WO2005008718A1

WO2005008718A1 - Continuous surface-treating apparatus for film shape of polymer and continuous surface-treating method thereof

Info

Publication number: WO2005008718A1
Application number: PCT/KR2003/002109
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: KR20030074512A; AU2003269527A1; KR100442309B1

Abstract

The present invention provides a continuous surface treatment apparatus, and a continuous surface method on the surface of film-shaped polymer by plasma ion-implantation of negative voltage pulse, for improving the antistatic characteristics and the conductibility of the surface of the polymer. In the continuous surface treatment apparatus of film-shaped polymer including a high frequency power supplying device for generating plasma and thus, 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, and a processing chamber having a vacuum pump and the like, the continuous surface treatment apparatus further includes 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, spouts located in partitions between the leading-in chamber and the processing chamber, and between the processing chamber and the leading-out chamber respectively, for passing the film-shaped polymer therethrough, a cylindrical plate for holding the film-shaped polymer inside the processing chamber, and a cylindrical-shaped grid located near the cylindrical plate, the cylindrical plate and the cylindrical-shaped grid being electrically connected to a high voltage pulse generating unit.

Description

CONTINUOUS SURFACE-TREATING APPARATUS FOR FILM SHAPE OF POLYMER AND CONTINUOUS SURFACE-TREATING METHOD THEREOF

Technical Field The present invention relates to a continuous surface treatment of film-shaped polymer.

More particularly, the present invention relates to an apparatus for continuously performing a

surface-treatment on film-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 a suiface-treatinent on film-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, biocompatibility, 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 NH₃ (see

U.S. 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

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 hydrophilic property of polypropylene, polyethylene,

polystylene, etc. (see M. Morra, E. Occhiello, 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 athin 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 JUS, 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, but are.

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 tridmensional 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

for improving antistatic characteristics and conductibility of the surface of film-shaped polymer

by plasma ion implantation by negative voltage pulse, 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 film-shaped polymer including a high frequency power

supplying device for generating plasma and thus, 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,

and a processing chamber having a vacuum pump and the like, and further including 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, grooves

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

the processing chamber and the leading-out chamber respectively, for passing the film-shaped

polymer therethrough, a cylindrical plate for holding the film-shaped polymer inside the

processing chamber, and a cylindrical-shaped grid located near the cylindrical plate, the

cylindrical plate and the cylindrical-shaped grid being electrically connected to a high voltage

pulse generating unit.

The processing chamber may be structured such that two discrete chambers are

provided in parallel for the treatment of both surfaces of the film-shaped polymer, and a second processing chamber may be provided in parallel with the processing chamber, the structure of the

second processing chamber being identical or similar to the structure of the processing chamber.

In the leading-in chamber, there may be installed an unprocessed roll stock having

unprocessed material wound thereon for trarisferring the film-shaped polymer to the processing

chamber, and rotating means for rotating the unprocessed roll stock.

In the leading-out chamber, there may be installed a processed roll stock for winding

material, surface-treated inside the processing chamber, and rotating means for rotating the

processed roll stock.

Preferably, the rotating means in the leading-in chamber and the rotating means in the

leading-out chamber may be arranged to operate under synchronous rotary speed in order to roll

or unroll the film-shaped polymer at a given rate.

In another aspect of the present invention, the present invention provides a continuous

surface treatment method for film-shaped polymer by surface modification using plasma ion

implantat on technology, which may include the steps of (1) mounting the unprocessed roll stock

having the film-shaped polymer to be processed wound thereon inside the gas-exhaustible

leading-in chamber, and mounting the processed roll stock, which the surface-treated film-shaped

polymer will be wound on, inside the gas-exhaustible leading-out chamber (leading-in); (2)

decompressing and gas-exhausting the inside of the leading-in chamber having the unprocessed

roll stock installed therein, and the inside of the leading-out chamber having the processed roll

stock, which the surface-treated film-shaped polymer is folded on, installed therein (first

vacuumization); (3) transferring the film-shaped polymer from the unprocessed roll stock inside

the leading-in chamber to the processing chamber (first transfer); (4) treating the surface of the

film-shaped polymer, which is transferred into the processing chamber, by using plasma (surface- treatment); (5) transferring the surface-treated film-sliaped polymer into the vacuumized leading-

out chamber (second transfer); and (6) drawing the processed roll stock mounted inside the

leading-out chamber out of the leading-out chamber after the film-shaped polymer on the

unprocessed roll stock is run out (leading-out). Preferably, before or after the (2) first vacuumization step, the method may further

include a pre-treatment step by applying hot air on the film-shaped polymer product inside the

leading-in chamber to remove moisture therefrom.

In the (4) surface-treatment step, process gas including argon, nitrogen, or these rriixture

is continuously supplied to the processing chamber at a rate of 15 to 100 seem under the process

conditions of 15 to 25 ms of pulse width, 500 to 1,500 Hz of high frequency for plasma

generation, and 26 to 30 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 incorporated 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 invention.

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

continuous surface treatment apparatus of film-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 drawings.

As shown in FIG. 1, the continuous surface treatment apparatus of film-shaped polymer

according to one embodiment of the present invention is structured to 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 matching box 26,

and an antenna 28; 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 41, which are installed before and

after the processing chamber 21 respectively with adjacent thereto, and are adapted to be gas-

exhaustible; the spout located in partitions between the leading-in chamber 11 and the processing

chamber 21, and between the processing chamber 21 and the leading-out chamber 41

respectively, for passing the film-shaped polymer 52 therethrough; a cylindrical plate 25 for

holding the film-shaped polymer 52 and a cylindrical-shaped grid 24 encompassing the

cylindrical plate 25 remote a little therefrom inside the processing chamber 21 ;, and the cylindrical

plate 25 and the cylindrical-shaped grid 24 are electrically connected to a high voltage pulse

generating unit 23. It can be understood that the surface treatment apparatus of film-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 matching box 26, and

the antenna 28; 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 vacuumized 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

41, 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, especially a

film-shaped polymer 52 and the leading-in chamber 11 and the leading-out chamber 41 are gas

exhaustible. In the leading-in chamber 11, an unprocessed roll stock 51 is installed, and the

unprocessed roll stock 51 has the film-shaped polymer 52 as an object wound therethrough. In

the leading-out chamber 41, a processed roll stock 61 is installed, and the processed roll stock 61

has the surface-treated film-shaped polymer 52 wound therethrough Then, the leading-in chamber 11, the processing chamber 21, and the leading-out chamber 41 are vacuumized by a

vacuum pump 12, a vacuum pump 22, and a vacuum pump 32 respectively. The film-shaped

polymer 52 is unrolled from the unprocessed roll stock 51, and passes through the spout located

on 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 41, in which each of

the grooves has a size enough to pass the film-shaped polymer 52 therethrough, and the film-

shaped polymer 52 is surface-treated by plasma ion implantation in the processing chamber 21 in

the path of the above. Then, the surface-treated film-shaped polymer 52 out of the processing

chamber 21 goes into the leading-out chamber 41, and is rolled into the processed roll stock 61

thereinside. The film-shaped polymer 52 can be continuously surface-treated through the above

structural path.

The processing chamber 21 includes a cylindrical plate 25 for holding the film-shaped

polymer 52, and a cylindrical-shaped grid 24 encompassing the cylindrical plate 25 remote a little

therefrom. In the above structure, the film-shaped polymer 52 to be surface-treated is transferred

in contact with the cylindrical plate 25, and when passing under the grid 24, the ions induced by

the grid 24 are injected into the film-shaped polymer 52 so that the surface of the film-shaped

polymer 52 is treated.

The cylindrical plate 25 and the cylindrical-shaped grid 24 are electrically connected to

the high voltage pulse generating unit 23. With this, ions of the plasma are electrostatically

induced by the grid 24 and the cylindrical plate 25, and injected into the surface of the film-shaped

polymer passing between the grid 24 and the cylindrical plate 25.

Further, in the leading-in chamber 11, there is provided a pre-processing device for pre-

treating the film-shaped polymer 52 to be surface-treated by applying a dried hot air at a temperature of 70°C to 85°C, and the pre-processing device may be a fan for supplying hot air,

and to the pre-processing device, a cutoff valve for cutting off the flow of the hot air, and an air

compressor for generating hot air, or the like are connected to the pre-processing device. The

pre-treatment by the pre-processing device helps the ion to implant more deφly into the surface

of the film-shaped polymer 52 by pro-heating the film-shaped polymer 52 to be surface-treated.

In the pre-treatment, hot air at a temperature of 70°C to 85°C is applied on the surface of the

polymer product to remove moisture, and the film-shaped polymer 52 can be partially heate

The heating temperature varies depending on the types, physical properties, size, and the like of

the polymer of polymer products, and appropriate heating temperature can be deteπnined

theoretically or experimentally by experience of those in the art.

The processing chamber 21 can be structured such that two discrete chambers are

provided in parallel for the treatment of both surfaces of the film-shaped polymer 52, and for this

purpose, a second processing chamber 31 can be provided, in which the structure of the second

processing chamber 31 is identical or similar to the structure of the processing chamber 21. That

is, the second processing chamber 31 may include a vacuum pump 32, a second high voltage

pulse generating unit 33, a second grid 34, a second cylindrical plate 35, a second matching box

36, a second high frequency power supplying unit 37, and a second antenna 38, or the like. As

such, the second processing chamber 31 has a structure identical or similar to the structure of the

processing chamber 21, and the front surface of the film-shaped polymer 52 is surface-treated in

the processing chamber 21, and the back surface of the film-shaped polymer 52 is surface-treated

in the second processing chamber 31. Thus, the structures as above allow the selective treatment

of the surfaces of the film-shaped polymer 52, that is, by the operation of the chamber 21 or the

chamber 31, one surface of the film-shaped polymer 52 can be treated, or by the operation of the both the chamber 21 and the chamber 31, the both surfaces of the film-shaped polymer 52 can be

treated.

The leading-in chamber 11 includes a unprocessed roll stock 51 having unprocessed

roll wound, for traι_sferring the film-shaped polymer 52 to the processing chamber 21, and

rotating means for rotating the unprocessed roll stock 51. The leading-out chamber 41 includes

a processed roll stock 61 for winding a polymer roll, which is surface-treated in the processing

chamber 21, wound, and rotating means for rotating the processed roll stock 61. The rotating

means may employ a typical geared motor, or the like. It can be understood that the geared motor

is publicly known as much as it is commercially available to those in the art. Preferably, the

rotating means of the leading-in chamber 11 and the rotating means of the leading-out chamber

41 can be arranged to operate under synchronous rotary speed in order to roll or unroll the film-

shaped polymer 52 at a constant given rate. Thus, by the synchronization, the film-shaped

polymer 52 can pass through the processing chamber 21 (or the second processing chamber 31)

in arranged processing sequences, and can be smoothly wound on the processed roll stock 61. Now, describing the specific processing sequences of the surface treatment by the

above structure with reference to FIG. 1, the unprocessed roll stock 51 having the film-shaped

polymer 52 wound thereon is installed inside the leading-in chamber 11, and the processed roll

stock 61, which the surface-treated film-shaped polymer 52 will be wound on, is installed inside

the leading-out chamber 41. Then, the leading-in chamber 11, the processing chamber 21, and

the leading-out chamber 41 are all vacuumized. The film-shaped polymer 52 inside the leading-

in chamber 11 passes through the pre-processing device, and then, between the cylindrical plate

25 and the grid 24 inside the processing chamber 21, and then, is rolled on the processed roll stock

61 inside the leading-out chamber 41, so as to operate the surface treatment. The plasma treatment is the same as or similar to a typical conventional plasma

treatment, which operates such that a process gas is supplied, and the high frequency power

supplying unit 27, the matching box 26, and the high voltage pulse generating unit 23, or the like

are driven, and high frequency power is applied through the antenna 28 to generate plasma, and

positive ions are electrostatically induced toward the grid 24 having high voltage pulse applied

thereon, so that the ions are injected into the surface of the film-shaped polymer 52 inside the grid

24. Then, if the unprocessed roll stock 51 inside the leading-in chamber 11 is run out, the

processed roll stock 61 inside the leading-out chamber 41 is drawn out of the chamber 41, so that

the film-shaped polymer 52 can be surface-treated continuously. Jn addition, the continuous surface treatment method of the film-shaped polymer

according to the present invention, employing plasma ion implantation technology for surface

modification, includes the steps of: (1) mounting the unprocessed roll stock 51 having the film-

shaped polymer 52 to be processed wound thereon inside the gas-exhaustible leading-in chamber

11, and mounting the processed roll stock 61, which the surface-treated film-shaped polymer 52

will be wound on, inside the gas-exhaustible leading-out chamber 41 (leading-in); (2)

decompressing and gas-exhausting the inside of the leading-in chamber 11 having the

unprocessed roll stock 51 installed therein, and the inside of the leading-out chamber 41 having

the processed roll stock 61, having the surface-treated film-shaped polymer 52 wound thereon,

installed therein (first vacuumization); (3) trar_3fe_ring the film-shaped polymer from the

unprocessed roll stock 51 inside the leading-in chamber 11 to the processing chamber 21 (first

transfer); (4) treating the surface of the film-shaped polymer 52, which is transferred into the

processing chamber 21, by using plasma (surface-treatment); (5) transferring the surface-treated

film-shaped polymer 52 into the vacuumized leading-out chamber 41 (second transfer); and (6) drawing the processed roll stock 61 mounted inside the leading-out chamber 41 out of the

chamber 41 after the film-shaped polymer 52 on the unprocessed roll stock 51 is run out (leading-

out).

The (1) leading-in step is to install the unprocessed roll stock 51 having the film-shaped

polymer 52 to be processed wound thereon inside the gas-exhaustible leading-in chamber 11 , and

install the processed roll stock 61, which the surface-treated fihn-shaped polymer 52 will be

wound on, inside the gas-exhaustible leading-out chamber 41.

The (2) first vacuumization step is to decompress and gas-exhaust the inside of the

leading-in chamber 11 having the unprocessed roll stock 51 installed therein, and the inside of the

leading-out chamber 41 having the processed roll stock 61, having the surface-treated film-shaped

polymer 52 wound thereon, installed therein, and to accomplish a vacuum state for surface-

treatment by plasma

The (3) first transfer step is to transfer the film-shaped polymer 52 from the unprocessed

roll stock 51 inside the leading-in chamber 11 to the processing chamber 21, and in (4) surface-

treatment step, surface-treatment is performed on the film-shaped polymer 52, which is

transferred into the processing chamber 21 , by using plasma

Then, the (5) second transfer step is to transfer the surface-treated film-shaped polymer

52 into the vaeuumized leading-out chamber 41, and in (6) leading-out step, after the film-shaped

polymer 52 on the unprocessed roll stock 51 is run out, the processed roll stock 61 mounted inside

the leading-out chamber 41 is drawn out of the chamber 41, and thus, the film-shaped polymer 52

wound on the unprocessed roll stock 51 can be placed under continuous surface treatment.

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

by applying hot air on the polymer product inside the leading-in chamber 11 to remove moisture or the like therefrom. The pre-treatment is intended to pre-heat the polymer product inside the

leading-in chamber 11, and to facilitate the ion-implantation more deep into the surface of the

polymer product. In the pre-treatment, hot air at a temperature of 70 °C to 85 °C is applied on

the surface of the polymer product to remove moisture, and the film-shaped polymer 52 can be

partially heated. The heating temperature is varied depending on the kinds of the polymer

forming the film-shaped polymer 52 product, physical properties and size thereof, or the like.

Appropriate heating temperature can be determined theoretically, or experimentally by experience

to those skilled in the art.

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

nitrogen, or rnixture 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 15 ms to 25 ms, a high frequency

for plasma generation is 500 Hz to 1,500 Hz, and a high voltage is 26 KV to 30 KV. The

process condition can be varied depending on the kinds, size, shape of the film-shaped polymer

52, 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 well understood to those skilled in the art.

The film-shaped polymer 52 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

group, such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high

density polyethylene (HDPE), polypropylene (PP), polystyrene (PS) or the like, nylon group such

as nylon 6, nylon 11, nylon 12, nylon 66, or the like, polycarbonate (PC), polyethylene

terephthalate (PET), acrylorύtrile-butadiene-styrene copolymer (ABS), styrene-acrylonitrile copolymer (SAN), polyphenylene sulfide (PPS), polyetherimide (PEI), polyimide (PI), modified

poly phenylene oxide (MPPO), modified polysulfone (MPSU), modified polyefher (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 to 3 By using the apparatus illustrated in FIG. 1, the film-shaped polymer 52 made of

polyethylene to be processed is installed inside the leading-in chamber 11 in the form of the

unprocessed roll stock 51, and the processed roll stock 61 having the surface-treated film-shaped

polymer 52 wound thereon is installed inside the leading-out chamber 41. The respective

insides of the leading-in chamber 11, the processing chamber 21, and the leading-out chamber 41

are decompressed, gas-exhausted, and vacuumized. Sequentially, the film-shaped polymer 52 is

unrolled from the unprocessed roll stock 51 inside the leading-in chamber 11, and is placed under

the surface- treatment while passing through the cylindrical plate 25 and the grid 24 of the

processing chamber 21. The plasma surface-treatment is performed with process conditions

described in following Table 1. When the unprocessed roll stock 51 inside the leading-in

chamber 11 is run out, the vacuum is released. Then, the processed roll stock 61 is drawn out of

the leading-out chamber 41, and thus, the surface-treatment is completed. As a result, the ion

density during the process, and the surface resistance of the film-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 polymer, or the like, and continuous surface treatment for the film-shaped polymer 52 is possible, thereby making the mass-production of the film-shaped polymer product easy.

While the present invention has been described and illustrated herein with reference to the preferred embodiments thereofj it will be apparent to those skilled in the art that various modifications and variations can be made therein without departing 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 film-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 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; 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; spouts located in partitions between the leading-in chamber and the processing

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

passing the film-shaped polymer therethrough; a cylindrical plate for holding the film-shaped polymer inside the processing chamber,

and a cylindrical-shaped grid located near the cylindrical plate, the cylindrical plate and the

cylindrical-shaped grid being electrically connected to a high voltage pulse generating unit.

2. The apparatus as claimed in claim 1, wherein the processing chamber is structured

such that two discrete chambers are provided in parallel for the treatment of both surfaces of the

film-shaped polymer, and a second processing chamber is provided in parallel with the processing

chamber, the structure of the second processing chamber being identical or similar to the structure

of the processing chamber.

3. The apparatus as claimed in claim 1, wherein the leading-in chamber comprises an

unprocessed roll stock having unprocessed polymer material wound thereon for transferring the

film-shaped polymer to the processing chamber, and rotating means for rotating the unprocessed

roll stock.

4. The apparatus as claimed in claim 1, wherein the leading-out chamber comprises a

processed roll stock for winding polymer material, surface-treated inside the processing chamber,

and rotating means for rotating the processed roll stock.

5. The apparatus as claimed in claim 3 or 4, wherein the rotating means in the leading-in

chamber and the rotating means in the leading-out chamber are arranged to operate under

synchronous rotary speed in order to roll or unroll the film-shaped polymer at a given rate.

6. A continuous surface treatment method for film-shaped polymer by surface

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

(1) mounting the unprocessed roll stock having the film-shaped polymer to be

processed wound thereon inside the gas-exhaustible leading-in chamber, and mounting the

processed roll stock, which the surface-treated film-shaped polymer will be wound on, inside the

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

unprocessed roll stock installed therein, and the inside of the leading-out chamber having the

processed roll stock, which the surface-treated film-shaped polymer is wound on, installed therein

(first vacuumization); (3) transferring the film-shaped polymer from the unprocessed roll stock inside the

leading-in chamber to the processing chamber (first transfer);

(4) treating the surface of the film-shaped polymer, which is transferred into the

processing chamber, by using plasma (surface-treatment); (5) transferring the surface-treated film-shaped polymer into the vacuumized leading-

out chamber (second transfer); and

(6) drawing the processed roll stock mounted inside the leading-out chamber out of the

leading-out chamber after the film-shaped polymer on the unprocessed roll stock is run out

(leading-out).

7. The method as claimed in claim 6, 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 film-

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

8. The method as claimed in claim 6, 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 15 to 25 ms of

pulse width, 500 to 1,500 Hz of high frequency for plasma generation, and 26 to 30 KV of high

voltage pulse.