JPH06324A - Method and device for preventing increase in contact angle on surface of substrate or base material - Google Patents
Method and device for preventing increase in contact angle on surface of substrate or base materialInfo
- Publication number
- JPH06324A JPH06324A JP4180538A JP18053892A JPH06324A JP H06324 A JPH06324 A JP H06324A JP 4180538 A JP4180538 A JP 4180538A JP 18053892 A JP18053892 A JP 18053892A JP H06324 A JPH06324 A JP H06324A
- Authority
- JP
- Japan
- Prior art keywords
- contact angle
- substrate
- increase
- filter
- air
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000000463 material Substances 0.000 title claims abstract description 30
- 239000011521 glass Substances 0.000 claims abstract description 29
- 239000000126 substance Substances 0.000 claims description 16
- 239000000356 contaminant Substances 0.000 abstract description 6
- 239000007789 gas Substances 0.000 description 25
- 239000000428 dust Substances 0.000 description 24
- 239000010419 fine particle Substances 0.000 description 18
- 239000002585 base Substances 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 235000012431 wafers Nutrition 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
- 239000013618 particulate matter Substances 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 5
- 238000011109 contamination Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 231100001261 hazardous Toxicity 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 239000011265 semifinished product Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 239000005368 silicate glass Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000005385 borate glass Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000075 oxide glass Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000005365 phosphate glass Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Central Air Conditioning (AREA)
- Treating Waste Gases (AREA)
- Cleaning In General (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、基材又は基盤表面の接
触角の増加を防止する方法及び装置に係り、特に半導体
や液晶などの先端産業における原材料、半製品、製品の
基材や基盤表面の接触角の増加防止に関する。本発明の
適用分野の例を以下に示す。 （１）半導体工場におけるウエハの接触角増加防止。 （２）液晶工場におけるガラス基盤の接触角増加防止。 （３）精密機械工場における基盤の接触角増加防止。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and apparatus for preventing an increase in the contact angle of a substrate or substrate surface, and more particularly to a raw material, a semi-finished product, a substrate or substrate for advanced industries such as semiconductors and liquid crystals. Preventing an increase in the contact angle of the surface. The following are examples of fields of application of the invention. (1) Prevention of increase in wafer contact angle in semiconductor factories. (2) Prevent increase of contact angle of glass substrate in LCD factory. (3) Preventing the increase of the contact angle of the board in the precision machinery factory.
【０００２】[0002]
【従来の技術】従来の技術に関して、半導体工場におけ
るクリーンルームの空気清浄を例に説明する。従来のク
リーンルームの空気清浄方法あるいはその装置を大別す
ると、 （１）機械的ろ過方法（例えばＨＥＰＡフィルター） （２）静電的に微粒子の捕集を行う高電圧による荷電及
び導電性フィルターによるろ過方式（例えばＨＥＳＡフ
ィルター） であるが、これらの方式は、いずれも微粒子（粒子状物
質）除去を目的としており、炭化水素（Ｈ．Ｃ），ＳＯ
ｘ，ＮＯｘ，ＨＣｌ，ＮＨ3 のような接触角を増加させ
るガス状の汚染物（有害成分）の除去には効果がない欠
点があった。ガス状の汚染物（有害成分）であるＨ．
Ｃ．の除去法としては、燃焼分解法、触媒分解法、Ｏ3
分解法などが知られている。しかし、これらの方法はク
リーンルームへの導入空気に含有する極低濃度Ｈ．Ｃ．
除去には効果がない。2. Description of the Related Art A conventional technique will be described by taking air cleaning in a clean room in a semiconductor factory as an example. The air cleaning methods in the conventional clean room or the apparatus therefor are roughly classified into (1) a mechanical filtration method (for example, a HEPA filter) (2) filtration by a high voltage charged and conductive filter that electrostatically collects fine particles. Although these are methods (for example, HESA filter), all of these methods are intended to remove fine particles (particulate matter), and hydrocarbon (HC), SO
There is a drawback that it is ineffective in removing gaseous pollutants (toxic components) that increase the contact angle such as x, NOx, HCl and NH 3 . H.V., which is a gaseous pollutant (hazardous ingredient).
C. As a method for removing methane, combustion decomposition method, catalytic decomposition method, O 3
The decomposition method and the like are known. However, these methods have a very low H.V. concentration in the air introduced into the clean room. C.
It has no effect on removal.
【０００３】クリーンルームにおいては、自動車排ガス
に起因するような導入空気中の低濃度のＨ．Ｃ．も汚染
質として問題となる。また、クリーンルームにおける作
業で生じた各種の溶剤（例えば、アルコール、ケトン類
等）も汚染質として問題となる。また、Ｈ．Ｃ．以外の
有害成分としては、ＳＯｘ，ＮＯｘ，ＨＣｌ，ＮＨ3 な
どがあり、これらの除去法としては適宜のアルカリ性物
質や酸性物質を用いた中和反応や酸化反応に基づく方法
などが知られている。しかし、これらの方法も、成分濃
度がクリーンルームへの導入空気に含有するような極低
濃度の場合には効果が少ない。更に、微粒子とガス状汚
染物の中間体であるミストやクラスターのような物質
も、従来のフィルタでは除去できなかった。In a clean room, a low concentration of H.S. C. Also poses a problem as a pollutant. Further, various solvents (for example, alcohols, ketones, etc.) generated in the work in the clean room also pose a problem as contaminants. In addition, H. C. Other harmful components include SOx, NOx, HCl, NH 3 and the like. As a method for removing these, a method based on a neutralization reaction or an oxidation reaction using an appropriate alkaline substance or acidic substance is known. . However, these methods are also less effective when the component concentration is an extremely low concentration such as contained in the air introduced into the clean room. Furthermore, substances such as mist and clusters, which are intermediates between fine particles and gaseous pollutants, could not be removed by conventional filters.
【０００４】[0004]
【発明が解決しようとする課題】クリーンルームにおけ
る汚染物（粒子状物質及び接触角を増加させるガス状有
害物質）は、半導体製品の生産性（歩留り）を低下させ
る原因、すなわち、ウエハ、半製品、製品の基盤表面へ
の汚染物の沈着による破損となるため、これらの除去が
必要となってきている。即ち、ウエハ、半製品、製品の
基盤が、粒子状物質や接触角を増加させる有害成分に汚
染されると、基盤表面の接触角が増加する。Contaminants (particulate matter and gaseous toxic substances that increase the contact angle) in a clean room are factors that reduce the productivity (yield) of semiconductor products, that is, wafers, semi-finished products, These substances are required to be removed because they are damaged by the deposition of contaminants on the surface of the substrate of the product. That is, when a wafer, a semi-finished product, or a substrate of a product is contaminated with a particulate matter or a harmful component that increases the contact angle, the contact angle of the substrate surface increases.
【０００５】接触角とは、表面の汚染の程度を示すもの
であり、表面のぬれ性を表わす角度で表現され、接触角
が高いと汚染されており、逆に接触角が低いと汚染され
ていない。このため、半導体製品の生産性向上のため、
接触角の増加を防止する方法や装置が要求されている。
そこで、本発明は、上記した問題点に対応するための、
接触角を増加する汚染物質を効果的に除去できる接触角
の増加防止方法及びその装置を提供することを課題とす
る。The contact angle indicates the degree of contamination on the surface, and is expressed by an angle representing the wettability of the surface. A high contact angle results in contamination, and a low contact angle results in contamination. Absent. Therefore, in order to improve the productivity of semiconductor products,
There is a need for methods and devices that prevent an increase in contact angle.
Therefore, the present invention, in order to address the above problems,
It is an object of the present invention to provide a method for preventing an increase in contact angle and a device therefor capable of effectively removing contaminants that increase the contact angle.
【０００６】[0006]
【課題を解決するための手段】上記課題を解決するため
に、本発明では、基材又は基盤表面の接触角の増加を防
止する方法において、該基材又は基盤と接触する気体
を、ガラス及び／又はフッ素樹脂を含有する除去手段に
より、該気体中の有害物質を除去して、前記基材又は基
盤と接触させることとしたものである。また、本発明で
は、基材又は基盤表面の接触角の増加を防止する装置に
おいて、該基材又は基盤と接触する気体を通す、有害物
質を除去するためのガラス及び／又はフッ素樹脂を充填
した除去装置を備えたこととしたものである。In order to solve the above-mentioned problems, in the present invention, in a method for preventing an increase in the contact angle of a substrate or substrate surface, the gas contacting the substrate or substrate is treated with glass and The harmful substance in the gas is removed by a removing means containing a fluororesin and / or brought into contact with the base material or the substrate. Further, in the present invention, in a device for preventing an increase in the contact angle of the surface of the base material or the base material, glass and / or fluororesin for removing a harmful substance, which is permeable to a gas in contact with the base material or the base material, is filled. The removal device is provided.
【０００７】次に、本発明を接触する気体が空気である
場合を例として詳細に説明する。なお、接触する気体は
空気以外に不純物の少ないガスが好ましく、Ｎ2 ガス等
の不活性ガスでもよい。有害成分除去手段に用いる基材
は、空気中に存在する極低濃度の接触角を増加させる有
害成分が高効率に長時間安定して除去できるガラス又は
フッ素樹脂であり、これらは単独で又は、組合せて用い
ることができる。通常、ガラスとフッ素樹脂を組合せて
用いると効果的であることから好ましい。例えば、ガラ
スを繊維状とし、これにフッ素樹脂をバインダとして適
当な形状に成形することで、充填密度の高い有害ガスと
の接触表面積の広い有害成分除去フィルタができる。Next, the present invention will be described in detail by taking as an example the case where the gas in contact is air. The gas to be contacted is preferably a gas containing few impurities other than air, and may be an inert gas such as N 2 gas. The base material used for the harmful component removing means is glass or a fluororesin capable of stably removing a harmful component that increases the contact angle of an extremely low concentration existing in the air with high efficiency for a long time, and these are used alone or, It can be used in combination. Usually, it is preferable to use a combination of glass and a fluororesin because it is effective. For example, by forming glass into a fibrous shape and using fluororesin as a binder to form the glass into an appropriate shape, a harmful component removing filter having a wide contact surface area with a harmful gas having a high packing density can be obtained.
【０００８】使用するガラスとしては、酸化物ガラス
系、例えばケイ酸塩ガラス、リン酸塩ガラス、ホウ酸塩
ガラスが一般的である。この内、ケイ酸塩ガラスの一種
であるホウケイ酸ガラス（主要成分：Ｎ2 Ｏ−Ｂ2 Ｏ3
−ＳｉＯ2 ）が成形が容易で、効果が高く、かつ安価で
あることから好ましい。また、フッ素樹脂としては、四
フッ化樹脂、四−六フッ化樹脂、ＰＦＡ樹脂、三フッ化
エチレン樹脂、四フッ化エチレン−エチレン共重合体、
フッ化ビニリデン樹脂、フッ化ビニル樹脂等が使用でき
る。The glasses used are generally oxide glass systems such as silicate glasses, phosphate glasses and borate glasses. Of these, borosilicate glass (main component: N 2 O-B 2 O 3) which is a type of silicate glass
—SiO 2 ) is preferable because it is easy to mold, has a high effect, and is inexpensive. Further, as the fluororesin, tetrafluororesin, tetra-hexafluororesin, PFA resin, trifluoroethylene resin, tetrafluoroethylene-ethylene copolymer,
Vinylidene fluoride resin, vinyl fluoride resin, etc. can be used.
【０００９】これらの材料の使用形状は、フィルタ状、
網状、球状、ペレット状、格子状、棒状、プリーツ状な
どがある。一般にフィルタ状が効果が大きいことから好
ましい。フィルタ状で用いる場合の成形法の例として、
フッ素樹脂をバインダとして用い繊維状のガラス材をフ
ィルタ状に固めて用いる方法がある。有害成分除去フィ
ルタにおけるガラス及び／又はフッ素樹脂の充填密度
は、使用形状や要求性能などにより決めることができ
る。The shapes of these materials used are filters,
There are a net shape, a spherical shape, a pellet shape, a lattice shape, a rod shape, a pleated shape, and the like. Generally, a filter shape is preferable because it has a large effect. As an example of molding method when used in the form of a filter,
There is a method in which a fibrous glass material is solidified into a filter shape using a fluororesin as a binder. The packing density of the glass and / or the fluororesin in the harmful component removing filter can be determined according to the use shape and required performance.
【００１０】有害成分除去フィルタによる被処理空気の
処理速度は、通常ＳＶ（空間速度、ｈ-1）で１００〜１
０万、一般的には数千〜数万で用いる。これら材料の材
質や形状、組合せ、充填密度、処理速度の選択は、本装
置の利用分野、接触角を増加させる有害成分の種類や濃
度、装置規模、構造、効果、再生利用の有無、経済性な
どにより適宜予備試験を行い、決めることができる。The processing speed of the air to be processed by the harmful component removing filter is usually 100 to 1 in terms of SV (space velocity, h -1 ).
It is used at 0,000, generally several thousand to several tens of thousands. The materials, shapes, combinations, packing densities, and processing speeds of these materials are selected according to the field of use of this device, the type and concentration of harmful components that increase the contact angle, the scale of the device, the structure, the effect, the presence or absence of recycling, and the economic efficiency For example, preliminary tests can be conducted and determined appropriately.
【００１１】[0011]
【作用】ガラスあるいはフッ素樹脂による接触角を増加
させる有害成分の除去機構は、例えば空気中の有害成分
が数百種又は数千種以上の成分の混合物と言われている
ことから詳細は不明な点が多いが次のように考えられ
る。接触角の増加は、空気中有害成分の内特に分子量の
大きい物質や活性の高い物質の影響が大きいと推定さ
れ、これらの物質がガラスやフッ素樹脂により効果的に
吸着・捕集されることにより除去される。すなわち、多
種類の空気中の有害成分の内、接触角増加にどの成分が
どの程度関与するか不明な点が多いが、該有害成分除去
フィルタに通すことにより、接触角を増加する成分が除
去された気体が得られる。また、接触角を増加させる有
害成分は基材の種類（例えば、ウエハ、ガラス材等）や
基板上の薄膜の種類やその状態により様々である。The mechanism of removing harmful components by glass or fluororesin that increases the contact angle is not clear because the harmful components in the air are said to be a mixture of hundreds or thousands of components. Although there are many points, it can be considered as follows. It is presumed that the increase in contact angle is greatly influenced by substances having a large molecular weight and high activity among harmful components in the air, and these substances are effectively adsorbed and collected by glass and fluororesin. To be removed. That is, among many kinds of harmful components in the air, there are many unclear points about which component contributes to the increase of the contact angle, but by passing through the harmful component removal filter, the component increasing the contact angle is removed. The gas obtained is obtained. Further, the harmful components that increase the contact angle vary depending on the type of substrate (eg, wafer, glass material, etc.), the type of thin film on the substrate, and the state thereof.
【００１２】接触角の増加原因は、（１）、Ｈ．Ｃ．、
ＳＯｘ、ＮＯｘ、ＨＣｌ、ＮＨ3 などのようなガス状の
有害成分、（２）、微粒子のような粒子状物質、
（３）、（１）と（２）の中間物質の有害成分（例、ミ
スト、クラスター）、に大別できるが、通常の空気（通
常のクリーンルームにおける環境大気）中の濃度に対す
る影響では、（１）、微粒子のような粒子状物質、
（２）、Ｈ．Ｃ．のようなガス状の有害物質の関与が大
きい。一般に、通常の基材や基盤に介しては、ＳＯｘ、
ＮＯｘ、ＨＣｌ、ＮＨ3 は、夫々単一成分では、通常の
空気中の濃度レベルでは、接触角の増加に対し影響は少
ない。The cause of the increase in contact angle is (1), H. C. ,
Gaseous harmful components such as SOx, NOx, HCl, NH 3, etc. (2), particulate matter such as fine particles,
It can be roughly divided into harmful components (eg, mist, cluster) of the intermediate substances of (3), (1) and (2), but in the influence on the concentration in normal air (environmental air in a normal clean room), ( 1), particulate matter such as fine particles,
(2), H. C. Gaseous harmful substances such as are heavily involved. In general, SOx,
NOx, HCl, and NH 3 each have a single component and have little influence on the increase in the contact angle at normal concentration levels in air.
【００１３】しかし、ＳＯｘ、ＮＯｘ、ＨＣｌ、ＮＨ3
などの濃度が高い場合や、これら成分が複数共存する場
合、また基材や基盤が敏感な場合や特殊な場合（例え
ば、基材表面に特殊な薄膜を被覆した場合）、通常では
影響しない有害成分や濃度でも影響を受ける場合があ
る。クリーンルームにおいて、Ｈ．Ｃ．、ＳＯｘ、ＮＯ
ｘ、ＨＣｌ、ＮＨ3 のような有害ガスの発生があり、こ
れら成分の気体中の濃度が高い場合、あるいは基材や基
盤が特殊な処理をされ敏感な状態で取扱う場合は、本発
明がすでに提案した紫外線及び／又は放射線を有害ガス
に照射して、有害ガスを微粒子化し、該微粒子を捕集す
る方法（装置）（特願平３−２２，６８６号）を適宜に
組合せて用いることができる。However, SOx, NOx, HCl, NH 3
If the concentration is high, if multiple of these components coexist, or if the base material or substrate is sensitive or special (for example, if the surface of the base material is coated with a special thin film), it does not usually have an adverse effect. It may also be affected by the composition and concentration. In a clean room, H.264 C. , SOx, NO
If harmful gases such as x, HCl, and NH 3 are generated, and the concentrations of these components in the gas are high, or if the base material or substrate is subjected to special treatment and handled in a sensitive state, the present invention has already been achieved. The proposed method (apparatus) for irradiating harmful gas with ultraviolet rays and / or radiation to form harmful gas into fine particles and collecting the fine particles (Japanese Patent Application No. 3-22,686) may be used in appropriate combination. it can.
【００１４】また、このような場合は別の周知の有害ガ
ス除去材例えば活性炭、イオン交換繊維などを適宜組合
せて用いることができる。活性炭は、酸やアルカリなど
を添着したり、適宜の周知の方法により改質したものを
用いることができる。Ｈ．Ｃ．の除去においては、本発
明者がすでに提案した紫外線照射及び／又は放射線照射
によりＨ．Ｃ．を微粒子化して捕集する方法（特願平３
−１０５，０９２号）を併せて用いることができる。ま
た、本発明者が接触角の増加防止のためにすでに提案し
た別の発明（特願平３−３４１，８０２号）を適宜組合
せて用いることもできる。適用分野によっては、本発明
の捕集材（ガラス材及び／又はフッ素樹脂）に、この別
の発明の有害物質捕集材（例、シリカゲル、合成ゼオラ
イト、高分子化合物）を組合せて用いると、有害成分の
捕集性が顕著に向上するので好ましい。In such a case, another well-known harmful gas removing material such as activated carbon or ion exchange fiber can be appropriately combined and used. The activated carbon may be one which is impregnated with an acid or an alkali or which is modified by an appropriate known method. H. C. In the removal of H. C. Method to make fine particles and collect them (Japanese Patent Application No. 3
No. -105,092) can be used together. Further, another invention (Japanese Patent Application No. 3-341,802) already proposed by the present inventor for preventing an increase in contact angle can be used in combination as appropriate. Depending on the application field, when the scavenger of the present invention (glass material and / or fluororesin) is used in combination with the toxic substance scavenger of the other invention (eg, silica gel, synthetic zeolite, polymer compound), It is preferable because the ability to collect harmful components is significantly improved.
【００１５】なお、本発明においては、除塵フィルタと
有害成分除去フィルタを個別に設置しても良いが、適用
分野、装置の形状・構造、規模、微粒子濃度、効果、経
済性などによっては、除塵フィルタと有害成分除去フィ
ルタを一体化しても良く、適宜に選択することができ
る。一体化して行う場合は、ガラス材で成るＨＥＰＡあ
るいはＵＬＰＡフィルタのような除塵フィルタにフッ素
樹脂を適宜被覆あるいは含浸することにより達成でき
る。個別で用いるか、あるいは一体化して用いるかの判
断は通常次のように行う。In the present invention, the dust removing filter and the harmful component removing filter may be installed separately, but depending on the application field, the shape and structure of the device, the scale, the particle concentration, the effect, the economical efficiency, etc., the dust removing filter may be installed. The filter and the harmful component removing filter may be integrated and can be appropriately selected. When integrated, it can be achieved by appropriately coating or impregnating a dust removing filter such as a HEPA or ULPA filter made of a glass material with a fluororesin. The judgment as to whether they are used individually or as a unit is usually made as follows.
【００１６】微粒子濃度が高い場合は、個別に除塵フィ
ルタを設置する。すなわち、微粒子（粒子状物質）も接
触角増加に影響を及ぼすので個別の除塵フィルタで除去
する。また、接触角の増加を防止する装置で用いる有害
成分除塵フィルタに除塵性がない場合も、上記理由より
個別に除塵フィルタを設置する。微粒子濃度が低い場
合、あるいは微粒子濃度が低く、有害成分除去フィルタ
に除塵性がある場合は個別の除塵フィルタの設置は不用
とすることができる。If the particle concentration is high, a dust filter is installed separately. That is, since fine particles (particulate matter) also affect the increase in contact angle, they are removed by a separate dust filter. Further, even if the harmful component dust removal filter used in the device for preventing an increase in the contact angle does not have dust removal performance, the dust removal filter is separately installed for the above reason. When the particle concentration is low, or when the particle concentration is low and the harmful component removing filter has dust removing property, the installation of a separate dust removing filter can be omitted.
【００１７】上記のように、接触角に影響を及ぼす物
質は多岐にわたっていること、また接触角の増加の防
止を行いたい現場の立地条件（環境により存在する物質
の種類や濃度、更にはクリーンルームの条件）が夫々に
異なることから、夫々の現場に好適な方法、即ち、有害
成分除去フィルタの構成や形状や充填密度ＳＶや更に種
々の方法の組合せを利用するクリーンルームについて、
汚染物（微粒子、Ｈ．Ｃ．、他の有害成分）の濃度、種
類、適用装置の種類、構造、規模、要求性能・効率、経
済性などで適宜に予備試験を行い決めることが好まし
い。媒体が空気の場合に限らず、窒素やアルゴンなど他
の気体に不純物として微粒子状やガス状あるいはミスト
状の有害物質が含まれる場合も同様に実施できることは
言うまでもない。As described above, there are a wide variety of substances that affect the contact angle, and the site conditions at the site where it is desired to prevent an increase in the contact angle (the types and concentrations of substances that exist depending on the environment, as well as in the clean room). Since the conditions are different from each other, a method suitable for each site, that is, a clean room using a combination of various methods such as the configuration and shape of the harmful component removing filter, the packing density SV,
Preliminary tests are preferably performed and determined depending on the concentration and type of contaminants (fine particles, HC, and other harmful components), type of applicable equipment, structure, scale, required performance / efficiency, economical efficiency, and the like. It is needless to say that the present invention can be carried out not only when the medium is air but also when other harmful gases such as nitrogen and argon contain harmful substances in the form of fine particles, gas or mist as impurities.
【００１８】[0018]
【実施例】以下、本発明を実施例により具体的に説明す
るが、本発明はこれらの実施例に限定されない。 実施例１ 本発明の基材又は基盤表面の接触角の増加防止方法を、
半導体工場におけるエアーナイフ用の供給空気に適用し
た例を図１に示す。図１において、１はクラス１０，０
００のクリーンルームであり、クリーンルーム１ではク
リーンルーム内空気２が主に除塵フィルタ３及びガラス
材４−１とフッ素樹脂４−２より成る接触角の増加を防
止する装置５にて処理される。該装置後の空気６は、除
塵され、かつ接触角を増加させるガス状有害成分が除去
された清浄化空気となり、ウエハ洗浄におけるエアーナ
イフ装置７へ供給される。EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples. Example 1 A method for preventing an increase in the contact angle of a substrate or substrate surface of the present invention,
FIG. 1 shows an example applied to supply air for an air knife in a semiconductor factory. In FIG. 1, 1 is class 10,0
In the clean room 1, the air 2 in the clean room is treated by the dust filter 3 and the device 5 for preventing an increase in the contact angle of the glass material 4-1 and the fluororesin 4-2. The air 6 after the apparatus is cleaned air from which dust is removed and gaseous harmful components that increase the contact angle are removed, and is supplied to an air knife apparatus 7 for wafer cleaning.
【００１９】クリーンルーム１内の空気２は、外気８を
先ず粗フィルタ９や空気調和器１０で処理を行い、次い
で、ＨＥＰＡフィルタ１１により除塵され、クラス１
０，０００が保持されているが、外気８中の接触角を増
加させる有害成分（例Ｈ．Ｃ．、ＮＯｘ、ＳＯｘ、ＮＨ
3 ）は、上記粗フィルタ９、空気調和器１０、ＨＥＰＡ
フィルタ１１では除去できないため、クリーンルーム１
内に導入されてしまう。１２は接触角を増加させる有害
成分が共存する導入空気である。次に接触角の増加を防
止する装置５について詳しく述べる。微粒子と極低濃度
の接触角を増加させる有害成分を含むクリーンルーム１
内の空気２は、先ず、除塵フィルタ３にて微粒子が除去
される。除塵フィルタ３はクラス１０，０００のクリー
ンルームにおける微粒子を効率良く捕集できるものであ
れば何れでも良い。For the air 2 in the clean room 1, the outside air 8 is first treated by the coarse filter 9 and the air conditioner 10, and then the dust is removed by the HEPA filter 11 to obtain the class 1
10,000 is retained, but harmful components that increase the contact angle in the outside air 8 (eg HC, NOx, SOx, NH
3 ) is the coarse filter 9, the air conditioner 10, the HEPA
Clean room 1 as it cannot be removed by filter 11.
Will be introduced inside. Reference numeral 12 is introduced air in which harmful components that increase the contact angle coexist. Next, the device 5 for preventing the increase of the contact angle will be described in detail. Clean room 1 containing harmful components that increase the contact angle of fine particles and extremely low concentration
First, fine particles are removed from the air 2 inside by the dust filter 3. The dust removing filter 3 may be any one as long as it can efficiently collect fine particles in a class 10,000 clean room.
【００２０】通常、ＨＥＰＡフィルタやＵＬＰＡフィル
タが用いられる。本例ではＵＬＰＡフィルタを使用して
いる。除塵後の空気は、次いで有害成分除去フィルタ４
−１、４−２にて極低濃度の有害成分が効率良く除去さ
れる。このようにして、クリーンルーム１中の微量の微
粒子と接触角を増加させる有害成分が接触角の増加を防
止する装置５にて除去され、清浄空気６となりエアーナ
イフ装置７へ供給される。Usually, a HEPA filter or ULPA filter is used. In this example, a ULPA filter is used. The dust-removed air is then used in the harmful component removal filter 4
The extremely low concentration of harmful components is efficiently removed at -1 and 4-2. In this way, the trace amount of fine particles in the clean room 1 and harmful components that increase the contact angle are removed by the device 5 that prevents the increase of the contact angle, and become clean air 6 and are supplied to the air knife device 7.
【００２１】実施例２ 図１に示した接触角の増加を防止する装置でクリーンル
ームの空気中の微粒子及び有害成分の除去を行った洗浄
化空気にガラス基盤を暴露し、接触角の増加について調
べた。 クリーンルーム ： クラス１００，０００ 除塵フィルタ ： ＵＬＰＡ 有害成分除去フィルタ： 繊維状のホウケイ酸ガラスを
四フッ化樹脂でフィルタ状に成形したもの。 フィルタ部のＳＶ ： １０，０００（ｈ-1） 接触角の測定 ： 接触角計 ガラス基盤の前処理 ： 洗剤とアルコールで洗浄後、
Ｏ3 発生下で紫外線照射。Example 2 A glass substrate was exposed to cleaning air in which fine particles and harmful components in the air of a clean room were removed by the device shown in FIG. 1 for preventing an increase in contact angle, and the increase in contact angle was investigated. It was Clean room: Class 100,000 dust filter: ULPA Hazardous component removal filter: Fibrous borosilicate glass molded into a filter shape with tetrafluoride resin. SV of filter part: 10,000 (h -1 ) Measurement of contact angle: Contact angle meter Pretreatment of glass substrate: After washing with detergent and alcohol,
UV irradiation under O 3 generation.
【００２２】結果 １５０時間暴露した接触角（θ、度）を図２に示す。図
２において、本発明のものは−〇−で示し、また、比較
として、クリーンルームの空気にそのまま暴露したもの
（−●−）、除塵フィルタのみ通した空気（−□−）、
を示す。尚、用いた接触角計の接触角を検出し得る度数
（検出下限の接触角、θ、度）は、３〜４度であり、本
発明の除塵フィルタと有害成分除去フィルタを同時に用
いたものは、検出限界（↓）を示す。Results The contact angles (θ, degrees) exposed for 150 hours are shown in FIG. In FIG. 2, those of the present invention are indicated by − ◯ −, and, for comparison, those directly exposed to the air in the clean room (− ● −), air that has passed only the dust removal filter (− □ −),
Indicates. The contact angle of the used contact angle meter can detect the contact angle (lower limit of contact angle, θ, degree) is 3 to 4 degrees, and the dust filter of the present invention and the harmful component removing filter are used at the same time. Indicates the detection limit (↓).
【００２３】実施例３ クラス１，０００のクリーンルームで実施例２と同様に
試験し、接触角の増加について調べた。 有害成分除去フィルタ：ガラス素材のＵＬＰＡフィルタ
に四化フッ化樹脂を被覆したもの（除塵フィルタと有害
成分除去フィルタが一体化したもの）。 （実施例２において除塵フィルタ３がないもの） 結果 １５０時間暴露した接触角を図３に示す。図３におい
て、本発明のものは−〇−で示し、また比較としてクリ
ーンルームの空気にそのまま暴露したもの（−●−）を
示す。Example 3 A test was conducted in the same manner as in Example 2 in a clean room of Class 1,000 to examine an increase in contact angle. Toxic component removal filter: A glass material ULPA filter coated with tetrafluoride resin (a dust filter and a harmful component removal filter are integrated). (Those without the dust removal filter 3 in Example 2) Results The contact angles exposed for 150 hours are shown in FIG. In FIG. 3, those of the present invention are indicated by − ◯ −, and, for comparison, those directly exposed to the air in the clean room (− ● −) are indicated.
【００２４】実施例４ 実施例２における接触角の増加を防止する装置の前に
「酸性ガス吸着材が充填された吸着材充填部」を設置
し、酸洗浄しているクリーンルームで用い、クリーンル
ーム内空気に暴露したウエハの接触角と該装置出口の清
浄化空気に暴露したウエハの接触角を比較した。 クリーンルーム ： クラス１００，０００ 除塵フィルタ ： ＵＬＰＡ 有害成分除去フィルタ ： 実施例２と同じ。Example 4 An "adsorbent filling section filled with an acidic gas adsorbent" was installed in front of the apparatus for preventing an increase in contact angle in Example 2, and was used in a clean room where acid cleaning was performed. The contact angle of the wafer exposed to air and the contact angle of the wafer exposed to the cleaning air at the outlet of the apparatus were compared. Clean room: Class 100,000 dust removal filter: ULPA Hazardous component removal filter: Same as in Example 2.
【００２５】酸性ガス吸着材の充填部の吸着材 ：活性
炭（添着炭）及びイオン交換繊維（１：１） フィルタ部のＳＶ ： １０，０００（ｈ-1） 吸着材の充填部のＳＶ ： １，０００（ｈ-1） クリーンルームにおける酸処理 ： 硝酸と硫酸を使用 クリーンルームにおいて、クリーンルーム空気をウエハ
に暴露した空気中、ＮＯｘ、ＳＯｘ、ＮＨ3 濃度 ：
１０〜５０ｐｐｍ 接触角の測定及びガラス基盤の前処理は実施例と同じ。Adsorbent in the filled part of the acidic gas adsorbent: Activated carbon (impregnated carbon) and ion exchange fiber (1: 1) SV of the filter part: 10,000 (h -1 ) SV of the filled part of the adsorbent: 1 000 (h -1 ) Acid treatment in clean room: Using nitric acid and sulfuric acid NOx, SOx, NH 3 concentration in clean room air exposed to wafer in clean room:
10 to 50 ppm Measurement of contact angle and pretreatment of glass substrate are the same as in the example.
【００２６】結果 １５０時間暴露した接触角を図４に示す。図４におい
て、本発明のものは−〇−で示し、また比較としてクリ
ーンルームの空気にそのまま暴露したもの（−●−）、
また除塵フィルタ及び有害成分除去フィルタのみのもの
（−■−）を示す。Results The contact angles exposed for 150 hours are shown in FIG. In FIG. 4, those of the present invention are indicated by − ◯ −, and for comparison, those exposed as they are to the air of a clean room (− ● −),
In addition, only dust removal filters and harmful component removal filters (-■-) are shown.
【００２７】[0027]
【発明の効果】本発明によれば以下のような効果を奏す
る。 １）接触角の増加を防止するにあたり、気体をガラス及
び／又はフッ素樹脂を含有する除去手段と接触すること
により、気体中の接触角を増加させる有害成分が除去さ
れる。得られた清浄化気体を、半導体や液晶などの先端
産業における基材や基盤上に暴露しておくことで該基材
や基盤の表面汚染が防止でき、その結果該基材や基盤の
接触角が増加しない効果が生じる。The present invention has the following effects. 1) In preventing an increase in the contact angle, the gas is brought into contact with a removing means containing glass and / or a fluororesin to remove harmful components which increase the contact angle in the gas. By exposing the obtained cleaning gas to the base material or substrate in the advanced industry such as semiconductor or liquid crystal, surface contamination of the base material or substrate can be prevented, and as a result, the contact angle of the base material or substrate can be prevented. Does not increase.
【００２８】２）ガラス及び／又はフッ素樹脂の除去手
段の形状をフィルタ状とすることにより、 （１）気体が広い面積のガラス及び／又はフッ素樹脂と
接触するので気体中の接触角を増加させる有害成分が効
率良く除去できる。 （２）また、フィルタにより、共存する微粒子（粒子状
物質）も除去されるので、接触角を増加させない気体が
更に効果的に得られる。 従って、微粒子が比較的高濃度共存する場合であっても
（２）の清浄気体を、基材や基盤上に暴露しておくこと
で該基材や基盤の表面汚染が防止でき、その該基材や基
盤の接触角が増加しない効果が生じる。2) By making the shape of the means for removing glass and / or fluororesin into a filter shape, (1) since the gas comes into contact with glass and / or fluororesin in a large area, the contact angle in the gas is increased. Harmful components can be removed efficiently. (2) Further, since the filter removes coexisting fine particles (particulate matter), a gas that does not increase the contact angle can be obtained more effectively. Therefore, even when the fine particles coexist in a relatively high concentration, the clean gas of (2) can be exposed on the base material or the substrate to prevent surface contamination of the base material or the substrate. The effect that the contact angle of the material or the base does not increase occurs.
【００２９】３）有害成分が高濃度存在する場合、接触
角の増加を防止するにあたり、本ガラス及び／又はフッ
素樹脂による除去法に該有害成分の任意の除去法（紫外
線照射又は放射線照射、あるいは活性炭やイオン交換繊
維を用いる方法等）を適宜組合せることにより、ＨＣ、
ＳＯｘ、ＮＯｘ、ＨＣｌ、ＮＨ3 などに対し、真に接触
角を増加させる有害成分、濃度に対応した（現場に対応
した）好適な除去を行うことができる。3) When the harmful component is present at a high concentration, in order to prevent an increase in the contact angle, the removal method using the glass and / or the fluororesin can be applied to any method for removing the harmful component (UV irradiation or radiation irradiation, or By appropriately combining (methods such as using activated carbon or ion exchange fiber), HC,
With respect to SOx, NOx, HCl, NH 3, etc., it is possible to perform suitable removal corresponding to the harmful component and concentration that truly increase the contact angle (corresponding to the site).
【図１】本発明の接触角の増加防止方法を適用した説明
図。FIG. 1 is an explanatory diagram to which a contact angle increase preventing method of the present invention is applied.
【図２】実施例２の結果を示すグラフ。FIG. 2 is a graph showing the results of Example 2.
【図３】実施例３の結果を示すグラフ。FIG. 3 is a graph showing the results of Example 3.
【図４】実施例４の結果を示すグラフ。FIG. 4 is a graph showing the results of Example 4.
１：クリーンルーム、２：ルーム内空気、３：除塵フィ
ルタ、４−１：ガラスフィルタ、４−２：フッ素樹脂フ
ィルタ、５：接触角増加防止装置、６：浄化空気、７：
エアーナイフ装置、８：外気、９：粗フィルタ、１０：
空気調和器、１１：ＨＥＰＡフィルタ、１２：除塵空気1: Clean room, 2: Room air, 3: Dust filter, 4-1: Glass filter, 4-2: Fluororesin filter, 5: Contact angle increase prevention device, 6: Purified air, 7:
Air knife device, 8: outside air, 9: coarse filter, 10:
Air conditioner, 11: HEPA filter, 12: Dust removal air
───────────────────────────────────────────────────── フロントページの続き (72)発明者 鈴木 作 神奈川県藤沢市本藤沢４丁目２番１号 株 式会社荏原総合研究所内 (72)発明者 坂本 和彦 埼玉県浦和市南元宿２−４−１ ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Saku Suzuki, 4-2-1 Honfujisawa, Fujisawa-shi, Kanagawa Inside the EBARA Research Institute, Inc. (72) Inventor, Kazuhiko Sakamoto 2-4-1 Minamimotojuku, Urawa City, Saitama Prefecture
Claims (3)
する方法において、該基材又は基盤と接触する気体を、
ガラス及び／又はフッ素樹脂を含有する除去手段によ
り、該気体中の有害物質を除去して、前記基材又は基盤
と接触させることを特徴とする接触角の増加防止方法。1. A method for preventing an increase in the contact angle of a substrate or substrate surface, wherein a gas contacting the substrate or substrate is:
A method for preventing an increase in contact angle, which comprises removing harmful substances in the gas with a removing means containing glass and / or a fluororesin, and bringing the substance into contact with the base material or the substrate.
する除去手段が、フィルタ状であることを特徴とする請
求項１記載の接触角の増加防止方法。2. The method for preventing an increase in contact angle according to claim 1, wherein the removing means containing the glass and / or the fluororesin has a filter shape.
する装置において、該基材又は基盤と接触する気体を通
す、有害物質を除去するためのガラス及び／又はフッ素
樹脂を充填した除去装置を備えたことを特徴とする接触
角の増加防止装置。3. A device for preventing an increase in the contact angle of a substrate or substrate surface, which is filled with glass and / or a fluororesin for removing harmful substances, which allows a gas in contact with the substrate or substrate to pass therethrough. A device for preventing an increase in contact angle, which is provided with a device.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4180538A JP2582706B2 (en) | 1992-06-16 | 1992-06-16 | Method and apparatus for preventing increase in contact angle of substrate or substrate surface |
| US09/620,247 US6340381B1 (en) | 1991-12-02 | 2000-07-20 | Method and apparatus for the preparation of clean gases |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4180538A JP2582706B2 (en) | 1992-06-16 | 1992-06-16 | Method and apparatus for preventing increase in contact angle of substrate or substrate surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06324A true JPH06324A (en) | 1994-01-11 |
| JP2582706B2 JP2582706B2 (en) | 1997-02-19 |
Family
ID=16085022
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4180538A Expired - Fee Related JP2582706B2 (en) | 1991-12-02 | 1992-06-16 | Method and apparatus for preventing increase in contact angle of substrate or substrate surface |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2582706B2 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52129070A (en) * | 1976-04-22 | 1977-10-29 | Ntn Toyo Bearing Co Ltd | Device for removing minute foreign matter in gas |
| JPS60157035A (en) * | 1984-01-27 | 1985-08-17 | Toshiba Corp | Method for evaluating cleanliness of environment |
| JPS6312315A (en) * | 1986-07-01 | 1988-01-19 | Ebara Res Co Ltd | Filter for gas cleaning apparatus |
| JPH03119200A (en) * | 1989-09-29 | 1991-05-21 | Ohtsu Tire & Rubber Co Ltd :The | Porous glass paper |
-
1992
- 1992-06-16 JP JP4180538A patent/JP2582706B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52129070A (en) * | 1976-04-22 | 1977-10-29 | Ntn Toyo Bearing Co Ltd | Device for removing minute foreign matter in gas |
| JPS60157035A (en) * | 1984-01-27 | 1985-08-17 | Toshiba Corp | Method for evaluating cleanliness of environment |
| JPS6312315A (en) * | 1986-07-01 | 1988-01-19 | Ebara Res Co Ltd | Filter for gas cleaning apparatus |
| JPH03119200A (en) * | 1989-09-29 | 1991-05-21 | Ohtsu Tire & Rubber Co Ltd :The | Porous glass paper |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2582706B2 (en) | 1997-02-19 |
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