump for a certain period of time, for example, when the pump is operated (the check valve device repeats opening and closing operations at this time), the pump This frequently occurs after the stop (the check valve device maintains the closed state at this time) is repeated several hundred times.
In addition, this problem frequently occurs in a small precision check valve device having a low set pressure (for example, 50 KPa or less) and good response.

For the above problems, the umbrella valve constituting the first check valve device and the second check valve device is treated with a surface treatment agent containing alkoxysilane, and the surface thereof is made of SiO ₂ . It is also conceivable that non-adhesiveness (adhesion prevention effect) is expressed by forming a film (surface treatment layer).

However, the above problem cannot be solved even by a check valve device using an umbrella valve treated with such a surface treatment agent.
This is because the surface treatment layer to be formed (SiO ₂ -based coating) has low adhesion to rubber, so that the surface treatment can occur due to impact during operation of the air pump (when the check valve device is repeatedly opened and closed). This is because the layer is detached and scattered, and the anti-adhesion effect by the surface treatment layer is reduced / disappeared in a very short time.

The present invention has been made based on the above situation.
The first object of the present invention is a non-adhesive umbrella valve that constitutes a check valve device, and the umbrella-shaped portion is in contact with a partition wall portion (closed state) for a certain period of time ( Provided is an umbrella valve in which the umbrella-shaped portion does not stick to the partition wall portion even after being held for 5 minutes or more, and can be reliably separated from the partition wall portion by positive flow. There is.
A second object of the present invention is a check valve device used for an air pump, which reliably opens a valve by a positive flow even after being held in a closed state for a certain time (more than 5 minutes). An object of the present invention is to provide a check valve device for an air pump capable of performing
The third object of the present invention is to reliably operate the check valves (the first check valve device and the second check valve device) constituting the same even if the operation is once stopped and then restarted. An object of the present invention is to provide an air pump.

The umbrella valve of the present invention is a rubber umbrella valve constituting a check valve device, which is represented by the formula (1): Si (OR ¹ ) ₄ (wherein R ¹ is an alkyl group having 1 to 4 carbon atoms). A tetraalkoxysilane represented by formula (2): Ti (OR ² ) ₄ (wherein R ² represents an alkyl group having 2 to 4 carbon atoms) and Formula (3): Si (OR ³ ) _m R ⁴ _3-m — (CH ₂ ) _n —R ⁵ (wherein R ³ represents an alkyl group or an alkoxyalkyl group, R ⁴ represents an alkyl group, m is an integer of 1 to 3, n is an integer of 0 to ^5. R ⁵ represents an organic functional group having reactivity with the polymer main chain of rubber.) Surface treatment agent containing an agent and a solvent for dissolving them (hereinafter referred to as “specific treatment agent”). Characterized in that it is more processed.

The tetraalkoxysilane constituting the specific treating agent has four alkoxy groups (—OR ¹ ) in the molecule, and the tetraalkoxy titanium also has four alkoxy groups (—OR ² ) in the molecule. Furthermore, the silane coupling agent has a hydrolyzable group (—OR ³ ) and a reactive organic functional group (—R ⁵ ) in the molecule.
In the surface treatment of an umbrella valve with a specific treatment agent, tetraalkoxysilane, tetraalkoxytitanium, and a silane coupling agent react (hydrolysis / condensation reaction) to form a Si—O bond and a Ti—O bond. A surface-treated layer (SiO ₂ —TiO ₂ film) having a cross-linked structure is formed, which makes the surface of the umbrella valve excellent non-adhesiveness (adhesion prevention effect superior to that of the SiO ₂ film) Is expressed.

Moreover, a reactive organic functional group (—R ⁵ ) derived from the silane coupling agent is introduced into the SiO ₂ —TiO ₂ film (or the structure in the film formation process) constituting the surface treatment layer. This organic functional group reacts with the polymer main chain of rubber constituting the umbrella valve. As a result, the surface treatment layer is chemically bonded to the polymer main chain of the rubber via the silane coupling agent. In this way, a chemical bond is formed between the surface treatment layer composed of the SiO ₂ —TiO ₂ based coating and the polymer main chain of the rubber via the silane coupling agent. The layer adheres firmly to the rubber constituting the umbrella valve.

In the umbrella valve of the present invention, the following modes are preferable.
[1] The tetraalkoxysilane contained in the specific treating agent is tetramethoxysilane or tetraethoxysilane, and the tetraalkoxytitanium is selected from tetraethoxytitanium, tetraisopropoxytitanium and tetra-n-butoxytitanium. Must be at least one kind.
[2] The specific treating agent contains an acid or a base.
[3] The specific treating agent contains tetraethoxysilane, tetraethoxytitanium or tetraisopropoxytitanium, a silane coupling agent, an acid or base, and an organic solvent.
[4] The specific treating agent contains 1 to 10% by mass of tetraalkoxytitanium with respect to the content of tetraalkoxysilane.
[5] The specific treating agent contains 3 to 10% by mass of tetraalkoxytitanium with respect to the content of tetraalkoxysilane.

  The check valve device for an air pump according to the present invention is provided in a partition wall in which a channel hole communicating with a pump space whose volume is increased or decreased by a piston or a diaphragm is formed, and in the partition wall so that the channel hole can be closed. An air valve check valve device that opens and closes the flow path hole when the umbrella valve is deformed according to the pressure in the pump space, and the umbrella valve is an umbrella valve according to the present invention. It is characterized by being.

  The check valve device for an air pump of the present invention preferably operates at a pressure of 50 KPa or less.

  The air pump of the present invention is divided into a housing; and an interior of the housing into an intake chamber communicating with the primary side, a pump chamber including a pump space whose volume is increased or decreased by a piston or a diaphragm, and an exhaust chamber communicating with the secondary side. A first check valve device that includes an umbrella valve provided in a partition partitioning the intake chamber and the pump chamber, and that allows only a gas flow from the intake chamber to the pump space; and the pump A second check valve device that includes an umbrella valve provided in a partition wall that separates the chamber and the exhaust chamber, and that allows only a gas flow from the pump space to the exhaust chamber; The umbrella valve constituting the check valve device and the second check valve device is the umbrella valve of the present invention.

[1] According to the umbrella valve of the present invention in which a surface treatment layer (SiO ₂ —TiO ₂ film) with a specific treatment agent is formed, excellent non-adhesiveness (better than that with a SiO ₂ film) Anti-adhesion effect).
Therefore, in the check valve device constituted by the umbrella valve of the present invention, after holding the umbrella-shaped part of the umbrella valve in contact with the partition wall part (closed state) for a certain time (more than 5 minutes). Even if it exists, the said umbrella-shaped part will not adhere to a partition part, but the said umbrella-shaped part can be reliably spaced apart from a partition part by a normal flow.

[2] Since the surface treatment layer (SiO ₂ —TiO ₂ based coating) with a specific treatment agent is firmly attached to the rubber constituting the umbrella valve, the air pump is in operation (of the check valve device). The surface treatment layer is not detached or scattered even by an impact at the time of repeating the opening and closing operation, and an excellent anti-adhesion effect can be stably exhibited over a long period of time.
Therefore, even after the air pump provided with the umbrella valve of the present invention has been used (operated and stopped) for a long period of time, the umbrella-shaped portion is caused by the positive flow (flow from the primary side to the secondary side) during re-operation. Can be reliably separated from the partition wall portion.

[3] According to the check valve device for an air pump provided with the umbrella valve of the present invention, even when the valve is in a closed state accompanying the stop of the air pump and maintained for a certain time (5 minutes or more), The valve can be reliably opened by a positive flow (flow from the primary side to the secondary side).
Moreover, even after the air pump provided with the umbrella valve of the present invention has been used (operated and stopped) for a long period of time, the valve can be reliably opened by the positive flow during the re-operation.

[4] According to the air pump including the umbrella valve of the present invention, the check valve (the first check valve device and the second check valve) can be used even if the operation is stopped and then restarted. Valve device) can be operated reliably.
Moreover, even after use (operation and stop) for a long period of time, the check valve constituting this can be operated reliably.

Hereinafter, the present invention will be described in detail.
<Umbrella valve>
FIG. 2 is an explanatory view showing a part of the umbrella valve of the present invention in a cutaway manner.
The umbrella valve 30 shown in the figure is a rubber molded product including an umbrella-shaped portion 31 and a shaft portion 33 in which a diameter-enlarging portion 32 for retaining is formed.
The height (T) of the umbrella valve 30 is, for example, 7 to 15 mm, and preferably 7 to 11 mm. Moreover, as a diameter (D) of the umbrella-shaped part 31, it is 5-15 mm, for example, Preferably it is 5.5-12 mm.

<Check valve device>
3 and 4 are cross-sectional views showing an air pump check valve device (the check valve device of the present invention) provided with the umbrella valve of the present invention.
This check valve device is mounted between the pump space S1 and the exhaust chamber S2, and allows only the flow of gas from the pump space S1 to the exhaust chamber S2. Corresponds to a “valve stop device”.

This check valve device includes a partition wall 20 that partitions the pump space S1 and the exhaust chamber S2, and an umbrella valve 30 (an umbrella valve of the present invention shown in FIG. 2) provided in the partition wall 20.
The partition wall 20 is formed with a plurality of flow path holes 21 communicating the pump space S1 and the exhaust chamber S2. The diameter (d) of the flow path hole 21 is, for example, 0.5 to 2 mm, and preferably 0.5 to 1.5 mm. The number of flow path holes 21 is 3 to 6, for example.
The umbrella valve 30 is provided so that the umbrella-shaped portion 31 can block the flow path hole 21 formed in the partition wall 20.

  When the pressure in the pump space S1 becomes higher than the pressure in the exhaust chamber S2 and the pressure difference reaches a set pressure, the umbrella-shaped portion 31 of the umbrella valve 30 is placed in the flow path hole 21 as shown in FIG. The valve is separated from the opening to open, and the gas in the pump space S1 flows into the exhaust chamber S2 to ensure a positive flow (flow from the primary side to the secondary side). On the other hand, even if the pressure in the pump space S1 is lower than the pressure in the exhaust chamber S2, the umbrella-shaped portion 31 maintains the state of closing the flow path hole 21 (the state shown in FIG. 3). The gas in S2 does not flow (backflow) into the pump space S1.

The set pressure of the check valve device shown in FIGS. 3 and 4 is preferably 50 KPa or less, and more preferably 30 KPa or less.
Although the check valve device that operates at such a low pressure is excellent in responsiveness, it is easily affected by the adhesive force between the umbrella valve (umbrella-shaped portion) and the partition wall.
Therefore, the non-adhesiveness (adhesion prevention effect) achieved by the present invention is particularly important in such a precise and small check valve device having a low set pressure.

  In the above description, the check valve device (second check valve device) that allows only the gas flow from the pump space S1 to the exhaust chamber S2 has been described. It is of course possible to use it as a check valve device (first check valve device) that is mounted between the pump space and the pump space and allows only gas flow from the intake chamber to the pump space.

  The umbrella valve of the present invention is characterized in that it is surface-treated with a specific treatment agent, thereby providing excellent non-adhesiveness (anti-adhesion effect) and its stability (durability of anti-adhesion effect). It can be demonstrated.

<Specific treatment agent>
The specific treating agent contains tetraalkoxysilane, tetraalkoxytitanium, a silane coupling agent, and a solvent for dissolving them as essential components.
In the above formula (1) indicating tetraalkoxysilane, R ¹ represents an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group. Specific examples of the tetraalkoxysilane include tetramethoxysilane (TMOS) and tetraethoxysilane (TEOS), and TEOS is particularly preferable.

In the above formula (2) indicating tetraalkoxytitanium, R ² represents an alkyl group having 2 to 4 carbon atoms such as an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group. To express. Specific examples of tetraalkoxytitanium include tetraethoxytitanium, tetraisopropoxytitanium and tetra-n-butoxytitanium, with tetraethoxytitanium and tetraisopropoxytitanium being particularly preferred.

In the above formula (3) showing a silane coupling agent, R ³ represents an alkyl group or an alkoxyalkyl group, R ⁴ represents an alkyl group, m is an integer of 1 to 3, preferably 3, and n is 0 An integer of -5, preferably an integer of 0-3. R ⁵ represents an organic functional group having reactivity with the polymer main chain of rubber.

In the above formula (3), the group represented by Si (OR ³ ) _m R ⁴ _3-m — has at least one, preferably three hydrolyzable groups (—OR ³ ). Thereby, the silane coupling agent represented by the above formula (3) is composed of tetraalkoxysilane having four alkoxy groups (—OR ¹ ) and tetraalkoxy titanium having four alkoxy groups (—OR ² ). Either can react.

Here, the group represented by Si (OR ³ ) _m R ⁴ _3-m — is preferably a trialkoxysilyl group such as a trimethoxysilyl group or a triethoxysilyl group.

Examples of the organic functional group (R ⁵ ) having reactivity with the polymer main chain of rubber include amino group, mercapto group, vinyl group, (meth) acryloyloxy group, epoxy group and ureido group. . Among these, preferred are a mercapto group having reactivity with a polymer main chain of a rubber having an unsaturated bond, and a vinyl group having reactivity with a polymer main chain of a rubber having no unsaturated bond. be able to.

  The solvent constituting the specific treatment agent can be selected from those that can dissolve any of tetraalkoxysilane, tetraalkoxytitanium, and silane coupling agent, and varies depending on the type of hexane, Examples of the organic solvent include methanol, ethanol, tetrahydrofuran, dichloromethane, chloroform, benzene, ethyl acetate, dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF), toluene, and acetone. Among these, hexane , Methanol, ethanol, dichloromethane and acetone are preferred.

  The specific treating agent may contain various optional components in addition to the essential components as long as the effect is not impaired.

  Specific treatment agents are identified from the viewpoint of promoting the formation of a crosslinked structure by efficiently carrying out the reaction (hydrolysis / condensation reaction) of tetraalkoxysilane, tetraalkoxytitanium, and silane coupling agent. The treating agent is preferably acidic or alkaline, and particularly preferably acidic (pH is 6 or less, particularly 2 to 5).

The acid contained in order to make a specific treating agent acidic may be an inorganic acid or an organic acid. Here, examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid and the like, and hydrochloric acid is preferable. Examples of the organic acid include formic acid, acetic acid, propionic acid, butanoic acid and pentanoic acid, and acetic acid is preferred.
Examples of the base contained for making the specific treating agent alkaline include ammonia water and various amines.

  As a content rate of the tetraalkoxysilane which is an essential component of a specific processing agent, it is preferable that it is 0.5-20 mass% of the whole composition, More preferably, it is 2-10 mass%. The content ratio of the tetraalkoxysilane can be adjusted to an appropriate ratio mainly by adjusting the amount of the solvent used.

  The tetraalkoxytitanium, which is an essential component of the specific treating agent, is preferably contained in a proportion of 1 to 10% by mass, more preferably 3 to 10% by mass, particularly preferably relative to the content of tetraalkoxysilane. Is 6 to 10% by mass.

When the content ratio of tetraalkoxytitanium (relative ratio with respect to tetraalkoxysilane) is too small, the surface treatment layer formed from the resulting composition cannot exhibit a sufficient anti-adhesive effect.
On the other hand, when the content ratio of tetraalkoxytitanium (relative ratio with respect to tetraalkoxysilane) is excessive, the obtained composition is cured in a short time, and workability such as applicability is lowered.

  The silane coupling agent that is an essential component of the specific treating agent is preferably contained in a proportion of 0.1 to 100% by mass with respect to the total content of tetraalkoxysilane and tetraalkoxytitanium, Preferably it is 0.5-20 mass%, Most preferably, it is 1-10 mass%.

When the content ratio of the silane coupling agent (relative ratio with respect to the total of tetraalkoxysilane and tetraalkoxytitanium) is too small, the surface treatment layer formed by the resulting composition is used for the rubber constituting the umbrella valve. However, it does not have sufficient adhesion.
On the other hand, when the content ratio of the silane coupling agent (relative ratio relative to the total of tetraalkoxysilane and tetraalkoxytitanium) is excessive, formation of a crosslinked structure by the resulting composition becomes insufficient, and the umbrella valve It becomes difficult to completely cover the surface (formation of a surface treatment layer).

  In the specific treating agent, the content of the solvent is preferably 3 to 50 times the total content (mass) of tetraalkoxysilane, tetraalkoxytitanium, and silane coupling agent, and more preferably 10 to 10 times. 30 times.

  When the content ratio of the solvent is too small, the surface treatment layer formed from the resulting composition may not exhibit sufficient adhesion to the rubber constituting the umbrella valve. On the other hand, if this ratio is excessive, the ratios of tetraalkoxysilane, tetraalkoxytitanium and silane coupling agent in the resulting composition will be too small, leading to a decrease in coating efficiency.

  The specific treating agent can be easily produced by dissolving tetraalkoxysilane, tetraalkoxytitanium, silane coupling agent, and optional components in a solvent. In addition, when the obtained composition is left still for a long time at room temperature, there exists a possibility that the condensate of a structural component (especially tetraalkoxysilane and tetraalkoxytitanium) may be formed and a precipitate may be produced. For this reason, it is preferable to use a specific treating agent within 24 hours after production, and it is important to stir the composition sufficiently (for example, 1 to 6 hours) to homogenize the composition before use. . Moreover, you may heat to 60-70 degreeC as needed.

  The rubber (raw rubber) constituting the umbrella valve includes natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), chloroprene rubber (CR), butyl rubber (IIR), styrene butadiene rubber (SBR), and nitrile. Rubber (NBR), ethylene propylene rubber (EPM, EPDM), acrylic rubber (ACM, ANM), epichlorohydrin rubber (CO, ECO), silicone rubber (VMQ, FVMQ), urethane rubber (AU, EU), fluorine rubber (FKM, FEPM) and the like can be exemplified, and among these, ethylene propylene rubber is preferable.

Examples of the method for surface-treating the umbrella valve (rubber base material) include a method of applying a specific treatment agent to the umbrella valve and heating the coating film with the treatment agent.
The method for applying the specific treatment agent is not particularly limited, such as a dipping method in which an umbrella valve is immersed in the treatment agent, or a method using an application means such as a brush or a roller.
In addition, after apply | coating a processing agent, it is preferable to perform a drying process in order to remove a solvent from the coating film formed in the surface of an umbrella valve | bulb. The drying condition varies depending on the type and content ratio of the solvent constituting the treatment agent, but is, for example, 1 minute to 24 hours at room temperature, and preferably 3 minutes to 1 hour.
The method for heating the coating film is not particularly limited, and examples include heating with an oven. The heating condition is, for example, 50 to 150 ° C. for 5 minutes to 24 hours, and preferably 80 to 120 ° C. for 10 to 120 minutes.

By heating the coating film (coating film with a specific treatment agent) formed on the surface of the umbrella valve, tetraalkoxysilane (—OR ¹ ), tetraalkoxy titanium (—OR ² ), and a silane coupling agent ( -OR ³ ) reaction (hydrolysis / condensation reaction) proceeds to form a surface treatment layer (SiO ₂ —TiO ₂ film) having a cross-linked structure with Si—O bonds and Ti—O bonds. Thus, an umbrella valve (an umbrella valve of the present invention) having excellent non-adhesiveness (adhesion prevention effect) can be obtained. Here, the anti-adhesion effect exhibited by the surface treatment layer (SiO ₂ —TiO ₂ film) is much superior to that exhibited by the surface treatment layer (SiO ₂ film) having a siloxane cross-linked structure. ing.
Accordingly, in the check valve device (the check valve device of the present invention) constituted by the umbrella valve of the present invention, the umbrella-shaped portion of the umbrella valve is in contact with the partition wall portion (closed state) for a certain period of time. Even if it is held (for 5 minutes or more), the umbrella-shaped part does not stick to the partition wall part, and the umbrella-shaped part is reliably separated from the partition wall part by a forward flow, so that the check valve device of the present invention Can be opened.

Thus, the reactive organic functional group derived from the silane coupling agent is present in the structure of the SiO ₂ —TiO ₂ film constituting the surface treatment layer or the formation process (hydrolysis / condensation reaction process). (—R ⁵ ) has been introduced, and this organic functional group (—R ⁵ ) reacts with the polymer main chain of the rubber constituting the umbrella valve. As a result, the finally formed surface treatment layer is chemically bonded to the polymer main chain of the rubber via the silane coupling agent. In this way, a chemical bond is formed between the surface treatment layer composed of the SiO ₂ —TiO ₂ based coating and the polymer main chain of the rubber via the silane coupling agent. The layer (SiO ₂ —TiO ₂ -based coating) can be firmly adhered to the rubber constituting the umbrella valve, and can be applied by impact during operation of the air pump (when the check valve device is repeatedly opened and closed). The surface treatment layer is not detached or scattered, and an excellent anti-adhesion effect can be stably exhibited over a long period of time.
Therefore, even after the air pump provided with the umbrella valve of the present invention has been used (operated and stopped) for a long period of time, the umbrella-shaped portion is caused by the positive flow (flow from the primary side to the secondary side) during re-operation. Can be reliably separated from the partition wall portion, and the check valve device of the present invention can be opened.

<Air pump>
FIG. 5 is an explanatory diagram showing a configuration of a diaphragm pump which is an air pump of the present invention.
The diaphragm pump shown in FIG. 1 includes a resin housing 1; a pump chamber 5 and a secondary chamber including a pump space 5A whose volume is increased or decreased by a diaphragm 7; A resin-made partition wall 20 partitioned into an exhaust chamber 6 communicating with the side; and an umbrella provided so as to block a flow path hole 21 formed in the partition wall 20 (20a) separating the intake chamber 4 and the pump chamber 5 A first check valve device that includes a valve 30 (an umbrella valve of the present invention) and allows only a gas flow from the intake chamber 4 to the pump space 5A; a partition wall 20 that separates the pump chamber 5 and the exhaust chamber 6 ( 20b) is provided with an umbrella valve 30 (an umbrella valve according to the present invention) provided so as to be able to close the flow passage hole 21 formed in 20b), and only allows gas flow from the pump space 5A to the exhaust chamber 6. Comprising a second check valve device for.

  The diaphragm pump shown in FIG. 5 includes the umbrella valve 30 of the present invention surface-treated with a specific treatment agent as the umbrella valve constituting the first check valve device and the second check valve device. It has the characteristics. The other configuration is the same as that shown in FIG.

  The resin constituting the housing 1 is not particularly limited, and examples thereof include engineering plastics such as polybutylene terephthalate, polyphenylene sulfide, polycarbonate, polyamide, polyacetal, and modified polyphenylene ether.

The resin constituting the partition wall 20 is not particularly limited, and it is preferable to use the same resin as the constituent material of the housing 1.
Moreover, the housing 1 and the partition 20 may be integrally molded.

  Examples of the rubber constituting the diaphragm 7 include nitrile rubber, chloroprene rubber, fluorine rubber, silicone rubber, butyl rubber, ethylene propylene rubber, and fluorosilicone rubber.

The inner diameter (cylinder diameter) of the driving chamber 5B of the diaphragm is, for example, 15 to 100 mm, and preferably 20 to 50 mm.
Further, the diameter (piston diameter) of the piston 8 to which the central portion of the diaphragm 7 is fixed is, for example, 5 to 90 mm, and preferably 8 to 40 mm.
The effective pressure receiving area of the diaphragm is, for example, 0.9 to 70 cm ^2, and preferably 1.0 to 15 cm ² .
The height of the diaphragm 7 is preferably 10 mm or less.
Further, the stroke of the diaphragm 7 is, for example, 2 to 20 mm, and preferably 2 to 10 mm.

According to the diaphragm pump including the umbrella valve 30 of the present invention, the first check valve device and the second check valve device constituting the diaphragm pump can be reliably configured even when the operation is once stopped and then restarted. Can be operated.
Moreover, even after use (operation and stop) for a long period of time, the check valve constituting this can be operated reliably.

  Examples of the present invention will be described below, but the present invention is not limited thereto.

[Production example (production of umbrella valve)]
70.0 parts by mass of ethylene propylene rubber “JSR EP33” (manufactured by JSR), 45.0 parts by mass of ethylene propylene rubber “JSR EP96” (manufactured by JSR), and 5.0 parts by mass of zinc oxide Parts, stearic acid 1.0 part by weight, FEF black 90.0 parts by weight, paraffinic process oil 25.0 parts by weight, anti-aging agent (TMDQ) 1.0 part by weight, anti-aging agent (MBI ) 0.5 parts by mass, 0.3 parts by mass of sulfur, and 3.0 parts by mass of a peroxide vulcanizing agent were kneaded with an 8-inch roll, and the resulting unvulcanized rubber composition was heated using a hot press. By performing heat treatment (160 ° C. × 30 minutes), an umbrella valve having a shape as shown in FIG. 2 (height (T) = 7.6 mm, umbrella-shaped diameter (D) = 7.8 mm) is obtained. Produced.

<Example 1>
(1) Preparation of specific treatment agent:
According to the formulation shown in Table 1 below, tetraethoxysilane (TEOS) 0.40 g, tetraisopropoxy titanium 0.004 g, silane coupling agent “A-189” (manufactured by Nihon Unicar Co., Ltd.) 0.01 g, By adding 0.05 g of hydrochloric acid (0.1N) to 7.91 g of acetone and stirring the system at room temperature for 1 hour, a specific treating agent (TEOS concentration = about 4.8% by mass, tetraiso Propoxy titanium concentration = about 0.05 mass%, silane coupling agent concentration = about 0.12 mass%) was prepared.

(2) Umbrella valve surface treatment:
By immersing the umbrella valve obtained in the production example in the specific treatment agent obtained by the above (1) (treatment agent immediately after the end of the stirring operation for 1 hour) at room temperature for 3 minutes, the umbrella valve is obtained. A specific treatment agent was applied to the surface of the film. Next, the umbrella valve was allowed to stand at room temperature for 10 minutes to dry the coating film, and then heat-treated in an oven at 100 ° C. for 60 minutes, whereby the umbrella valve (SiO ₂ —TiO ₂ coating film of the present invention was used. An umbrella valve having a surface treatment layer formed of was manufactured.

(3) Manufacture of relief valves:
The air pump of the present invention having the structure as shown in FIG. 5, comprising the umbrella valve surface-treated according to the above (2) as a constituent member of the first check valve device and the second check valve device. Manufactured. The main specifications and specifications of the obtained air pump are as follows.

(A) Housing resin: polybutylene terephthalate (b) Partition resin: polybutylene terephthalate (molded with housing)
(C) Cylinder diameter (diaphragm drive chamber inner diameter): 30 mm
(D) Piston diameter: 18 mm
(E) Effective pressure receiving area of the diaphragm: 4.5 cm ²
(F) Diaphragm height: 8 mm
(G) Diaphragm stroke: 6 mm
(H) Channel hole formed in partition: diameter 1.0 mm × 6 locations (i) Piston drive source: electromagnet connected to 50 Hz AC current (j) set pressure: about 25 KPa

<Example 2>
A specific treating agent (tetraisopropoxytitanium concentration = about 0.14) in the same manner as in Example 1 (1) except that the amount of tetraisopropoxytitanium used was changed to 0.012 g according to the formulation shown in Table 1 below. Mass%) was prepared, and the umbrella valve of the present invention was produced in the same manner as in Example 1 (2) except that this treatment agent was applied. The obtained umbrella valve was used as the first check valve device and The air pump of the present invention provided as a constituent member of the second check valve device was manufactured.

<Example 3>
A specific treating agent (tetraisopropoxytitanium concentration = about 0.29) in the same manner as in Example 1 (1) except that the amount of tetraisopropoxytitanium used was changed to 0.024 g according to the formulation shown in Table 1 below. Mass%) was prepared, and the umbrella valve of the present invention was produced in the same manner as in Example 1 (2) except that this treatment agent was applied. The obtained umbrella valve was used as the first check valve device and The air pump of the present invention provided as a constituent member of the second check valve device was manufactured.

<Example 4>
A specific treating agent (tetraisopropoxytitanium concentration = about 0.38) in the same manner as in Example 1 (1) except that the amount of tetraisopropoxytitanium used was changed to 0.032 g according to the formulation shown in Table 1 below. Mass%) was prepared, and the umbrella valve of the present invention was produced in the same manner as in Example 1 (2) except that this treatment agent was applied. The obtained umbrella valve was used as the first check valve device and The air pump of the present invention provided as a constituent member of the second check valve device was manufactured.

<Example 5>
A specific treating agent (tetraisopropoxytitanium concentration = about 0.48) in the same manner as in Example 1 (1) except that the amount of tetraisopropoxytitanium used was changed to 0.040 g according to the formulation shown in Table 1 below. Mass%) was prepared, and the umbrella valve of the present invention was produced in the same manner as in Example 1 (2) except that this treatment agent was applied. The obtained umbrella valve was used as the first check valve device and The air pump of the present invention provided as a constituent member of the second check valve device was manufactured.

<Example 6>
According to the formulation shown in Table 1 below, the amount of tetraisopropoxy titanium used was changed to 0.024 g, and the amount of silane coupling agent used was changed to 0.02 g. Prepare a specific treatment agent (TEOS concentration = about 4.8% by mass, tetraisopropoxytitanium concentration = about 0.29% by mass, silane coupling agent concentration = about 0.24% by mass) and apply this treatment agent Except for the above, the umbrella valve of the present invention was manufactured in the same manner as in Example 1 (2), and the obtained umbrella valve was provided as a component of the first check valve device and the second check valve device. The air pump of the present invention was manufactured.

<Example 7>
Example 1 except that the amount of tetraisopropoxy titanium used was changed to 0.012 g and 0.1 g of aqueous ammonia (NH ₃ = 28 to 30%) was added instead of hydrochloric acid according to the formulation shown in Table 1 below. A specific treating agent was prepared in the same manner as in (1), and the umbrella valve of the present invention was produced in the same manner as in Example 1 (2) except that this treating agent was applied. The air pump of the present invention provided as a constituent member of the first check valve device and the second check valve device was manufactured.

<Comparative Example 1>
A comparative air pump comprising the umbrella valve obtained in the manufacturing example (untreated surface umbrella valve) as a constituent member of the first check valve device and the second check valve device was manufactured.

<Comparative example 2>
According to the formulation shown in Table 1 below, a treating agent was prepared in the same manner as in Example 1 (1) except that tetraisopropoxytitanium was not used, and Example 1 (2) except that this treating agent was applied. In the same manner, a comparative umbrella valve was manufactured, and an air pump comprising the obtained umbrella valve as a constituent member of the first check valve device and the second check valve device was manufactured.

<Comparative Example 3>
In accordance with the formulation shown in Table 1 below, a treating agent was prepared in the same manner as in Example 1 (1) except that no silane coupling agent was used, and Example 1 (2) except that this treating agent was applied. In the same manner, a comparative umbrella valve was manufactured, and an air pump comprising the obtained umbrella valve as a constituent member of the first check valve device and the second check valve device was manufactured.

<Evaluation Experiment 1 (Air Pump Durability Test)>
For each of the air pumps manufactured according to Examples 1 to 7 and Comparative Examples 1 to 3, operation for 10 seconds (at this time the check valve device repeats opening and closing operations) and stop for 10 minutes (at this time the check valve device is 1) cycle (most often), and the first check valve device and / or the second check valve device does not operate during re-operation. The number of cycles when the pump stopped was measured. The results are shown in Table 1 (in 100 cycle units).

  Here, during the operation of the air pump (10 seconds), the number of reciprocations of the piston for deforming the diaphragm was set to 50 times / second. Therefore, each of the umbrella valves constituting the first check valve device and the second check valve device has also been opened and closed 50 times in one second. The primary side of the air pump was set to atmospheric pressure, and the secondary side was set to a pressurized state of 25 KPa.

<Evaluation Experiment 2 (Non-stickiness of umbrella valve)>
About each of the umbrella valve | bulb obtained by Examples 1-7 and Comparative Examples 2-3 and the umbrella valve | bulb (umbrella valve | bulb obtained by the manufacture example) used in Comparative Example 1, the adhesive force with respect to stainless steel was measured.
Further, after performing an endurance test (evaluation experiment 1) of an air pump including each of these umbrella valves (in the air pump according to Examples 1 to 7, after completion of 1600 cycles, In such an air pump, after the completion of the cycle shown in Table 1, the adhesive strength against stainless steel was measured again.
The measuring method is as follows. The results are also shown in Table 1.

(Measurement method of adhesive strength)
The shaft portion of the umbrella valve is inserted into the through hole formed in the stainless steel plate, and the umbrella-like portion is brought into contact with the surface of the stainless steel plate (around the through hole) (contact area≈0.42 cm ² ), and the contact area is 10N. The load of was applied.
Next, the tip portion of the shaft portion inserted through the through hole was pressed from the back side of the stainless steel plate to separate the umbrella-shaped portion of the umbrella valve from the stainless steel plate. The adhesive force per unit area was measured by measuring the pressing force at this time.

  The umbrella valve of the present invention is suitably used as a constituent member of an air pump check valve device.

It is explanatory drawing which shows the structure of the conventional air pump (diaphragm pump). It is explanatory drawing which fractures | ruptures and shows a part of umbrella valve | bulb of this invention. It is sectional drawing which shows the non-return valve apparatus (valve closing state) for air pumps of this invention. It is sectional drawing which shows the non-return valve apparatus (valve open state) for air pumps of this invention. It is explanatory drawing which shows the structure of the air pump (diaphragm pump) of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Housing 20 Partition 21 Flow path hole 30 Umbrella valve 31 Umbrella-shaped part 32 Expanded part 33 Shaft part 4 Intake chamber 4p Intake pipe 5 Pump chamber 5A Pump space 5B Diaphragm drive chamber 6 Exhaust chamber 6p Exhaust pipe 7 Diaphragm 8 Piston

Claims (9)

A rubber umbrella valve constituting a check valve device,
A tetraalkoxysilane represented by the formula (1): Si (OR ¹ ) ₄ (wherein R ¹ represents an alkyl group having 1 to 4 carbon atoms);
Equation ^{(2): Ti (OR 2} ) 4 ( wherein, R ² represents an alkyl group having 2 to 4 carbon atoms.) And tetraalkoxy titanium represented by the
Formula (3): Si (OR ³ ) _m R ⁴ _3-m — (CH ₂ ) _n —R ⁵ (wherein R ³ represents an alkyl group or an alkoxyalkyl group, R ⁴ represents an alkyl group, m Is an integer of 1 to 3, n is an integer of 0 to ^5. R ⁵ represents an organic functional group having reactivity with the polymer main chain of rubber. When,
An umbrella valve which is treated with a surface treatment agent containing a solvent for dissolving them.   The tetraalkoxysilane contained in the surface treatment agent is tetramethoxysilane or tetraethoxysilane, and the tetraalkoxytitanium is at least one selected from tetraethoxytitanium, tetraisopropoxytitanium and tetra-n-butoxytitanium. The umbrella valve according to claim 1 which is a seed.   The umbrella valve according to claim 1 or 2, wherein the surface treatment agent contains an acid or a base.   The umbrella valve according to claim 1, wherein the surface treatment agent contains tetraethoxysilane, tetraethoxytitanium or tetraisopropoxytitanium, a silane coupling agent, an acid or a base, and an organic solvent.   The umbrella valve | bulb in any one of Claim 1 thru | or 4 in which the said surface treating agent contains 1-10 mass% tetraalkoxy titanium with respect to content of tetraalkoxysilane.   The umbrella valve in any one of Claim 1 thru | or 4 in which the said surface treating agent contains 3-10 mass% tetraalkoxy titanium with respect to content of tetraalkoxysilane. A partition wall formed with a flow path hole communicating with a pump space whose volume is increased or decreased by a piston or a diaphragm, and an umbrella valve provided in the partition wall so as to close the flow path hole, the pressure of the pump space A check valve device for an air pump that opens and closes the flow path hole by deforming the umbrella valve according to
A check valve device for an air pump, wherein the umbrella valve is the umbrella valve according to any one of claims 1 to 6.   The check valve device for an air pump according to claim 7, which operates at a pressure of 50 KPa or less. A housing;
A partition that divides the interior of the housing into an intake chamber that communicates with the primary side, a pump chamber that includes a pump space whose volume is increased or decreased by a piston or a diaphragm, and an exhaust chamber that communicates with the secondary side;
A first check valve device comprising an umbrella valve provided in a partition wall separating the intake chamber and the pump chamber, and allowing only a gas flow from the intake chamber to the pump space;
A second check valve device that includes an umbrella valve provided in a partition that separates the pump chamber and the exhaust chamber, and that allows only a gas flow from the pump space to the exhaust chamber;
The air pump which is the umbrella valve in any one of Claims 1 thru | or 6 in which the umbrella valve which comprises a 1st check valve apparatus and a 2nd check valve apparatus is.

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