WO2005007728A1

WO2005007728A1 - Continuous surface-treating apparatus for three-dimensional shape of polymer and continuous surface-treating method thereof

Info

Publication number: WO2005007728A1
Application number: PCT/KR2003/002110
Authority: WO
Inventors: Yong Rak Choi
Original assignee: EPON Co Ltd
Current assignee: EPON Co Ltd
Priority date: 2003-07-22
Filing date: 2003-10-13
Publication date: 2005-01-27
Anticipated expiration: 2006-01-22
Also published as: AU2003269528A1; KR100439942B1; KR20030066557A; JP2007520569A

Abstract

The present invention provides a continuous surface treatment apparatus of tridimensional-shaped polymer by plasma ion implantation, which includes a high frequency power supplying device for generating plasma for injecting ions, and having a high frequency power supplying unit, a matching box, and an antenna, a gas introducing unit for supplying process gas to be ionized for plasma, a gas supplying unit connected to the gas introducing unit, a processing chamber having a vacuum pump and the like, a leading-in chamber, and an leading-out chamber, which are installed before and after the processing chamber respectively with adjacent thereto, and are adapted to be gas-exhaustible, a transferring unit installed to sequentially pass by through the leading-in chamber, the processing chamber, and the leading-out chamber, transferring means for driving the transferring unit, and doors being positioned in the leading-in chamber and the leading-out chamber respectively, and in partitions between the leading-in chamber and the processing chamber, and between the processing chamber and the leading-out chamber respectively, and automatically capable of being opened/closed so that the transferring unit can pass by therethrough.

Description

CONTINUOUS SURFACE-TREATING APPARATUS FOR THREE-DIMENSIONAL SHAPE OF POLYMER AND CONTINUOUS SURFACE-TREATING METHOD

THEREOF

Technical Field

The present invention relates to a continuous surface treatment of tridimensional-shaped

polymer. More particularly, the present invention relates to an apparatus for continuously

performing surface-treatment on tridimensional-shaped polymer through plasma ion implantation

by negative voltage pulses to improve the antistatic characteristics, the conductibility, or other

properties of the surface of the polymer, and a method of continuously performing surface-

treatment on tridimensional-shaped polymer using the same.

Background Art

A polymer material is widely used for various applications due to the lightness of

weight, shape-forming property, processability, transparency, electric insulating property, or the

like. In cases, it is necessary to modify only the surface properties of the polymer depending on

its uses, and thus, it is necessary to perform a specific treatment on the surface of the polymer

material, without changes in other properties of the entire polymer material. In specific, since the

hydrophilic or hydrophobic property of the surface will significantly affect the wettability,

printability, colorability, biocompatibiJity, antielectrostatic property, adhesiveness, water proofing

property, vapor proofing property, and the like of the polymer material, various techniques are

used in order to improve those properties.

Among the surface treatment methods for such a polymer material, there are a chemical

treatment, a corona treatment, a plasma treatment, or the like. One of the typical methods of the chemical treatment is a surface treatment method of fluorine-based polymer using Na H (see

US. Patent No. 2,789,063, British Patent GB 793,731). The method has an advantage of

allowing to foresee the functional group formed on the surface of the polymer material by normal

chemical reaction, but has a disadvantage of requiring complicated treatment processes, and

causing waste materials as contaminants.

In the meantime, the corona discharge treatment, which is carried out under the

atmospheric pressure, is used in the surface treatment of polyolefine or polyethylenetelephthalate

film, etc. as packaging material (see J. Pochan, L. Gerenser, and J. Elman, Polymer, vol. 27 at

page 1058, 1986 publication). However, the method has a disadvantage that since its modified

layer is very thin, it may be easily deteriorated as time goes by. Further, it is difficult to optimize

the conditions of treatment process parameters such as atmospheric humidity, or the like.

The polymer surface treatment method using plasma under a low pressure includes a

use of oxygen plasma to improve hyαtophilic property of polypropylene, polyethylene,

polystylene, etc. (see M. Morra, E. OcchieUo, and F. Garbassi, Journal of Applied Polymer

Science, vol.39 at page 249, 1999 publication), or the like.

Plasma is known as the fourth state of substance distinguishable from solid, liquid and

gas, and may be referred to as partially ionized gas. It usually comprises electrons, positive ions,

neutral atoms, and neutral molecules, etc. When an electric power is applied to a gas particle,

the peripheral electrons of the gas atoms are departed from the orbit and become free electrons,

and the gas atom exhibits positive charge. Such electrons and ionized gas atoms generated as

the above maintain the neutral state all together, and emit specific light by the mutual interaction

of the component elements, so that the elements are activated and excited to allow high reactivity.

The plasma treatment has advantages of allowing to select a reactant gas and control the process parameters such as treatment pressure, etc. with compared to the corona treatment, but it also has

a problem of the deterioration as time goes by after being treated since its modified surface layer is

thin.

Further, there is recently introduced a method of injecting the ion beam of inert atoms

(Ar) into a polymer material in the presence of oxygen to improve its hydrophilic property (see S.

Koh, S. Song, W. Choi, and H. Jung, Journal of Materials Research, vol. 10 at page 2390, 1995

publication), but this method has disadvantages of the rapid decrease of the hydrophilic property

as time goes by, and the complicated apparatus structure because of using the ion beam inevitably,

and difficulty in treating the surface with large size uniformly. In the meantime, U.S. Patent No. 4,764,394 titled "Method and apparatus for plasma

source ion implantation" is known as a prior art suitable for an ion implantation of a

tridimensional object.

Korean Patent Publication KR 1987-7562 discloses a surface treatment method which

performs various surface treatment on the surface of semiconductors, metal or insulating

materials, such as surface etching, surface modification, surface cleaning, impurities implantation

into the surface, thin film deposition on the surface, or the like, and a surface treatment apparatus

used in the same. Herein, the method includes a process of applying an ion beam including at

least one species of atoms on the surface of a solid target, so as to scatter particles from the surface

of the target toward the front, and generate a scattering particle beam including the at least one

species of atoms, and injecting the particle beam toward the surface of an object, thereby etching

or modifying the surface of the object, or depositing a thin film on the surface of the object.

Korean Patent Publication KR 1997-73239 discloses a surface modification method for

improving the hydrophilic property or hydrophobic property of the surface of a polymer material by plasma ion implantation, and an apparatus used in the same. The method includes steps of:

locating a sheet-shaped polymer material on a plate inside a vacuum chamber; introducing plasma

source gas into the vacuum chamber, generating ion plasma from the introduced plasma source

gas; and implanting the ions extracted from the plasma with a high energy into the surface of the

polymer material by applying negative high voltage pulse into the polymer object, in which the

pulse voltage is -1 kV to -20 kV, the voltage in the pulse-off is 0 V to -1 kV, the pulse width is 1

μs to 50 μs, and the pulse frequency is 10 Hz to 500 kHz.

However, the methods are not intended to improve the antielectrostatic property and the

conductibility property, or the like but good for improving the hydrophilic property or

hydrophobic property of the polymer materials.

In the case of antielectrostatic and conductive polymer, conductive carbon and carbon

fiber are mixed with the polymer and, but after forming, the carbon and the particles of the carbon

fiber are peeled off from the antielectrostatic and conductive polymer to cause a serious damage

on the polymer product, and particles are attached on electronics, semiconductors, and LCD

(liquid crystal display) to cause a serious damage on the patterns or the chips thereof.

Sometimes, it is impossible to expect the antielectrostatic effect in case of the use of the

antielectrostatic material for the antielectrostatic effect since the antielectrostatic effect itself is

disappeared as time goes by.

In the case of the product, which is fabricated by immersing itself into a solution made

by dissolving conductive polymer of polypyrrole and polyaniline, or a solution including aromatic

polymer and atactic polymer, taking out, and drying, the product is so vulnerable to scratch or

moisture to lose the antielectrostatic effect and the conductibility. Further, in the case of the surface modification of polymer using an ion beam, a mass

production through continuous process is hardly expected in the aspect of production yield, and

the fabrication process involves difficult and inconvenient steps and tools in which a beam should

be accelerated, and the area having neutrons should be isolated with the beam scattered, and

furthermore, a jig for rotating an object should be employed to perform ion implantation in three-

dimensional space.

Korean Patent Publication KR 2002-20010 discloses a surface modification method for

improving the surface properties and conductibility of a tridimensional polymer material and a

product thereof, and an apparatus used in the same, by using plasma ion implantation technology.

The method discloses surface treatment of tridimensional polymer material by plasma ion

implantation using a grid, and includes the steps of: (a) locating tridimensional polymer material

in a grid inside a vacuum chamber, (b) locating the grid distanced from the material surface inside

the vacuum chamber, (c) generating gas plasma ions to form a graphite layer on the material

surface inside the vacuum chamber to decrease resistivity, and (d) applying negative voltage pulse

on the grid so as to inject the gas plasma ion into the material surface. However, the method has

a problem of being not suitable to be employed in mass production.

Disclosure of the Invention

Accordingly, the present invention is directed to a continuous surface treatment method

of tridimensional-shaped polymer by plasma ion implantation by negative voltage pulse, for

improving antistatic characteristics of the polymer surface, conductibility, and the like, that

substantially obviates one or more of the problems due to limitations and disadvantages of the

related art. Additional features and advantages of the invention will be set forth in the description

which follows, and in part will be apparent from the description, or may be learned by practice of

the invention. The objectives and other advantages of the invention will be realized and attained

by the structure particularly pointed out in the written description and claims thereof as well as the

appended drawings.

To achieve these and other advantages and in accordance with the purpose of the

present invention, as embodied and broadly described, the present invention provides a

continuous surface treatment apparatus of tridimensional-shaped polymer, which may include a

high frequency power supplying device for generating plasma and thus, injecting ions, and having

a high frequency power supplying unit, a matehing box, and an antenna; a gas introducing unit for

supplying process gas to be ionized for plasma a gas supplying unit connected to the gas

introducing unit; a processing chamber having a vacuum pump and the like; a leading-in

chamber, and an leading-out chamber, which are installed before and after the processing

chamber respectively with adjacent thereto, and are adapted to be gas-exhaustible; a transferring

unit installed to sequentially pass by through the leading-in chamber, the processing chamber, and

the leading-out chamber, trarisferring means for driving the traraferring unit; and doors being

positioned in the leading-in chamber and the leading-out chamber respectively, and in partitions

between the leading-in chamber and the processing chamber, and between the processing

chamber and the leading-out chamber respectively, and automatically capable of being

opened/closed so that the trarisferring unit can pass by therethrough.

The transferring means may be trarisferring rollers installed to be rotatable. The transferring unit may include a trarisferring plate; a transferring wing integrally

fixed on top of the transferring plate and variable with contact on the transferring rollers; and a fixture integrally fixed on bottom of the transferring plate and adapted to hang or fix a

tridimensional-shaped polymer.

The surface treatment apparatus may further include a pre-processing chamber, which

is installed with adjacent to the leading-in chamber in order to pre-treat the tridimensional-shaped

polymer to be surface-treated by supplying a dried hot air at a temperature of 70°C to 85°C to the

tridimensional-shaped polymer, and the pre-processing chamber may include a fan for supplying

hot air into the pre-processing chamber, a first cutoff valve for cutting off the flow of the hot air

supplied to the fan, a second cutoff valve for cutting off the flow of the air to be discharged from

the pre-processing chamber to vacuumize the pre-processing chamber, and a vacuum pump for

discharging the air from the pre-processing chamber through the second cutoff valve.

An air compressor may be further connected to the first cutoff valve to generate hot air. The pre-processing chamber can be stmctured such that two discrete chambers are

provided in parallel, and for this purpose, a second pre-processing chamber may be installed with

adjacent to the pre-processing chamber. The second pre-processing chamber may include a

second fan for supplying hot air into the pre-processing chamber, a third cutoff valve for cutting

off the flow of the hot air supplied to the second fan, a fourth cutoff valve for cutting off the flow

of the air to be discharged from the second pre-processing chamber to vacuumize the pre¬

processing chamber, and a vacuum pump for discharging the air from the pre-processing chamber

through the fourth cutoff valve. The vacuum pump may be one vacuum pump, which can be

commonly used passing through the second cutoff valve and the fourth cutoff valve. Further,

the air compressor for generating hot air may be commonly used passing through the third cutoff

valve. To further achieve these and other advantages and in accordance with the purpose of

the present invention, the present invention provides a continuous surface treatment method for

tridimensional-shaped polymer by surface modification using plasma ion implantation

technology, and the method may include steps of: (1) loading a tridimensional-shaped

polymer product to be processed into a gas-exhaustible leading-in chamber (leading-in); (2)

decompressing and gas-exhausting the inside of the leading-in chamber into which the

tridimensional-shaped polymer product is loaded (first vacuumization); (3) transferring the

tri(iunensional-shaped polymer product inside the leading-in chamber to a processing chamber

(first transfer); (4) performing surface-treatment on the tridmensional-shaped polymer product

inside the processing chamber by using plasma (surface treatment); (5) decompressing and gas-

exhausting the inside of a gas-exhaustible leading-out chamber (second vacuumization); (6)

transferring the surface-treatment completed tridimensional-shaped polymer product into the

vacuumized leading-out chamber (second transfer); and (7) urύoading the tridimensional-shaped

polymer product inside the leading-out chamber to the exterior (leading-out). Before or after the (2) first vacuumization step, the method may further include a step of

performing another pre-treatment by applying hot air on the tridimensional-shaped polymer

product inside the leading-in chamber to remove moisture therefrom.

The (4) surface-treatment step may be carried out by continuously supplying process

gas including argon, nitrogen, or these mixture to the processing chamber at a rate of 15 to 100

seem under the process conditions of 20 to 30 ms of pulse width, 500 to 1,500 Hz of high

frequency for plasma generation, and 21 to 25 KV of high voltage pulse. It is to be understood that both the foregoing general description and the following

detailed description are exemplary and explanatory and are intended to provide further

explanation of the invention as claimed.

Brief Description of the Drawings

The accompanying drawings, which are included to provide a further understanding of

the invention and are inco orated in and constitute a part of this specification, illustrate

embodiments of the invention and together with the description serve to explain the principles of

the mvention.

In the drawings:

FIG. 1 is a view to illustrate the structural configuration of one specific example of a

continuous surface treatment apparatus of tridm ensional-shaped polymer according to one mbodiment of the present invention;

FIG. 2 is a perspective view to illustrate one specific example of a transferring unit

being used in the apparatus of FIG. 1 ; and

FIG. 3 is a view to illustrate the structural configuration of one specific example of a

pretreatment unit adapted to be connected to the continuous surface treatment apparatus of

triόjinensional-shaped polymer according to one embodiment of the present invention.

Best Mode for Carrying Out the Invention

Reference will now be made in detail to the preferred embodiments of the present

invention, examples of which are illustrated in the accompanying clrawings. As shown in FIG. 1, the continuous surface treatment apparatus of tridimensional-

shaped polymer according to one embodiment of the present invention is structured to essentially

include a surface treatment apparatus, which is composed of a high frequency power supplying

device for generating plasma and thus, injecting ions, and having a high frequency power

supplying unit 27, a mafching box 26, and an antenna 25; a gas introducing unit 71 for supplying

process gas to be ionized for plasma; a gas supplying unit 72 connected to the gas introducing unit

71; and a processing chamber 21 having a vacuum pump and the like. The continuous surface

treatment apparatus further includes a leading-in chamber 11, and an leading-out chamber 31,

which are installed before and after the processing chamber 21 respectively with adjacent thereto,

and are adapted to be gas-exhaustible; a transferring unit 51 installed to sequentially pass by

through the leading-in chamber 11, the processing chamber 21, and the leading-out chamber 31;

transferring means for driving the transferring unit 51; and doors being positioned in the leading-

in chamber 11 and the leading-out chamber 31 respectively, and in partitions between the teading-

in chamber 11 and the processing chamber 21, and between the processing chamber 21 and the

leading-out chamber 31 respectively, and automatically capable of being opened/closed so that

the transferring unit 51 can pass by therethrough.

It can be understood that the surface treatment apparatus of tridimensional-shaped

polymer, which is composed of the high frequency power supplying device for generating plasma

and thus, injecting ions, and having the high frequency power supplying unit 27, the matehing

box 26, and the antenna 25; the gas introducing unit 71 for supplying process gas to be ionized for

plasma; the gas supplying unit 72 connected to the gas introducing unit 71; and the processing

chamber 21 having a vacuum pump and the like, is publicly known as much as commercially

available to those skilled in this art. In the surface treatment apparatus using plasma, process gas to be ionized is supplied into the vacuuniized processing chamber 21 , and a high frequency power

is applied to a strong magnetic field to partially ionize the process gas and thus, generate plasma,

so called a fourth material state. Then, an object to be processed is placed on a plate or the like,

charged by a high voltage, or inside a grid 24. Among the ions in the plasma, ions having an

opposite polarity to that of the current applied to the plate or the grid 24 are electrostatically

induced by the high voltage pulse mostly applied to the grid 24 or the like, and applied on the

surface of the object, so as to achieve an ion injection on the surface of the object. That is, in a

typical surface treatment apparatus described as above, the surface treatment apparatus according

to the present invention further includes the leading-in chamber 11, and the leading-out chamber

31, which are installed before and after the processing chamber 21 adjacent thereto respectively,

in order to continuously perform a surface treatment on an object to be processed, in the typical

surface treatment apparatus. The leading-in chamber 11 , and the leading-out chamber 31 have

vacuum pumps or the like respectively, in order to exhaust gas therefrom. In addition, the

surface treatment apparatus according to the present invention includes the transferring unit 51,

which is installed in the leading-in chamber 11, the processing chamber 21, and the leading-out

chamber 31, capable of passing by through those chambers sequentially, and transferring means

for driving the trarisferring unit 51.

Further, the trarisferring unit 51 can be moved by the trarisferring means, and

preferably, the transferring means may employ tramferring rollers 61, which are installed in the

leading-in chamber 11, the processing chamber 21, and the leading-out chamber 31, being able to

rotate thereinside.

The tr-ffisferring unit 51 , being moved by the transferring rollers 61 , as shown in FIG.2,

includes a transferring plate 52, a trarisferring wing 53 integrally fixed on top of the transferring plate 52 and variable with contact on the rollers, and a fixture 54 integrally fixed on bottom of the

transferring plate 52 and adapted to hang or fix a tridimensional-shaped polymer 41. The above

description is limited to specific examples of the transferring roller 61 and the transferring unit 51

being movable by the trarisferring rollers 61, but other means are possible if they can transfer the

tridimensional-shaped polymer 41. Further, other means are possible only if material making of

the transferring unit 51 and the transferring roller 61 equal to or similar to a stainless steel making

of the processing chamber 21, and the material gives no impact on plasma, or high frequency

power, high voltage pulse, or the like.

To transfer the triάimensional-shaped polymer 41 by the transferring unit 51, the

continuous surface treatment apparatus of the present invention further includes doors which are

installed in the leading-in chamber 11, the leading-out chamber 31, and the partition between the

leading-in chamber 11 and the processing chamber 21, and the partition between the processing

chamber 21 and the leading-out chamber 31, and capable of being automatically opened/closed to

allow the trarisferring unit 51 to pass therethrough. The doors can be opened/closed by driving

means such as solenoid, pneumatic cylinder, hydraulic cylinder, or the like, which are publicly

known. When they are opened, the trarisferring unit 51 fixing the tridimensional-shaped

polymer 41 fixed thereon can pass therethrough, and when they are closed, they can intercept the

permeation of air, so that the chambers can maintain a

vacuum state. More

preferably, the doors have sliding door-typed structures so as to be opened/closed in a short time

so that the chambers are sealed right after the tridimensional-shaped polymer 41 pass

merethrough, and thus, the doors are opened/closed as narrow opening width as the lowest width

level of the tridimensional-shaped polymer 41 so that the tridimensional-shaped polymer 41 pass

therethrough, which are understood to be publicly known to those skilled in the art As shown in FIG. 3, a pre-processing chamber 81 is further provided with adjacent to

the leading-in chamber 11 in order to pre-treat the tridimensional-shaped polymer 41 to be

surface-treated by supplying a dried hot air at a temperature of 70°C to 85°C to the tridimensional-

shaped polymer 41. The pre-processing chamber 81 includes a fan 82 for supplying hot air into

the pre-processing chamber 81, a first cutoff valve 83 for cutting off the flow of the hot air

supplied to the fan 82, a second cutoff valve 85 for cutting off the flow of the air to be discharged

from the pre-processing chamber 81 to vacuumize the pre-processing chamber 81, and a vacuum

pump for discharging the air from the pre-processing chamber 81 through the second cutoff valve

85. An air compressor 84 may be further connected to the first cutoff valve 83 to generate hot

air.

The pre-processing chamber 81 can be structured such that two discrete chambers are

provided in parallel, and for this purpose, a second pre-processing chamber 87 is installed with

adjacent to the pre-processing chamber 81. The second pre-processing chamber 87 includes a

second fan 88 for supplying hot air into the pre-processing chamber 81, a third cutoff valve 89 for

cutting off the flow of the hot air supplied to the second fan 88, a fourth cutoff valve 90 for cutting

off the flow of the air to be discharged from the second pre-processing chamber 87 to vacuumize

the pre-processing chamber 81, and a vacuum pump for discharging the air from the pre¬

processing chamber 81 through the fourth cutoff valve 90. The vacuum pump may be one

vacuum pump, which can be commonly used passing through the second cutoff valve 85 and the

fourth cutoff valve 90. Further, the air compressor 84 for generating hot air may be commonly

used passing through the third cutoffvalve 89.

Further, a pre-treatment can be performed in the leading-in chamber 11 by employment

of hot air therein even without the installation of the pre-processing chamber 81, by ήistalling on the leading-in chamber 11 the fan 82, cutoff valves for cutting off the flow of hot air, and the air

compressor 84 passing these valves and connected thereto, which are installed in the pre¬

processing chamber 81.

In the construction described as above, and in reference to FIG. 1, the first door 13 is

opened, and the transferring unit 51 for transferring the tridimensional-shaped polymer 41 with

the tridimensional-shaped polymer 41 fixed thereto, is loaded into the leading-in chamber 11

through the first open door 13, and then, the first door 13 is closed. The inside of the leading-in

chamber 11 is vacuumized sufficiently by the operation of the vacuum pump, and the second

door 28 between the leading-in chamber 11 and the processing chamber 21 is opened. By

driving the transferring roller 61, the trarisferring unit 51 is transferred into the processing chamber

21 to locate the tridimensional-shaped polymer 41 fixed to the transferring unit 51 inside the grid

24 inside the processing chamber 21, and then, the second door 28 is closed. Then, plasma

treatment is performed. The plasma treatment is identical to, or similar to a conventional plasma

treatment. That is, the inside of the processing chamber 21 is vacuumized, process gas is

introduced thereinto, and a high frequency power is applied thereto through the antenna 25 by

driving the high frequency power supplying unit 27, the matching box 26, and the high voltage

pulse generating unit 23, so as to generate plasma As a result, positive ions are

electrostatistically induced toward the grid 24, liaving high voltage pulses applied thereon, and

injected into the surface of the tridimensional-shaped polymer 41 located inside the grid 24.

After the surface treatment is completed, the third door 33 between the processing chamber 21

and the leading-out chamber 31 is opened, and by driving the traraferring roller 61, the

ttHisferring unit 51 is transferred into the leading-out chamber 31. The tt isferring unit 51,

which is transferred into the leading-out chamber 31, passes through the fourth door 34, and is moved out of the leading-out chamber 31 to the exterior by driving the transferring roller 61.

With the opening of the fourth door 34, the transferring unit 51 is loaded out, and then, with the

closing of the fourth door 34, the inside of the leading-out chamber 31 is vacuumized. The

vacuumization of the leading-out chamber 31 serves to prevent the exterior air from being

introduced into the processing chamber 21 during the opening of the third door 33 in the

subsequent step, so that the process conditions for performing subsequent steps are recovered in

the processing chamber 21 in quick time, and thus, helps the processing chamber 21 to be

prepared to perform surface treatment. By the above method, the tridimensional-shaped

polymer 41 can be continuously surface-treated. The trarisferring unit 51 can be repeatedly used

by loading the tridimensional-shaped polymer 41 to be processed into the leading-in chamber 11

with the polymer 41 fixed thereto, and taking off the tridimensional-shaped polymer 41, which is

processed and loaded out.

In addition, the description will be made on the continuous surface treatment method of

a tridimensional-shaped polymer according to the present invention to modify the surface thereof

using plasma ion injection technology, and the method includes the steps of: (1) loading the

tridimensional-shaped polymer product to be processed into a leading-in chamber, which is gas-

exhaustible (leading-in); (2) decompressing the inside of the leading-in chamber into which the

tridimensional-shaped polymer is loaded, and exhausting the gas therefrom (first vacuumization);

(3) tr-uisferring the tridimensional-shaped polymer inside the leading-in chamber to the processing

chamber (first transfer); (4) treating the surface of the tridimensional-shaped polymer, which is

transferred into the processing chamber, by using plasma (surface-treatment); (5) decompressing

the inside of the leading-out chamber, which is gas-exhaustible, and exhausting gas therefrom

(second vacuumization); (6) traijjsferring the surface-treated the tridimensional-shaped polymer to the vacuumized leading-out chamber (second transfer); and (7) unloading the tridimensional-

shaped polymer inside the leading-out chamber to the exterior (leading-out).

The (1) leading-in step is to load the tridimensional-shaped polymer 41 product to be

processed into the gas-exhaustible leading-in chamber 11 in order to serve as a pre-treatment

process such that the tridimensional-shaped polymer 41 product is continuously supplied into the

processing chamber 21 without any influence on the vacuum degree in the processing chamber

21. Then, the (2) first vacuumization step is to decompress and gas-exhaust the inside of the

leading-in chamber 11 into which the tridimensional-shaped polymer 41 product is loaded. By

vacuumizing the inside of the leading-in chamber 11 in the (2) first vacuumization step as above,

when the trid-mensional-shaped polymer 41 product to be processed inside the leading-in

chamber 11 is transferred to the processing chamber 21 by the transferring unit, the internal

process conditions inside the processing chamber 21, such as the vacuum degree of the processing

chamber 21, or the like are little influenced, and the processing chamber 21 is prepared enough

with the conditions for transferring the tridimensional-shaped polymer 41 product into the

processing chamber 21. Then, the (3) first transfer step is to transfer the tridixiensional-snaped

polymer 41 product inside the leading-in chamber 11 to the processing chamber 21.

Subsequently, in the (4) surface-treatment step, surface-treatment is performed on the

tridimensional-shaped polymer 41 product transferred into the processing chamber 21 by using

plasma. The (5) second vacuumization step is to decompress and gas-exhaust the inside of the

gas-exhaustible leading-out chamber 31. On the contrary, by vacuumizing the inside of the

leading-out chamber 31, the surface-treatment completed tridimensional-shaped polymer 41

product can be transferred into the leading-out chamber 31 without any influence on the vacuum

degree inside the processing chamber 21. Then, in the (6) second transfer step, the surface- treatment completed tridimensional-shaped polymer 41 product is transferred into the leading-out

chamber 31, which is vacuumized. In the (7) leading-out step, the tridimensional-shaped

polymer 41, which is transferred into the leading-out chamber 31, is loaded out of the leading-out

chamber 31 after surface-treatment is completed, and another tridimensional-shaped polymer 41

product is loaded in continuously for surface-treatment.

Before or after the (2) first vacuumization step, a pre-treatment can be further performed

by applying hot air on the tridimensional-shaped polymer 41 product inside the leading-in

chamber 11 to remove moisture or the like therefrom. The pre-treatment is intended to heat the

tridimensional-shaped polymer 41 product previously, to facilitate the ion-injection into the

surface of the tridimensional-shaped polymer 41 more deeply. In the pre-treatment, hot air at a

temperature of 70 °C to 85 °C can be applied thereon to remove moisture, and the tridimensional-

shaped polymer 41 can be locally heated. The heating temperature is varied depending on the

kinds of the polymer forming the tridimensional-shaped polymer 41 product, physical properties

and size thereof, or the like. Appropriate heating temperature can be determined by experiment

theoretically or by experience to those skilled in the art.

The (4) surface-treatment step is performed by supplying process gas including argon,

nitrogen, or nmture thereof to the processing chamber 21 continuously at a rate of 15 to 100

seem, and applying process conditions in that a pulse width is 20 ms to 30 ms, a high frequency

for plasma generation is 500 Hz to 1,500 Hz, and a high voltage is 21 KV to 25 KV. The

process condition can be varied depending on the kinds, size, and shape of the tridimensional-

shaped polymer 41, or the like, and appropriate processing conditions can be determined

theoretically or by experience, and ion-injection for the surface-treatment can be performed

according thereto, which can be understood to those skilled in the art. The tridimensional-shaped polymer 41 as an object, which is processed by the surface-

treatment apparatus and the surface-treatment method according to the present invention

described as above, may include all kinds of publicly known polymer, and preferably includes

vinyl polymer 41 group, such as low density polyethylene (LDPE), linear low density

polyethylene (LLDPE), high density polyethylene (HOPE), polypropylene (PP), polystyrene (PS)

or the like, nylon group such as nylon 6, nylon 11, nylon 12, nylon 66, or the like, and

polycarbonate (PQ, polyethylene terephthalate (PET), acrylomtrUe-butadiene-styrene copolymer

(ABS), styrene-acrylonitrile copolymer (SAN), polyphenylene sulfide (PPS), polyelherimide

(PET), polyimide (PI), modified poly phenylene oxide (MPPO), modified polysulfone (MPSU),

modified polyether (MPES), polyether ether ketone (PEEK), or the like.

Now hereinafter, preferred embodiments and comparative examples according to the

present invention will be described.

The description on following embodiments is just intended to provide exemplary

examples of the present invention, and it is to be understood not to limit the scope of the present

invention.

Embodiments 1 and 2

By using the apparatus illustrated in FIG. 1, the tridimensional-shaped polymer 41 to be

processed, polyethylene product is loaded into the leading-in chamber 11, and the inside of the

leading-in chamber 11 is decompressed, gas-exhausted, and vacuumized. After the

vacuumization is completed, the tridimensional-shaped polymer 41 product inside the leading-in

chamber 11 is transferred into the processing chamber 21, and plasma surface-treatment is

performed with process conditions described in following Table 1. Then, after the inside of the

leading-out chamber 31 is decompressed, gas-exhausted, and vacuumized, the surface-treatment completed tridimensional-shaped polymer 41 product is transferred into the vacuumized leading- out chamber 31, and is finally transferred out of the leading-out chamber 31. As a result, the ion density during processing, and the surface resistance of the tridimensional-shaped polymer as an object after the treatment are measured, and the results are shown in Table 1. [Table 1]

Industrial Applicability

Therefore, according to the present invention, the surface resistance as low as 10 to 10

Ω/cm² is obtained, thereby improving the antistatic characteristics and the conductibility of the surface of the tridimensional-shaped polymer 41 , or the like, and continuous surface treatment for the tridimensional-shaped polymer 41 is possible, thereby making it easier to mass-produce the tridimensional-shaped polymer 41 product.

While the present invention has been described and illustrated herein with reference to the preferred embodiments thereof, it will be apparent to those skilled in the art that various modifications and variations can be made therein without dφarting from the spirit and scope of the invention. Thus, it is intended that the present invention covers the modifications and variations of this invention that come within the scope of the appended claims and their equivalents.

Claims

What Is Claimed Is:

1. A continuous surface treatment apparatus of tridimensiorial-shaped polymer

comprising a high frequency power supplying device for generating plasma and thus, injecting

ions, and including a high frequency power supplying unit, a mafching box, and an antenna; a gas

introducing unit for supplying process gas to be ionized for plasma; a gas supplying unit

connected to the gas introducing unit; and a processing chamber having a vacuum pump and the

like, the continuous surface treatment apparatus further comprising: a leading-in chamber, and an leading-out chamber, which are installed before and after

the processing chamber respectively with adjacent thereto, and are adapted to be gas-exhaustible; a transferring unit installed to sequentially pass by through the leading-in chamber, the

processing chamber, and the leading-out chamber, transferring means for driving the transferring unit; and doors being positioned in the leading-in chamber and the leading-out chamber

respectively, and in partitions between the leading-in chamber and the processing chamber, and

between the processing chamber and the leading-out chamber respectively, and automatically

capable of being opened/closed so that the transferring unit can pass by therethrough.

2. The apparatus as claimed in claim 1, wherein the trarisferring means is transferring

rollers installed to be able to rotate.

3. The apparatus as claimed in claim 1, wherein the transferring unit comprises: a

trarisferring plate; a transferring wing integrally fixed on top of the ϋansferring plate and variable with contact on the transferring rollers; and a fixture integrally fixed on bottom of the traroferrng

plate and adapted to hang or fix a tridimensional-shaped polymer.

4. The apparatus as claimed in claim 1, further comprising a pre-processing chamber,

which is installed with adjacent to the leading-in chamber in order to pre-treat the tridimensional-

shaped polymer to be surface-treated by supplying a dried hot air at a temperature of 70°C to

85°C to the tridimensional-shaped polymer, the pre-processing chamber including a fan for

supplying hot air into the pre-processing chamber, a first cutoff valve for cutting off the flow of

the hot air supplied to the fan, a second cutoff valve for cutting off the flow of the air to be

discharged from the pre-processing chamber to vacuumize the pre-processing chamber, and a

vacuum pump for discharging the air from the pre-processing chamber through the second cutoff

valve.

5. The apparatus as claimed in claim 4, wherein the first cutoff valve further include an

air compressor connected thereto to generate hot air.

6. The apparatus as claimed in claim 4, further comprising a second pre-processing

chamber, which is installed with adjacent to the pre-processing chamber, the second pre¬

processing chamber including a second fan for supplying hot air into the pre-processing chamber,

a third cutoff valve for cutting off the flow of the hot air supplied to the second fan, a fourth cutoff

valve for cutting off the flow of the air to be discharged from the second pre-processing chamber

to vacuumize the pre-processing chamber, and a vacuum pump for discharging the air from the

pre-processing chamber through the fourth cutoff valve.

7. A continuous surface treatment method for tridimensional-shaped polymer by

surface modification using plasma ion implantation technology, the method comprising steps of:

(1) loading a tridimensional-shaped polymer product to be processed into a gas-

exhaustible leading-in chamber (leading-in); (2) decompressing and gas-exhausting the inside of the leading-in chamber into which

the tridimensional-shaped polymer product is loaded (first vacuumization);

(3) transferring the tridimensional-shaped polymer product inside the leading-in

chamber to a processing chamber (first transfer);

(4) performing surface-treatment on the tridimensional-shaped polymer product inside

the processing chamber by using plasma (surface treatment);

(5) decompressing and gas-exhausting the inside of a gas-exhaustible leading-out

chamber (second vacuumization);

(6) transferring the surface-treatment completed tridimensional-shaped polymer product

into the vacuumized leading-out chamber (second transfer); and (7) unloading the tridimensional-shaped polymer product inside the leading-out

chamber to the exterior (leading-out).

8. The method as claimed in claim 7, before or after the (2) first vacuumization step, the

method further comprising a step of performing a pre-treatment by applying hot air on the

tridimensional-shaped polymer product inside the leading-in chamber to remove moisture

therefrom.

9. The method as claimed in claim 7, wherein the (4) surface-treatment step is carried

out by continuously supplying process gas including argon, nitrogen, or these mixture to the

processing chamber at a rate of 15 to 100 seem under the process conditions of 20 to 30 ms of

pulse width, 500 to 1,500 Hz of high frequency for plasma generation, and 21 to 25 KV of high

voltage pulse.