JP5436118B2 - Surface modification apparatus and surface modification method - Google Patents

Description

  The present invention relates to a surface modification apparatus and a surface modification method using the same. In particular, the present invention relates to a surface reforming apparatus including a plurality of vaporization chambers and having a small concentration change of a modifier compound contained in a fuel gas, and a surface reforming method using the same.

Surfaces of solid substances such as silicone rubber, fluororubber, and polyethylene resin are often hydrophobic and water repellent, and surface treatment such as adhesion of other members, printing, and ultraviolet coating is generally difficult.
Also, metal surfaces such as stainless steel and magnesium have insufficient adhesion and surface smoothness among metals, and the coating film peels off easily when UV curable paints are applied directly. The problem of end.
In addition, attempts have been made to disperse inorganic particles such as titanium oxide and zirconium oxide as a photocatalyst in a polymer material, but these inorganic particles have poor dispersibility and are not easy to handle. It is done.

Thus, in order to solve these problems, a surface modification method for a solid substance using a predetermined surface modification apparatus has been disclosed (for example, see Patent Document 1).
More specifically, as shown in FIG. 9, by spraying a fuel gas flame 234 containing a modifier compound 214 having a specific boiling point onto the solid substance 250 (silicic acid flame treatment or the like), Even when a relatively large amount of a modifier compound containing a silicon-containing compound or the like is used, even if it is easy to burn and the oxidization flame treatment step is omitted, the surface modification to the solid substance 250 is performed. Disclosed is a method for modifying the surface of a solid material that can be carried out uniformly and sufficiently.

Also disclosed is a surface reformer in which the temperature of the storage chamber and the temperature of the vaporization chamber are defined so as to satisfy a predetermined relational expression in order to solve the temperature change of the vaporization chamber due to the supplied modifier compound. (For example, refer to Patent Document 2).
More specifically, when the temperature of the vaporizing chamber is T1 (° C.) and the temperature of the storage chamber is T2 (° C.), the T1 and T2 are controlled so as to satisfy the following temperature relational expression (1). More preferably, a surface reforming apparatus is disclosed in which the temperature (T1) of the vaporizing chamber and the temperature (T2) of the storage chamber are values within a range of less than 10 to 40 ° C.
T2-15 ° C. ≦ T1 ≦ T2 + 15 ° C. (1)

WO03 / 069017 (Claims) JP 2008-50629 A (Claims)

However, in the case of the surface modification method for a solid substance disclosed in Patent Document 1, when the modifier compound 214 is additionally mixed from the storage chamber, the modifier compound 214 stored in the storage chamber is generally mixed. Since the temperature is not controlled, there is a problem that the temperature of the vaporization chamber 212 is easily changed as shown by a line B in FIG.
As a result, the evaporation state in the vaporization chamber 212 becomes unstable, the concentration of the modifier compound contained in the fuel gas becomes unstable, and as a result, the surface of the solid substance can be stably reformed. There was a problem of difficulty.

Moreover, since the surface modification apparatus described in Patent Document 2 must always be controlled not only to the temperature of the vaporization chamber but also to the temperature of the storage chamber, the structure of the apparatus tends to be complex and easy to maintain. There was a problem that was not.
In addition, when a modifier compound is additionally mixed from the storage chamber to the vaporization chamber, or when the environmental temperature changes greatly, a temperature change occurs in the vaporization chamber. There was also a problem that the evaporation state of the sample was easily changed.

Therefore, as a result of intensive studies, the present inventor has provided a plurality of vaporization chambers, and even while supplying a modifier compound to one vaporization chamber, a different vaporization chamber is used to obtain a predetermined value. The present inventors have found that the silicic acid flame treatment can be carried out continuously and have completed the present invention.
That is, the present invention eliminates the effects of temperature changes and concentration changes in the vaporization section, and consequently, there is little change in the concentration of the modifier compound contained in the fuel gas, and the surface of the solid substance is modified stably and continuously. It is an object of the present invention to provide a surface modifying apparatus capable of improving the quality and a surface modifying method using the same.

According to the present invention, the modifier compound has a vaporization section having a plurality of vaporization chambers, and even when the surface modification is performed while supplying the modifier compound to the vaporization section. Is a surface reforming apparatus that separates a vaporization chamber supplied with a vaporization chamber used for surface reforming and suppresses a change in concentration of the modifier compound contained in the fuel gas,
A storage chamber for storing a silicon-containing compound as a modifier compound;
A vaporizer for supplying a modifier compound from the storage chamber and evaporating at a predetermined temperature to produce a gaseous modifier compound,
A transfer unit for introducing air as a carrier gas into the vaporization unit and transferring the gaseous modifier compound as a part of the fuel gas to the injection unit;
An injection unit for blowing a flame derived from a fuel gas containing a modifier compound;
Contains
As a plurality of vaporization chambers, a plurality of vaporization chambers including at least a first vaporization chamber and a second vaporization chamber are provided, and a switching device for alternately using the first vaporization chamber and the second vaporization chamber is provided. ,
There is provided a surface reforming apparatus characterized in that the carrier gas introduction port in the first vaporization chamber and the second vaporization chamber is provided in an eccentric position with respect to the central axis of the vaporization chamber. Can be solved.
In other words, since the surface reforming apparatus of the present invention includes a plurality of vaporization chambers, a predetermined temperature is supplied while supplying a modifier compound to either the first vaporization chamber or the second vaporization chamber. A predetermined silicic acid flame treatment can be continuously performed in cooperation with the transfer unit and the injection unit while operating the other vaporization chamber.
Therefore, even when the modifier compound is supplied to the vaporization section while performing the predetermined silicic acid flame treatment, the temperature change and concentration change in the vaporization section are compared with the case where there is only one vaporization chamber. Thus, the concentration change of the modifier compound contained in the fuel gas is small, and the surface of the solid substance can be stably and continuously reformed.

In addition, the carrier gas is supplied in a cyclone shape by configuring the carrier gas introduction port in the first vaporization chamber and the second vaporization chamber to be in an eccentric position with respect to the central axis of the vaporization chamber. Therefore, the modifier compound can be further uniformly mixed, and the predetermined evaporation state can be more stably maintained even during the introduction of the carrier gas.

Further, in configuring the surface reforming apparatus of the present invention, it is preferable that the volume per one in the first vaporization chamber and the second vaporization chamber is set to a value within the range of 10 to 200 cm ³ .
By comprising in this way, the temperature of any vaporization chamber supplied with the modifier compound can be adjusted to a predetermined temperature in a short time, and the predetermined evaporation state can be recovered quickly and stably. Can do.
In addition, when configured in this manner, the surface area of the modifier compound exposed to the air is relatively narrowed in the vaporization chamber, for example, a value within the range of 0.1 to 10 cm ² can be modified. The consumption of the agent compound can be controlled to be small.
Note that the volume of the vaporizing chamber in the conventional surface reforming apparatus is usually 1500 cm ³ or more, and the surface area of the modifier compound exposed to air is relatively large, usually 30 cm ² or more. It has been found.

Further, in configuring the surface modification apparatus of the present invention, it is preferable that the supply port of the modifier compound from the storage chamber is provided at the bottom of the first vaporization chamber and the second vaporization chamber.
By configuring in this way, it is possible to suppress the undulation of the liquid level that occurs when the modifier compound is dropped from above the vaporization chamber, so that the predetermined evaporation state can be quickly recovered.

In configuring the surface modification apparatus of the present invention, it is preferable that the first vaporization chamber and the second vaporization chamber have a columnar shape or a prismatic shape.
By comprising in this way, carrier gas and modifier compound can be mixed more stably using the space of a length direction, As a result, a predetermined evaporation state is stably Can be maintained.
In addition, by configuring the vaporization chamber in this way, in the case of a cyclonic carrier gas, it is easy to rise smoothly along the wall, and the modifier compound can be mixed more uniformly.

In constructing the surface reforming apparatus of the present invention, the first vaporizing chamber is the main vaporizing chamber, and is always operating except when the modifier compound is replenished. However, it is preferable that the preliminary vaporization chamber operates only when the first vaporization chamber is replenished with the modifier compound.
By comprising in this way, the aspect of a 1st vaporization chamber and a 2nd vaporization chamber can be changed, As a result, expensive sensors (pressure sensor) from the 2nd vaporization chamber of a preliminary vaporization chamber Or the liquid level sensor) can be omitted, or the constituent materials can be made relatively inexpensive and lightweight.

Further, another aspect of the present invention has a vaporization section including a plurality of vaporization chambers, and supplies a modifier compound to one vaporization chamber, while supplying a carrier to another vaporization chamber. A surface reforming method using a surface reforming apparatus that introduces gas to generate a modifier compound in a gaseous state and suppresses a concentration change of the modifier compound contained in the fuel gas,
Surface modification equipment
A storage chamber for storing a silicon-containing compound as a modifier compound;
A vaporizing unit for supplying the modifier compound from the storage chamber and evaporating at a predetermined temperature to generate a modifier compound in a gaseous state;
A transfer unit for introducing air as a carrier gas into the vaporization unit and transferring the gaseous modifier compound as a part of the fuel gas to the injection unit;
And an injection part for blowing a flame derived from the fuel gas containing the modifier compound,
In the surface reforming method, the vaporization section includes a plurality of vaporization chambers including at least a first vaporization chamber and a second vaporization chamber, and uses a surface modification device including a switching device for alternately using the vaporization chamber. There,
It is a surface modification method characterized by including the process of implementing the following process (a) and (b) simultaneously.
(A) A step of supplying a modifier compound from the storage chamber to either the first vaporization chamber or the second vaporization chamber.
(B) Of the first vaporization chamber and the second vaporization chamber, carrier gas is supplied to the vaporization chamber different from the vaporization chamber in which the step (a) is performed, with respect to the central axis of the vaporization chamber. A step of transferring a vaporized modifier compound while introducing it in a cyclone form from an eccentric position , and injecting a flame derived from a fuel gas containing the vaporized modifier compound to an object to be processed in an injection unit. .
That is, in the surface modification method of the present invention, since the surface modification apparatus having a plurality of vaporization chambers is used, even if the step (a) and the step (b) are performed simultaneously. Compared with the case where there is only one vaporization chamber, the influence of temperature change and concentration change in the vaporization section is eliminated, and consequently the concentration change of the modifier compound contained in the fuel gas is small and stable and continuous. The surface of the solid material can be modified.
In the vaporization chamber in which the step (b) is performed by introducing the carrier gas into the vaporization chamber in a cyclone shape from an eccentric position with respect to the central axis of the vaporization chamber in the step (b). Since the carrier gas and the modifier compound can be more reliably and uniformly mixed, the predetermined evaporation state can be stably maintained.

In carrying out the surface modification method of the present invention, each of the first vaporization chamber and the second vaporization chamber is provided with a liquid level gauge, and it is detected that the modifier compound has a liquid level below a predetermined standard. It is preferable to perform the step (a) in the vaporized chamber.
By carrying out in this way, alternate use of the respective vaporization chambers in which the step (a) and the step (b) are carried out can be performed more reliably.

In carrying out the surface modification method of the present invention, in the step (a), it is preferable to set the temperature of the vaporizing chamber to a value within the range of 40 to 80 ° C.
By carrying out in this way, the predetermined evaporation state for carrying out the step (b) can be easily recovered.

FIGS. 1A to 1B are diagrams for explaining an outline of a surface modification apparatus and a surface modification method using the same according to the present invention. FIG. 2 is a diagram provided to explain the relationship between the volume of the vaporization chamber and the supply stability of the modifier compound. Drawing 3 is a figure offered in order to explain a vaporization part provided with a plurality of vaporization chambers. FIGS. 4A and 4B are diagrams for explaining the state of introduction of the carrier gas in the cyclone type vaporization chamber. FIGS. 5A and 5B are diagrams for explaining the prism sensor. FIGS. 6A and 6B are diagrams for explaining the micropump. FIG. 7 is a diagram for explaining the IR sensor. FIGS. 8A to 8B are views for explaining the state of introduction of the carrier gas in the non-cyclone type vaporization chamber. FIG. 9 is a diagram for explaining the structure of a conventional surface modification apparatus. FIG. 10 is a diagram for explaining the temperature change of the vaporization chamber in the conventional surface reforming apparatus.

[First Embodiment]
As shown in FIGS. 1A to 1B, the first embodiment includes a storage chamber 21 for storing a silicon-containing compound as the modifier compound 23, and a modifier compound from the storage chamber 21. 23 is supplied to the vaporizer 11 (11a, 11b) and the vaporizer 11 (11a, 11b) for evaporating at a predetermined temperature to generate a modifier compound 23 'in a gaseous state. The gas 41 was introduced and derived from the fuel gas containing the modifier compound 23 'and the transfer unit 30 for transferring the gas modifier compound 23' to the injection unit 50 as part of the fuel gas. A surface reforming apparatus 10 including an injection unit 50 for spraying a flame 51, wherein the vaporization unit 11 includes a plurality of vaporization chambers including at least a first vaporization chamber 11a and a second vaporization chamber 11b. The first vaporization chamber 11a and the first Switching device 60 for alternating use vaporization chamber 11b of the (60a, 60b, 60c, 60d, 60e, 60f) is a surface modification apparatus 10, characterized in that it comprises a.
More specifically, even if it has a vaporization section having a plurality of vaporization chambers and surface modification is carried out while supplying the modifier compound to the vaporization section, the modifier compound Is a surface reforming apparatus that separates a vaporization chamber supplied with a vaporization chamber used for surface reforming and suppresses a change in concentration of the modifier compound contained in the fuel gas, A storage chamber for storing a silicon-containing compound as a modifier compound, and a modifier compound are supplied from the storage chamber and evaporated at a predetermined temperature to generate a gaseous modifier compound A vaporizing section, a transfer section for introducing air as a carrier gas into the vaporizing section, and transporting the gaseous modifier compound as a part of the fuel gas to the injection section, and a modifier compound An injection unit for blowing a flame derived from a fuel gas containing And a switching device for providing a plurality of vaporization chambers including at least a first vaporization chamber and a second vaporization chamber as the plurality of vaporization chambers, and alternately using the first vaporization chamber and the second vaporization chamber. And a carrier gas inlet in the first vaporization chamber and the second vaporization chamber is provided at an eccentric position with respect to the central axis of the vaporization chamber.
Hereinafter, the surface modification apparatus as the first embodiment will be specifically described for each component.

1. Basic Configuration As shown in FIGS. 1A to 1B, the surface modification apparatus 10 of the present invention includes a storage chamber 21 that stores a specific modifier compound 23, at least a first vaporization chamber 11a, and Switching for alternately using the vaporization unit 11 including a plurality of vaporization chambers including the second vaporization chamber 11b, the transfer unit 30, the injection unit 50, and the first vaporization chamber 11a and the second vaporization chamber 11b. The apparatus 60 is basically included.
Here, in the surface modification device 10 of the present invention, as shown in FIG. 1A, when the modifier compound 23 is supplied to the first vaporization chamber 11a, the switching device 60a, It is possible to operate 60b, 60c, 60d, 60e, 60f to introduce the carrier gas 41 into the second vaporization chamber 11b, which is another vaporization chamber, and to carry out silicic acid flame treatment in the injection unit 50. it can.
Conversely, for example, as shown in FIG. 1B, when the modifier compound 23 is supplied to the second vaporization chamber 11b, the switching devices 60a, 60b, 60c, 60d, 60e, 60f is operated to introduce the carrier gas 41 into the first vaporization chamber 11a, which is another vaporization chamber, and the silicic acid flame treatment can be performed in the injection unit 50.
Therefore, in the surface modification device of the present invention, even when the surface modification is performed while supplying the modifier compound to the vaporization section, the vaporization chamber in which the modifier compound is supplied Since the vaporization chamber used for the surface modification is separate, the concentration change of the modifier compound contained in the fuel gas is reduced and the surface of the solid substance is stably modified. Can do.
The selective supply or introduction of the modifier compound or carrier gas to the plurality of vaporization chambers as the operation of the switching device can be appropriately performed using a solenoid valve, a cock, etc. It may be manual or computer controlled.
Further, as shown in FIGS. 1A to 1B, one injection unit is basically sufficient, but when a different modifier compound is used for each of a plurality of vaporization chambers, surface modification may be performed. For example, when it is desired to remove the silicon-containing compound deposited on the injection unit while performing the above, a plurality of injection units may be provided for each of the plurality of vaporization chambers.

2. Vaporization unit (1) Vaporization chamber The vaporization unit 11 of the present invention includes a plurality of vaporization chambers including at least a first vaporization chamber 11a and a second vaporization chamber 11b, and a switching device 60 ( 60a, 60b, 60c, 60d, 60e, 60f).
This is because the first vaporization chamber and the second vaporization chamber can be alternately used by providing a plurality of vaporization chambers in this way.
More specifically, as the alternate use of the first vaporization chamber 11a and the second vaporization chamber 11b, a predetermined amount of modifier compound is applied to the second vaporization chamber while operating the first vaporization chamber. Alternatively, the second vaporization chamber can be operated while supplying a predetermined amount of the modifier compound to the first vaporization chamber.
Therefore, the influence of temperature change, concentration change, etc. in the vaporization chamber when supplying a predetermined amount of the modifier compound can be substantially eliminated.
In addition, even if a failure occurs in either the first vaporization chamber 11a or the second vaporization chamber 11b, the vaporization chamber can be repaired without interrupting the predetermined surface modification treatment operation. Exchanges can be made.
In addition, the modifier compound accommodated in the vaporization chamber will be described in detail in the second embodiment.

Further, as an alternate use of the first vaporization chamber 11a and the second vaporization chamber 11b, the spare is only used when a malfunction occurs in the first vaporization chamber while operating the first vaporization chamber as the main vaporization chamber. It is also possible to switch to a typical second vaporization chamber.
Therefore, even if a problem occurs in a part of the surface modification apparatus 10, the predetermined surface modification treatment operation can be performed continuously without interruption.

Further, as alternate use of the first vaporization chamber 11a and the second vaporization chamber 11b, different surface modifiers are respectively accommodated, and depending on the type and mode of the solid substance to be surface-modified, either A silicic acid flame treatment using a surface modifier can also be performed.
Therefore, in the first stage, for example, a silicic acid flame treatment based on a surface modifier having a relatively low boiling point is performed using the first vaporization chamber 11a, and in the second stage, the second vaporization is performed. By utilizing the chamber 11b, for example, a silicic acid flame treatment based on a surface modifier having a relatively high boiling point can be performed, so that a surface treatment with an excellent surface modification effect can be obtained as a whole.

(2) Volume of vaporization chamber Moreover, it is preferable that at least one volume of the 1st vaporization chamber and the 2nd vaporization chamber shall be a value within the range of 10-200 cm < ³ >, respectively.
The reason for this is that by setting the volume of the vaporizing chamber in such a range, the temperature of the vaporizing chamber to which the modifier compound is supplied can be adjusted to a predetermined temperature in a short time, and a predetermined evaporation state can be easily achieved. This is because it can be recovered.
In addition, with such a volume, the evaporation area of the modifier compound becomes relatively small, so that it becomes easier to maintain a predetermined evaporation state and increase the accuracy of the mixing ratio with the carrier gas. it can.
More specifically, when the volume of the vaporization chamber becomes a value less than 10 cm ³ , the reduction of the modifier compound,
This is because, due to the influence of the introduced carrier gas, not only the fluctuation of the liquid level becomes excessively strong, but also the capacity of the modifier compound is lowered and the supply frequency is excessively increased.
Further, when the volume of the vaporizing chamber is less than 10 cm ³ , the evaporation area of the modifier compound becomes excessively small, the accuracy of the mixing ratio with the carrier gas is reduced, and the predetermined evaporation state is stably maintained. This is because it may be difficult to maintain.
On the other hand, when the volume of the vaporization chamber exceeds 200 cm ³ , it becomes difficult to recover the temperature of the vaporization chamber supplied with the modifier compound to a predetermined temperature in a short time, or the modifier compound. This is because the evaporation area becomes excessively large and the accuracy of the mixing ratio with the carrier gas may decrease.
Accordingly, the volume of the vaporization chamber, it is more preferably set to a value within the range of 12～100Cm ^3, still more preferably a value within the range of 15~80cm ^3.

Next, the relationship between the volume of the vaporization chamber and the supply stability of the modifier compound will be described with reference to FIG.
That is, FIG. 2 shows characteristic curves A to C in which the horizontal axis represents the carrier gas flow rate (L / min) and the vertical axis represents the modifier compound consumption (mL / hour).
Here, characteristic curves A to C are characteristic curves when the volume of the vaporizing chamber is 20, 100, and 500 cm ³ (evaporation area: 2, 10, and 50 cm ^2, respectively).

As understood from the characteristic curves A to C, as the volume of the vaporization chamber increases, the carrier gas flow rate and the consumption amount of the modifier compound show a correlation close to a direct proportion.
On the other hand, it can be seen that the smaller the volume of the vaporization chamber, the smaller the increase in the consumption amount of the modifier compound accompanying the increase in the flow rate of the carrier gas, and the lower the characteristic curve.
Therefore, from the characteristic curves A to C, by reducing the volume of the vaporizing chamber relatively, even if the flow rate of the carrier gas varies, for example, surface modification such as 8 to 15 mL / hour is performed. It can be understood that it is easy to stably maintain the consumption amount of the modifier compound which is not excessive or insufficient in carrying out the above.

(3) Supply port of modifier compound Further, as shown in FIG. 3, supply ports 12a and 12b of the modifier compound from the storage chamber 21 are provided at the bottoms of the plurality of vaporization chambers 11a and 11b, respectively. It is preferable.
The reason for this is that, by configuring in this way, the liquid level undulation can be suppressed and the modifier compound remaining in the vaporization chamber as compared with the case where the modifier compound is dropped from above the vaporization chamber. It is because it can mix rapidly and uniformly between.
Therefore, even when the volume of the vaporizing chamber and the evaporation area of the modifier compound are relatively small, the predetermined evaporation state can be quickly recovered.

(4) Shape of vaporization chamber Moreover, it is preferable that at least one of a plurality of vaporization chambers is cylindrical (cylinder shape) or prismatic shape.
This is because the carrier gas and the modifier compound can be mixed more reliably and stably by making the vaporizing chamber into such a shape.
Moreover, by setting it as such a shape, it becomes easy to produce | generate a cyclonic carrier gas and it can make the mixability between carrier gas and a modifier compound still more favorable.
Therefore, even during the introduction of the carrier gas, the predetermined evaporation state can be stably maintained.
That is, if at least one of the plurality of vaporization chambers has a predetermined shape, the introduced carrier gas is likely to generate an airflow in the direction along the inner wall, and the carrier gas and the modifier compound are This is because they can be mixed more stably.

In addition, when a vaporization chamber is cylindrical (cylinder shape), it is preferable to make the diameter into the value within the range of 0.5-5 cm, and it is more preferable to set it as the value within the range of 1-4 cm. More preferably, the value is in the range of 5 to 3 cm.
Moreover, when a vaporization chamber is cylindrical shape, it is preferable to make the height into the value within the range of 3-30 cm, It is more preferable to set it as the value within the range of 5-20 cm, It exists within the range of 8-15 cm. More preferably, it is a value.
On the other hand, when the vaporizing chamber is prismatic, one side of the cross section is preferably set to a value in the range of 0.5 to 5 cm, more preferably set to a value in the range of 1 to 4 cm, More preferably, the value is within a range of 3 cm.
Moreover, when a vaporization chamber is prismatic shape, it is preferable to make the height into the value within the range of 3-30 cm, It is more preferable to set it as the value within the range of 5-20 cm, It exists within the range of 8-15 cm. More preferably, it is a value.

(5) Carrier Gas Inlet As shown in FIG. 4, the carrier gas inlet 13 in at least one of the plurality of vaporization chambers 11a and 11b is eccentric with respect to the central axis 14 of the vaporization chamber. It is preferable to be provided at the position.
That is, for example, when assuming the central axis of a columnar or prismatic vaporization chamber, the carrier gas is not introduced toward the central axis, but the introduction direction of the carrier gas does not coincide with the central axis, so-called It is preferable to introduce a cyclonic carrier gas toward the eccentric position.
The reason for this is that by providing the carrier gas supply port at such a position, the carrier gas can be supplied in a cyclone form, so that even during the introduction of the carrier gas, the predetermined evaporation state is more stable. This is because it can be maintained.
Therefore, the carrier gas and the modifier compound can be more stably mixed by supplying the carrier gas in a cyclone form.

(6) Level gauge Further, it is preferable to provide a level gauge for measuring the level of the modifier compound in each of the plurality of vaporization chambers.
Examples of such a level gauge include a capacitance type level gauge, a flow type level gauge, an ultrasonic level gauge, a pressure type level gauge, a prism sensor (prism type level gauge), and the like.
However, it is preferable to use the prism sensor 15 as shown in FIGS. 5A and 5B because it is easy to reduce the size and weight of the facility.
As shown in FIG. 5B, the prism sensor 15 is basically composed of a light emitting element 15a and a light receiving element 15b, and is preferably composed of a rust preventive material such as stainless steel.
Further, the location where the sensor is provided is preferably an external location 16 communicating with the vaporizing chamber 11 as shown in FIG.
The reason for this is that the outer peripheral surface of the vaporization chamber is often covered with a heater, heat insulating material, etc., so providing a liquid level gauge that penetrates the outer peripheral surface of the vaporization chamber hinders temperature regulation of the vaporization chamber It is because there is a case to do.

(7) Liquid feed pump Moreover, it is preferable that a some vaporization chamber is equipped with the liquid feed pump used when circulating a modifier compound from a transfer part to a vaporization chamber.
For example, a gear pump, a vortex pump, a vortex turbine pump, etc. are mentioned as a liquid feeding pump, However It is preferable to provide the micro pump 17 especially as shown to Fig.6 (a).
This is because such a micropump 17 can finely adjust the amount of the modifier compound from the transfer path to the vaporization chamber and transfer it.
As shown in FIG. 6B, the micropump 17 basically moves the modifier compound contained in the cylinder 17b by a piston 17a that moves at a constant speed and moves in a predetermined direction. It is configured so that it can be fed in a small amount and at a constant speed.
Furthermore, as shown in FIG. 3, it is also preferable to provide a temperature sensor 18 (18a, 18b) in the vaporizing chamber.

(8) Temperature adjusting device Moreover, it is preferable that the plurality of vaporizing chambers include a thermostat or a heater for adjusting the temperature in the vaporizing chambers.
As shown in FIG. 3, the thermostat and the heater 19 (19 a, 19 b) may be provided on the outer peripheral surface of the vaporizing chamber 11 or inside the vaporizing chamber 11.
As the types of thermostats and heaters, sheath heaters, throwing heaters, fin heaters, cartridge heaters, super flat heaters, cast heaters, micro heaters, IH heaters, and the like are preferably used.
In addition, it is also preferable to cover the outer peripheral surface of the vaporizing chamber with a heat insulating material to reduce the influence of environmental temperature.

3. Storage Chamber As shown in FIGS. 1A to 1B, the storage chamber 21 supplies the modifier compound 23 to the vaporization chambers 11a and 11b, respectively. It is a member for storing 23.
The storage chamber 21 is basically connected to the vaporization chambers 11a and 11b by a pipe structure 70 so that the supply of the modifier compound 23 can be controlled by the electromagnetic valves 60a to 60f. For example, the configuration is not particularly limited, but as shown in FIG. 3, it is preferable to provide a modifier compound replenishment port 25, a residual pressure release 24, a liquid level gauge 22, and the like.

4). Transfer Unit As shown in FIGS. 1A to 1B, the transfer unit 30 includes a gaseous modifier compound 23 ′ transferred from any of the vaporization chambers 11a and 11b, and a compressed air source. This is a member for uniformly mixing the air 42 supplied from the fuel and the hydrocarbon gas 43 supplied from the hydrocarbon gas source into a fuel gas and transferring it to the injection unit 50.
Accordingly, in order to control the flow rate, the mixer 31a, 31b, which is a mixing chamber for mixing the gaseous modifier compound with the air transferred from the compressed air source to form fuel gas, is provided. It is preferable to have a tube structure equipped with a solenoid valve, a flow meter, or a pressure gauge for controlling the pressure of the fuel gas.

Further, in order to measure the concentration of the modifier compound in the fuel gas transferred to the injection unit, it is preferable to provide a gas concentration meter, and as shown in FIG. 7, an IR sensor 52 using infrared rays and It is preferable to include a control unit 52a including such a monitor.
This is because the concentration of the modifier compound in the fuel gas can be measured using the data signal from the IR sensor even in a non-contact manner, and then the concentration of the modifier compound is adjusted. This is because the amount of fuel gas supplied to the injection unit can be controlled. Therefore, the concentration of the modifier compound in the fuel gas can be finely and quickly adjusted based on the signal from the IR sensor.
More specifically, infrared rays are irradiated in a predetermined wavelength region, the height of the infrared absorption peak attributed to the modifier compound in the fuel gas is measured, and a calibration curve (reformer prepared in advance) is measured. The concentration of the modifier compound in the fuel gas can be calculated in light of the concentration of the compound and the height of the predetermined wavelength peak.

5. As shown in FIGS. 1A to 1B, the injection unit 50 burns the fuel gas sent through the transfer unit 30, and the obtained flame 51 is treated with the object 80. It is a member provided with a burner for spraying a certain solid substance.
The type of the burner is not particularly limited, and may be any of a premix burner, a diffusion burner, a partial premix burner, a spray burner, an evaporation burner, a pulverized coal burner, and the like.
Also, the form of the burner is not particularly limited. For example, as shown in FIGS. 1 (a) to (b), it expands toward the tip, and even if it has a fan-shaped configuration as a whole, It may be a rectangle or the like.

[Second Embodiment]
As shown in FIGS. 1A to 1B, the second embodiment is a surface modification method using the surface modification apparatus as the first embodiment, and includes the following steps (a) and It is a surface modification method characterized by including the process of implementing (b) simultaneously.
(A) A step of supplying a modifier compound from the storage chamber to any one of the plurality of vaporization chambers.
(B) Of the plurality of vaporization chambers, the carrier gas is made cyclonic from an eccentric position with respect to the central axis of the vaporization chamber with respect to a vaporization chamber different from the vaporization chamber in which the step (a) is performed. A step of injecting a flame derived from a fuel gas containing a vaporized modifier compound while being introduced to an object to be processed.
Hereinafter, the surface modification method according to the second embodiment will be specifically described while omitting the points overlapping with those of the first embodiment.

1. Step (a)
Step (a) is a step of supplying a modifier compound from a storage chamber to any of the vaporization chambers.

(1) Vaporization chamber The vaporization chamber used in step (a) requires a new supply of the modifier compound because the amount of the modifier compound in the vaporization chamber decreases due to the surface modification. It is a state vaporization chamber.
For example, this corresponds to the first vaporization chamber 11a in FIG. 1A or the second vaporization chamber 11b in FIG.
In addition, implementation of the surface modification while one of the vaporization chambers is supplied with the modifier compound is performed by another vaporization chamber as step (b) described later.
Therefore, according to the present invention, even when the supply of the modifier compound and the surface modification are performed simultaneously, the concentration change of the modifier compound contained in the fuel gas is small and stable. The surface of the solid material can be modified.

In addition, as shown in FIG. 3, in the vaporization chambers in which the plurality of vaporization chambers 11a and 11b are respectively provided with liquid level gauges 15a and 15b, and the modifier compound is detected to have a liquid level below a predetermined standard, It is preferable to carry out step (a).
This is because the vaporization chambers in which the step (a) and the step (b) are performed can be exchanged more reliably by carrying out in this way.
The supply standard of the modifier compound is not particularly limited, but generally, it may be before the volume of the modifier compound (liquid) is reduced to 1/10 or less of the volume of the vaporization chamber. preferable.

Further, in practicing the step (a), the final temperature of the vaporization chamber, it is preferably set to a value within the range of 40 to 80 ° C..
This is because the predetermined evaporation state for carrying out the step (b) can be easily recovered by setting the final vaporization chamber temperature within such a range.
That is, when the final vaporization chamber temperature is less than 40 ° C., depending on the boiling point of the modifier compound, it may be difficult to supply a sufficient amount of the modifier compound in the fuel gas. Because there is. On the other hand, when the final temperature of the vaporization chamber exceeds 80 ° C., the time until the evaporation state in which the step (b) can be carried out after the supply of the modifier compound to the vaporization chamber is excessively long becomes excessive. This is because it may be difficult to simultaneously perform the step (a) and the step (b).
Therefore, when performing the step (a), it is preferable to set the final vaporization chamber temperature to a value within the range of 40 to 70 ° C, and further to set the value within the range of 45 to 60 ° C. preferable.
Needless to say, the final temperature of the vaporization chamber when performing the step (a) is also the temperature of the vaporization chamber when performing the next step (b).

(2) Modifier Compound (2) -1 Boiling Point Further, the boiling point (under atmospheric pressure) of the modifier compound is preferably set to a value within the range of 10 to 200 ° C.
The reason for this is that when the boiling point of such a modifier compound is less than 10 ° C., the volatility is so strong that it may be difficult to handle.
On the other hand, when the boiling point of such a modifier compound exceeds 200 ° C., the miscibility with the air flow decreases, the surface modification of the solid substance becomes non-uniform, or the modification effect is sustained over a long period of time. This may be difficult.
Therefore, the boiling point of the modifier compound is more preferably set to a value within the range of 15 to 180 ° C, and further preferably set to a value within the range of 20 to 120 ° C.
The boiling point of the modifier compound can also be adjusted by limiting the structure of the modifier compound itself, but other than this, an azeotropic phenomenon is utilized to obtain an alkylsilane compound having a relatively low boiling point, etc. And an alkoxylane compound having a relatively high boiling point or the like can be used as appropriate.

Alternatively, together with the modifier compound described below, an alcohol compound such as methanol,
It is also preferable to add ethanol, propanol, butanol, amino alcohol, benzyl alcohol, glycol or the like.
The reason for this is that by adding such an alcohol compound, the boiling point of the modifier compound can be adjusted, and since it is easier to evaporate than the modifier compound, surface modification can be stably performed. Because it can be done.
In addition, by adding such an alcohol compound, it is possible to visually confirm that the modifier compound is sprayed on the surface of the solid substance by the flame reaction.
In addition, when adding an alcohol compound to the modifier compound mentioned later, it is preferable to make an alcohol compound into the value within the range of 1-80 weight part with respect to 100 weight part of modifier compounds, and 5-50 weight The value is more preferably in the range of parts by weight, and more preferably in the range of 8 to 30 parts by weight.

(2) -2 types In addition, a silicon-containing compound is used as the modifier compound.
The reason for this is that if it is a silicon-containing compound, the miscibility with the carrier gas is improved, and the hydroxyl group tends to appear on the surface, so that the predetermined silica particles having a large number of hydroxyl groups on the surface of the solid substance can be made uniform. This is because it can be formed and the surface of the solid substance can be effectively modified.
Examples of such silicon-containing compounds include alkylsilane compounds and alkoxysilane compounds.
Of these compounds, alkylsilane compounds are generally preferred modifier compounds because they generally have a low boiling point and can be easily vaporized by heating and uniformly mixed with air or the like.
Preferred examples of such alkylsilane compounds include tetramethylsilane, tetraethylsilane, dimethyldichlorosilane, dimethyldiphenylsilane, diethyldichlorosilane, diethyldiphenylsilane, methyltrichlorosilane, methyltriphenylsilane, dimethyldiethylsilane, tetramethoxy. Silane, tetraethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, trichloromethoxysilane, trichloroethoxysilane, triphenylmethoxysilane , Triphenylethoxysilane and the like alone or in combination of two or more.

The silicon-containing compound is more preferably a compound having at least one of a nitrogen atom, a halogen atom, a vinyl group, and an amino group in the molecule or at the molecular end, or a compound having a siloxane bond in the molecule.
More specifically, hexamethyldisilazane (boiling point: 126 ° C), vinyltrimethoxysilane (boiling point: 123 ° C), vinyltriethoxysilane (boiling point: 161 ° C), trifluoropropyltrimethoxysilane (boiling point: 144 ° C). ), Trifluoropropyltrichlorosilane (boiling point: 113 to 114 ° C), 3-aminopropyltrimethoxysilane (boiling point: 215 ° C), 3-aminopropyltriethoxysilane (boiling point: 217 ° C), hexamethyldisiloxane (boiling point) : 100 to 101 ° C.) and at least one compound of 3-chloropropyltrimethoxysilane (boiling point: 196 ° C.).
The reason for this is that such a silicon-containing compound improves the miscibility with the carrier gas, makes it easier for hydroxyl groups to appear on the surface, and a predetermined silica having many hydroxyl groups on the surface of the solid substance. This is because the particles can be formed more uniformly.
In addition, since the silicon-containing compound is likely to partially remain on the surface of the solid substance due to the boiling point in these compounds, the solid substance and the coating film made of various ultraviolet curable resins, etc. This is because an excellent adhesion can be obtained.

(2) -3 Average molecular weight Moreover, it is preferable to make the average molecular weight of a modifier compound into the value within the range of 50-1,000 in a mass-spectrum measurement.
This is because when the average molecular weight of the modifier compound is less than 50, the volatility is high and handling may be difficult. On the other hand, if the average molecular weight of the modifier compound exceeds 1,000, it may be difficult to easily mix with air or the like by being vaporized by heating.
Therefore, the average molecular weight of the modifier compound is more preferably set to a value within the range of 60 to 500, and further preferably set to a value within the range of 70 to 200 in the mass spectrum measurement.

(2) -4 Density The density of the modifier compound in the liquid state is preferably set to a value in the range of 0.3 to 0.9 g / cm ³ .
This is because when the density of the modifier compound is less than 0.3 g / cm ³ , handling may be difficult. On the other hand, if the density of the modifier compound exceeds 0.9 g / cm ³ , vaporization may be difficult.
Therefore, it is more preferable to set the density of the modifying compound a value within the range of 0.4 to 0.8 g / cm ^3, a value within a range of 0.5~0.7g / cm ³ Further preferred.

2. Step (b)
In the step (b), the carrier gas is introduced into a vaporization chamber different from the vaporization chamber in which the step (a) is performed among the plurality of vaporization chambers, and the fuel containing the vaporized modifier compound This is a step of injecting a flame derived from gas to an object to be processed.

(1) Introduction of carrier gas (1) -1 Vaporization chamber The vaporization chamber provided for the step (b) is a vaporization chamber different from the vaporization chamber in which the step (a) is performed. The vaporizing chamber is already in a state where the modifier compound is sufficiently supplied.
For example, it corresponds to the second vaporization chamber 11b in FIG. 1A or the first vaporization chamber 11a in FIG.
Therefore, in the present invention, while the step (b), that is, the surface modification is performed in any of the vaporization chambers, the surface modification is performed first, and the modifier compound is reduced. A new modifier compound is supplied to another vaporization chamber and is ready for the next surface modification.

(1) -2 Carrier gas In addition, as shown in FIGS. 1A to 1B, the introduction of the carrier gas into the vaporizing chamber in the step (b) is performed by connecting the carrier gas 41 supplied from the carrier gas source to the tube. This is done by direct introduction by structure 71.
Thereby, in the vaporization chambers 11a and 11b, the modifier compound 23 'vaporized at a predetermined temperature and the carrier gas 41 are transferred to the transfer unit 30 while being mixed.
The type of carrier gas is not particularly limited, but air is preferable because it is inexpensive and has high safety.

Further, at this time, as shown in FIGS. 4A to 4B, the carrier gas 41 is introduced from the central axis 14 of the vaporization chamber to the eccentric position with respect to the vaporization chambers 11 a and 11 b in the vaporization unit 11, It is preferable to supply in a cyclone form.
The reason for this is partly described above. By introducing the carrier gas in this way, the carrier gas and the modifier compound are more stably mixed in the vaporization chamber in which the step (b) is performed. It is because it can be made.
Therefore, even when the amount of the modifier compound used is relatively small, a predetermined surface modification effect can be obtained effectively.

(2) Flame injection (2) -1 Fluid flow As shown in FIGS. 1A to 1B, the modifier compound 23 transferred from the vaporization chambers 11a and 11b by the introduction of the carrier gas 41. The mixed gas of ′ and the carrier gas 41 is further mixed with the combustion air 42 supplied from the compressed air source in the first mixer 31 a provided in the transfer unit 30.
Next, in the second mixer 31b, it is mixed with the hydrocarbon gas 43 supplied from the hydrocarbon gas source to become the final fuel gas, and finally, the object to be processed is injected from the injection unit 50 while the fuel gas is burned. 80 is injected.
In addition, it is preferable to provide a flow rate adjusting valve with a flow meter at each outlet portion of the vaporizing chamber, the compressed air source, and the hydrocarbon source so that the flow rate of each fluid can be adjusted as appropriate.

Moreover, as a kind of hydrocarbon gas, it is preferable to use propane gas or LPG (liquefied petroleum gas other than propane gas alone), for example.
This is because such a type of hydrocarbon gas is inexpensive and can be burned at a predetermined temperature.
Accordingly, it is possible to stably thermally decompose a silicon-containing compound or the like, and to firmly and uniformly laminate predetermined silica particles having a large number of hydroxyl groups on the surface of any solid substance.
Examples of LPG include butane (normal butane, isobutane), mixed gas of butane / propane, ethane, pentane (normal pentane, isopentane, cyclopentane) and the like.

(2) -2 Content of modifier compound Further, the content of the modifier compound in the fuel gas is in the range of 1 × 10 ⁻¹⁰ to 10 mol% when the total amount of the fuel gas is 100 mol%. It is preferable to set the value within the range.
This is because when the content of the modifier compound is less than 1 × 10 ⁻¹⁰ mol%, the modification effect on the solid substance may not be exhibited.
On the other hand, if the content of the modifier compound exceeds 10 mol%, the mixing property between the modifier compound and air or the like is lowered, and as a result, oxidation of the modifier compound may become insufficient. It is.
Therefore, the content of the modifier compound in the fuel gas is more preferably set to a value in the range of 1 × 10 ^{−9 to} 5 mol%, when the total amount of the fuel gas is 100 mol%. More preferably, the value is in the range of × 10 ⁻⁸ to 1 mol%.

(2) -3 Air content In addition, the final air content in the fuel gas is set to a value in the range of 80 to 99.9 mol% when the total amount of the fuel gas is 100 mol%. It is preferable.
This is because when the air content is less than 80 mol%, not only the combustion of the silicon-containing compound is incomplete, but also the generation of hydroxyl groups may be insufficient. On the other hand, when the air content exceeds 99.9 mol%, the surface modification effect may not be sufficiently exhibited.
Therefore, the content of air in the fuel gas is more preferably in the range of 90 to 99.5 mol% when the total amount of the fuel gas is 100 mol%, and is preferably 93 to 99 mol%. More preferably, the value is within the range.

(2) -4 Hydrocarbon gas content Further, the hydrocarbon gas content in the fuel gas is a value within the range of 0.1 to 10 mol% when the total amount of the fuel gas is 100 mol%. It is preferable that
The reason for this is that when the hydrocarbon gas content is less than 0.1 mol%, the flame temperature is lowered and the combustion of silicon-containing compounds and the like becomes incomplete, and the generation of hydroxyl groups becomes insufficient. This is because there are cases. On the other hand, if the content of such hydrocarbon gas exceeds 10 mol%, incomplete combustion may occur, and similarly, the surface modification effect may not be sufficiently exhibited.
Therefore, the content of the hydrocarbon gas in the fuel gas is more preferably set to a value within the range of 0.5 to 8 mol%, when the total amount of the fuel gas is 100 mol%, More preferably, the value is within the range of 5 mol%.

(2) -5 Air / Hydrocarbon Gas Mixing Molar Ratio The air / hydrocarbon gas mixing molar ratio in the fuel gas is preferably set to a value in the range of 23-45.
This is because when the value of the mixing molar ratio is less than 23, the surface modification effect is not stably exhibited, the flame tends to misfire, or incomplete combustion tends to occur. This is because there are cases. On the other hand, when the mixing molar ratio exceeds 45, the wetness index of the object to be processed is likely to vary, or the flame may become unstable and misfire may occur.
Therefore, the air / hydrocarbon gas mixing molar ratio in the fuel gas is more preferably set to a value in the range of 25 to 40, and further preferably set to a value in the range of 28 to 35.

(2) -6 To-be-processed object The to-be-processed object to be surface-modified in the injection step is usually a solid substance.
Such solid materials include silicone rubber, fluorine rubber, natural rubber, neoprene rubber, chloroprene rubber, urethane rubber, acrylic rubber, olefin rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber. And at least one rubber selected from the group consisting of butadiene rubber, butyl rubber, styrene-based thermoplastic elastomer and urethane-based thermoplastic elastomer.
Other solid materials include polyethylene resins (high density polyethylene, medium density polyethylene, low density polyethylene, high pressure polyethylene, medium pressure polyethylene, low pressure polyethylene, linear low density polyethylene, branched low density polyethylene, high pressure normal. Low density polyethylene, ultra-solid polyethylene, cross-linked polyethylene), polypropylene resin, modified polypropylene resin, polymethylpentene resin, polyester resin, polycarbonate resin, polyethersulfone resin, polyacrylic resin, polyetheretherketone resin, polyimide resin, Polysulfone resin, polystyrene resin, polyamide resin, polyphenylene sulfide resin, ethylene-tetrafluoroethylene copolymer, polyvinyl fluoride resin, tetrafluoroethylene-polymer Fluoro ether copolymer, tetrafluoroethylene - hexafluoropropylene copolymer, polytetrafluoroethylene resin, polyvinylidene fluoride resin, polytrifluorochloroethylene resin and ethylene - trifluorochloroethylene copolymer.
Moreover, as a solid substance, epoxy resin, phenol resin, cyanate resin, urea resin,
A thermosetting resin such as guanamine resin can be used.

Examples of the solid substance include aluminum, magnesium, stainless steel, nickel, chromium, tungsten, gold, copper, iron, silver, zinc, tin, lead, and the like, or a combination of two or more metal materials.
For example, although aluminum is frequently used as a lightweight metal, there has been a problem that it is easy to form an oxide film on the surface and easily peels off even when an ultraviolet curable paint or the like is directly applied.
Therefore, by applying a silicic acid flame treatment to the aluminum surface, it has become possible to effectively prevent peeling even when an ultraviolet curable paint or the like is directly applied.
In addition, magnesium has been widely used as a recyclable metal member in personal computers and other housings in recent years, but because of its poor surface smoothness, it can be easily peeled off even when UV curable paint is applied directly. There was a problem of doing so. Therefore, by applying silicic acid flame treatment to the magnesium surface, it is possible to effectively prevent peeling even when an ultraviolet curable paint or the like is directly applied, and a colored magnesium plate or the like can be obtained. Now available.
Further, conventionally, when gold bumps or solder bumps in a semiconductor element are electrically connected to a film carrier or a circuit board, there has been a problem that interface peeling occurs under high temperature and high humidity conditions. Therefore, by applying silicic acid flame treatment to gold bumps or solder bumps, or by conducting silicic acid flame treatment to conductor parts of film carriers or circuit boards, it is possible to effectively prevent these interface peeling. I can do it now.
The silicic acid flame treatment or the like is a treatment using a flame containing silicon atoms, titanium atoms or aluminum atoms, and a silicon oxide layer, an oxidation is formed on all or part of the base material by flame pyrolysis of the base material. It is a flame treatment that can form a titanium layer or an alumina oxide layer.

In addition, as solid substances, titanium oxide, zirconium oxide, zinc oxide, indium oxide, tin oxide, silica, talc, calcium carbonate, lime, zeolite, gold, silver, copper, zinc, nickel, tin, lead, solder, glass, One kind alone or a combination of two or more kinds such as ceramics may also be mentioned.
By adding the inorganic filler in this manner, the physical properties such as mechanical strength, heat resistance, conductivity, or electrical insulation of the solid substance can be improved depending on the type of the inorganic filler.
In addition, when adding an inorganic filler with respect to a solid substance, it is preferable to make the addition amount into the value within the range of 0.01 to 80 weight% with respect to the whole quantity, and 0.1 to 50 weight% More preferably, the value is in the range of 1 to 30% by weight.

Furthermore, the form of the solid substance that is the object to be treated is not particularly limited. For example, the solid substance has a planar structure such as a plate, sheet, film, tape, strip, panel, string, However, it may have a three-dimensional structure such as a cylindrical shape, a columnar shape, a spherical shape, a block shape, a tube shape, a pipe shape, an uneven shape, a film shape, a fiber shape, a fabric shape, or a bundle shape. .
For example, by applying silicic acid flame treatment to fibrous glass or carbon fiber, the surface can be modified and activated, and uniformly in a matrix resin such as epoxy resin or polyester resin. Can be dispersed. Therefore, excellent mechanical strength, heat resistance and the like can be obtained in FRP and CFRP.

In addition, as a form of such an object to be processed, a composite structure in which such a structure made of a solid substance and a metal part, a ceramic part, a glass part, a paper part, a wooden part, and the like are combined is also preferable.
For example, by applying silicic acid flame treatment or the like to the inner surface of a metal tube or ceramic tube, the surface can be modified and activated, and a pipe in which a resin liner is laminated extremely firmly can be obtained. .
Further, by applying a silicic acid flame treatment or the like to the whole or part of a glass substrate or a plastic substrate as a substrate in a liquid crystal display device, an organic electroluminescence device, a plasma display device, or a CRT, a color filter, a deflection plate, Organic films such as a light scattering plate, a black matrix plate, an antireflection film, and an antistatic film can be laminated extremely uniformly and firmly.

Hereinafter, the present invention will be described in more detail with reference to examples.
However, the following description shows the present invention by way of example, and the present invention is not limited to these descriptions.

[Example 1]
As shown in FIG. 1, a cylindrical first vaporization chamber 11a (diameter 1.5 cm, length 10 cm, volume 17.7 ml) and a cylindrical second vaporization chamber 11b (diameter 1.5 cm, length 10 cm). 4) and a cyclone system in which the carrier gas inlet 13 is provided in an eccentric position with respect to the central axis 14 of the vaporization chamber as shown in FIGS. 4 (a) to 4 (b). A surface modification device 10 was prepared.
Next, while moving the burner 50 provided in the surface modification device 10, a mixture in which 10 parts by weight of ethanol was added to 100 parts by weight of hexamethyldisiloxane (boiling point: 101 ° C.) as the silicon-containing compound 23. The silicic acid flame treatment derived from the contained combustion gas was performed, and the surface treatment effect was confirmed.
Environmental temperature: 25 ° C
Vaporization chamber temperature: 40 ° C
Fuel gas: Flow rate 1 (air flow rate) 80 l / min
Flow rate 2 (propane gas flow rate) 2.5 liters / minute
Flow rate 3 (silicon-containing compound / carrier flow rate) 2 liters / minute
(Hexamethyldisiloxane concentration: about 0.00045 mol)
Burner moving speed: 20 m / min Number of treatments: 1 distance to burner: 20 mm

That is, after the first vaporization chamber is operated and the silicic acid flame treatment is continuously performed on the metal plate for 1 hour, the object to be treated is changed to a polypropylene plate (100 mm × 50 mm × 2 mm), The wetting index (25 ° C.) on the surface was measured using a standard solution (first measurement).
Next, the second vaporization chamber is operated, the solenoid valve in the moving part is switched, and further, the silicic acid flame treatment is continuously performed on the metal plate for 1 hour, and then the workpiece is changed to the polypropylene plate. The wetting index (25 ° C.) on the surface of the polypropylene plate was measured (second measurement).
Then, while the second vaporization chamber was operating, the first vaporization chamber was filled with a predetermined amount of silicon-containing compound.
Next, the first vaporization chamber is operated again, the electromagnetic valve in the moving part is switched, and after the silicic acid flame treatment is continuously performed on the metal plate for 1 hour, the workpiece is changed to a polypropylene plate, The wetting index (25 ° C.) on the surface of the polypropylene plate was measured (third measurement).

[Examples 2 to 4]
In Examples 2 to 4, the flow rate 3 (silicon-containing compound / carrier gas flow rate) was 1.5 liters / minute (Example 2), 2.5 liters / minute (Example 3), 3.0 liters / minute ( The wetness index (25 ° C.) on the surface of the first to third polypropylene plates was measured in the same manner as in Example 1 except that Example 4) was used.
In the table, “liter / minute” is expressed as “L / minute”.

[Examples 5 to 8]
In Examples 5 to 8, tetramethylsilane (boiling point: 27 ° C.) was used as the silicon-containing compound contained in the combustion gas, and the flow rate was 3.0 liters / minute (silicon-containing compound / carrier gas flow rate). Except for 5 liters / minute (Example 5), 4.0 liters / minute (Example 6), 4.5 liters / minute (Example 7), and 5.0 liters / minute (Example 8), In the same manner as in Example 1, the wetting index (25 ° C.) on the surface of the first to third polypropylene plates was measured.

[Comparative Example 1]
In Comparative Example 1, instead of the surface modification device used in Example 1, the conventional surface modification device shown in FIG. 9 was used, and the silicic acid flame treatment was continuously performed on the metal plate for 3 hours. A predetermined amount of silicon-containing compound was filled every 1 hour, and immediately after that, the wetting index (25 ° C.) on the surface of the polypropylene plate was measured in the same manner as in Example 1. The obtained results are shown in Table 1.

流量１:空気流量
流量２:プロパンガス流量
流量３:ケイ素含有化合物／キャリア流量

Flow rate 1: Air flow rate Flow rate 2: Propane gas flow rate Flow rate 3: Silicon-containing compound / carrier flow rate

[Examples 9 to 12]
In Example 9, the first to third steps are the same as in Example 1, except that the air flow rate is 70 liters / minute and the propane gas flow rate contained in the combustion gas is 2.5 liters / minute. The wetting index (25 ° C.) on the surface of the polypropylene plate was measured.
Further, in Example 10, the first to the same as in Example 1 except that the air flow rate was 75 liters / minute and the propane gas flow rate contained in the combustion gas was 1.25 liters / minute. The wetting index (25 ° C.) on the surface of the third polypropylene plate was measured.
Further, in Example 11, the first to the same as in Example 1 except that the air flow rate was 80 liters / minute and the propane gas flow rate contained in the combustion gas was 2.25 liters / minute. The wetting index (25 ° C.) on the surface of the third polypropylene plate was measured.
Further, in Example 12, the first to the same as in Example 1 except that the air flow rate was 85 liters / minute and the propane gas flow rate contained in the combustion gas was 2.5 liters / minute. The wetting index (25 ° C.) on the surface of the third polypropylene plate was measured.

流量１:空気流量
流量２:プロパンガス流量
流量３:ケイ素含有化合物／キャリア流量

Flow rate 1: Air flow rate Flow rate 2: Propane gas flow rate Flow rate 3: Silicon-containing compound / carrier flow rate

[Examples 13 to 16]
In Examples 13-16, the influence of the temperature of a vaporization chamber and environmental temperature was examined.
That is, in Examples 13 and 14, the wetting index (25) on the surface of the first to third polypropylene plates was the same as in Example 1 except that the temperature of the vaporization chamber was set to 30 ° C. and 50 ° C. ° C).
In Examples 15 to 16, the wetness index (25 ° C.) on the surfaces of the first to third polypropylene plates was the same as in Example 1 except that the environmental temperature was 10 ° C. and 15 ° C. It was measured.

流量１:空気流量
流量２:プロパンガス流量
流量３:ケイ素含有化合物／キャリア流量

Flow rate 1: Air flow rate Flow rate 2: Propane gas flow rate Flow rate 3: Silicon-containing compound / carrier flow rate

[Examples 17 to 20]
In Examples 17-20, the influence of the volume of the vaporization chamber was examined.
That is, in Example 17, the wetting index (25 ° C.) on the surface of the first to third polypropylene plates was measured in the same manner as in Example 1 except that the diameter of the cylindrical vaporization chamber was 1 cm. .
Further, in Example 18, except that the diameter of the cylindrical vaporization chamber was set to 1.25 cm, the wetting index (25 ° C.) on the surface of the first to third polypropylene plates was the same as in Example 1. It was measured.
In Example 19, the wet index (25 ° C.) on the surface of the first to third polypropylene plates was measured in the same manner as in Example 1 except that the diameter of the cylindrical vaporization chamber was 2 cm. .
Further, in Example 20, the wetness index (25 ° C.) on the surface of the first to third polypropylene plates was the same as in Example 1 except that the diameter of the cylindrical vaporization chamber was 2.5 cm. It was measured.

流量１:空気流量
流量２:プロパンガス流量
流量３:ケイ素含有化合物／キャリア流量

Flow rate 1: Air flow rate Flow rate 2: Propane gas flow rate Flow rate 3: Silicon-containing compound / carrier flow rate

[ Reference Examples 19-22 ]
In Reference Examples 19 to 22 , instead of the surface reforming apparatus adopting the cyclone method, the carrier gas inlet 13 in the vaporization section 11 (11a, 11b) shown in FIGS. In the same manner as in Examples 1 to 4, except for using a surface modification device (not shown) that employs a non-cyclone system that is not eccentric with respect to the central axis 14 of the first axis on the surface of the polypropylene plate, respectively. The third wetting index (25 ° C.) was measured.
For reference, FIGS. 8A to 8B show the flow of the carrier gas 41 in the vaporization section 11 (11a, 11b) in the non-cyclone system.

流量１:空気流量
流量２:プロパンガス流量
流量３:ケイ素含有化合物／キャリア流量

Flow rate 1: Air flow rate Flow rate 2: Propane gas flow rate Flow rate 3: Silicon-containing compound / carrier flow rate

According to the surface modification device of the present invention and the surface modification method using the same, while providing a plurality of vaporization chambers and supplying a modifier compound to any one of the vaporization chambers, By introducing the carrier gas, the concentration change of the modifier compound contained in the fuel gas can be suppressed even while the modifier compound is being supplied to the vaporization section.
As a result, even when surface modification is performed while supplying the modifier compound to the vaporization section, the concentration change of the modifier compound contained in the fuel gas is small and the surface modification treatment is continued. Even if implemented, the surface of the solid material can be stably modified.
Therefore, the surface modification apparatus and the surface modification method using the same of the present invention are expected to contribute significantly to the improvement in quality and efficiency of the surface treatment technology.

10: surface reformer, 11: vaporization section, 11a: first vaporization chamber, 11b: second vaporization chamber, 12 (12a, 12b): supply port for modifier compound, 13 (13a, 13b): Carrier gas inlet, 14: central axis of vaporization chamber, 15: prism sensor, 15a: light emitting element, 15b: light receiving element, 17: micropump, 17a: piston, 17b: cylinder, 18 (18a, 18b): temperature sensor , 19: heater (19a, 19b), 21: storage chamber, 22: liquid level gauge, 23: modifier compound, 23 ': gas modifier compound, 24: residual pressure release, 25: modifier Compound replenishment port, 30: transfer part, 31 (31a, 31b): mixer, 41: carrier gas, 50: injection part, 51: flame, 52: IR sensor, 52a: control part, 60 (60a, 60b, 60c, 60 , 60e, 60f): Switching device (solenoid valve), 70: tubular structure, 80: object to be processed

Claims (8)

A vaporization section having a plurality of vaporization chambers, and even when surface modification is carried out while supplying a modifier compound to the vaporization section, vaporization in which the modifier compound is supplied A surface reforming apparatus that separates the chamber and the vaporization chamber that is used for the surface modification, and suppresses the concentration change of the modifier compound contained in the fuel gas,
A storage chamber for storing a silicon-containing compound as the modifier compound,
A vaporization unit for supplying the modifier compound from the storage chamber and evaporating it at a predetermined temperature to generate a modifier compound in a gaseous state;
A transfer unit for introducing air as a carrier gas into the vaporization unit and transferring the gaseous modifier compound as a part of the fuel gas to the injection unit;
An injection unit for blowing a flame derived from the fuel gas containing the modifier compound;
Contains
The plurality of vaporization chambers include at least a first vaporization chamber and a second vaporization chamber, and a switching device for alternately using the first vaporization chamber and the second vaporization chamber ,
A surface reforming apparatus , wherein a carrier gas inlet in the first vaporization chamber and the second vaporization chamber is provided in an eccentric position with respect to a central axis of the vaporization chamber . 2. The surface reforming apparatus according to claim 1, wherein each of the first vaporization chamber and the second vaporization chamber has a volume within a range of 10 to 200 cm ³ .   3. The surface reforming apparatus according to claim 1, wherein a supply port of the modifier compound from the storage chamber is provided at a bottom of the first vaporization chamber and the second vaporization chamber. .   The surface modification apparatus according to any one of claims 1 to 3, wherein the first vaporization chamber and the second vaporization chamber are columnar or prismatic. The first vaporization chamber is a main vaporization chamber, and is constantly operating except when replenishing the modifier compound,
Any said second vaporization chamber, a preliminary vaporization chamber, said first vaporization chamber, of claims 1 to 4, characterized in that it operates only when refilling the modifying compound The surface modification apparatus according to claim 1. It has a vaporization section having a plurality of vaporization chambers, and supplies a modifier compound to one vaporization chamber, while introducing a carrier gas to another vaporization chamber to improve the gas state. A surface reforming method using a surface reformer that generates a material compound and suppresses a change in concentration of the modifier compound contained in the fuel gas,
The surface modifying device is
A storage chamber for storing a silicon-containing compound as the modifier compound;
A vaporization unit for supplying the modifier compound from the storage chamber and evaporating it at a predetermined temperature to generate a modifier compound in a gaseous state;
A transfer unit for introducing air as a carrier gas into the vaporization unit and transferring the gaseous modifier compound as a part of the fuel gas to the injection unit;
And an injection part for blowing a flame derived from the fuel gas containing the modifier compound,
The vaporization unit includes a plurality of vaporization chambers including at least a first vaporization chamber and a second vaporization chamber, and a switching device for alternately using the first vaporization chamber and the second vaporization chamber. And
The surface modification method characterized by including the process of implementing the following process (a) and (b) simultaneously.
(A) supplying the modifier compound from the storage chamber to either the first vaporization chamber or the second vaporization chamber;
(B) Of the first vaporization chamber and the second vaporization chamber, with respect to the vaporization chamber different from the vaporization chamber in which the step (a) is performed, the carrier gas is supplied to the center of the vaporization chamber. A step of injecting a flame derived from a fuel gas containing a vaporized modifier compound onto a workpiece while introducing the cyclone from an eccentric position with respect to an axis . In the vaporization chamber in which each of the first vaporization chamber and the second vaporization chamber is provided with a liquid level gauge and the modifier compound is detected to have a liquid level below a predetermined standard, the step (a) is performed. The surface modification method according to claim 6 , wherein the surface modification method is performed. The surface modification method according to claim 6 or 7 , wherein, in the step (a), the temperature of the vaporization chamber is set to a value within a range of 40 to 80 ° C.

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