JPH0314518B2 - - Google Patents
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- Publication number
- JPH0314518B2 JPH0314518B2 JP744987A JP744987A JPH0314518B2 JP H0314518 B2 JPH0314518 B2 JP H0314518B2 JP 744987 A JP744987 A JP 744987A JP 744987 A JP744987 A JP 744987A JP H0314518 B2 JPH0314518 B2 JP H0314518B2
- Authority
- JP
- Japan
- Prior art keywords
- waste liquid
- photoresist
- concentrated
- treating
- component
- 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.)
- Expired
Links
- 239000007788 liquid Substances 0.000 claims description 102
- 239000002699 waste material Substances 0.000 claims description 94
- 229920002120 photoresistant polymer Polymers 0.000 claims description 73
- 238000000034 method Methods 0.000 claims description 35
- 238000000108 ultra-filtration Methods 0.000 claims description 30
- 239000012528 membrane Substances 0.000 claims description 29
- 239000000126 substance Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 238000002485 combustion reaction Methods 0.000 claims description 6
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 28
- 238000011282 treatment Methods 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 238000011161 development Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000002518 antifoaming agent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 241000863032 Trieres Species 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
- Physical Water Treatments (AREA)
Description
［産業上の利用分野］
本発明は、プリント基板製造工程、印刷工業、
半導体製造工業等より排出される廃液の処理方法
に関する。特に、フオトレジスト成分含有廃液を
濃縮する前処理と電磁波または熱エネルギー照射
により廃液を固化する処分方法に関する。
［従来の技術］
従来のプリント基板製造の廃液処理技術では、
水溶性フオトレジストを含有する廃液は、第１図
に示すように酸添加によりPHを下げ、溶解レジス
トを不溶化し、固液分離した後、アルカリ剤でPH
を中性にし、希釈水により有機物の負荷を低減し
た後、生物処理、濾過、活性炭吸着を行なうもの
であつた。このような処理方法では、多量の酸・
アルカリを消費するとともに、大量の希釈水と大
極の単位処理装置を必要とするために廃液の処理
コストが極めて高いものであつた。
亦、従来、このフオトレジスト含有廃液の処理
法には、逆浸透法によるものもあるが、これに
は、次のような問題点がある。プリント基板製造
より排出される廃液は、無機質を２％程度含有し
ているため、高い濃縮倍率が確保できない。即
ち、浸透圧の上昇により５倍の濃縮の程度が実用
上の限界である。そのために、廃液の約1/5程度
の濃縮液が処理しなければならないものとして残
るものである。
一方、フオトレジスト含有廃液に光エネルギー
或いは熱を与え、生成する不溶分を固液分離する
方法、また、逆に電磁波エネルギーで高分子フオ
トレジスト分を分解、無害化する方法がある。然
し乍ら、これらの方法は、重合促進剤や光分解促
進剤等の添加を必要とし、付与エネルギーの必要
とあいまつて処理コストを高くする問題があつ
た。
本発明者らは廃液量と処理コストの大幅低減を
可能にする第３図に示す廃液の回収再利用の方法
を特許出願した（特願昭61−171894号）。この処
理法では限外濾過膜で濃縮した濃縮液に酸を添加
しフオトレジスト成分を不溶化し、固液分離した
後に、逆浸透或いは紫外線分解及び活性炭吸着或
いは生物処理法を適用するものである。この濃縮
液処理法は、濃縮液量が大幅に減じているため処
理コスト高に結びつかないものの、更に処理の簡
便化が望まれていた。
［発明が解決しようとする問題点］
プリント基板製造で排出される現像廃液及び剥
離廃液は、水溶性フオトレジスト樹脂及び消泡剤
等を溶解したアルカリ性廃液であり、また、
COD、BODが高く、廃液処理コストも高いもの
である。廃液は全量処分しなければならなく、少
しの減容では、コスト高を解決できない。これに
対して、本発明は、廃液処理コストの低減された
廃液処理方法を提供することを目的とする。ま
た、フオトレジスト成分含有廃液を薬剤を添加す
ることなく極めて簡便に且つ安価にフオトレジス
ト含有廃液を処理できる方法を提供することを目
的とする。
［発明の構成］
［問題点を解決するための手段］
本発明の要旨とするものは、フオトレジスト成
分を含有する廃液の処理方法において、フオトレ
ジスト成分含有廃液をフオトレジスト成分のみを
排除する限外濾過膜によりフオトレジスト成分を
濃縮し、得られた濃縮廃液に、太陽光等の電磁波
を照射し、または熱エネルギーを加え、フオトレ
ジスト成分を重合せしめ、固形物にして処理する
ことによるフオトレジスト含有廃液の処理方法で
ある。亦、得られた固形物を燃焼させて、その燃
焼熱により該濃縮廃液を更に蒸発せしめ、電磁波
照射による重合を促進せしめることができる。
［作用］
従来の廃液処理法では、廃液の全量を処理する
が、本発明による廃液処理法では、廃液自体を限
外濾過により、約1/10〜1/20以上に濃縮し、その
濃縮液に太陽光などの電磁波または熱エネルギー
を与え、含有フオトレジスト成分などの有機物を
重合させて固形分にし、固形分は、自燃され、容
易に処分され得るものである。
限外濾過による廃液処理法では、現像、剥離廃
液を各々アルカリ性に保持しつつ、限外濾過膜を
通じて、濾過し、これらフオトレジスト成分含有
廃液は、フオトレジスト樹脂成分が、限外濾過膜
を通過せずに、濃縮液として残り、その他のアル
カリ分、消泡剤等の有効添加成分は限外濾過膜を
自由に透過するため、透過液を現像液または剥離
液としてもどし再び利用できる。従つて、濃縮廃
液はフオトレジスト成分を濃度高く含有し、原廃
液量の1/10〜1/20の程度にまで濃縮可能である。
水溶性フオトレジスト廃液は、プリント基板製
造の場合、Na2CO3、NaOH或いはKOHを１〜
２％含有するアルカリ性水溶性である。この廃液
を分画分子量5000〜100000の限外濾過膜に通じる
と、フオトレジストに起因する有機物の濃度は
1.5重量％程度から15〜30重量％にまで濃縮され
る。一方、分子量の小さい、フオトレジストの溶
剤成分である無機アルカリ剤は殆ど濃縮されず
に、得られた濃縮液中には１ないし２％の含有率
に留まるものである。
フオトレジスト含有廃液は、フオトレジストの
溶剤としてのアルカリが存在するために、アルカ
リを中和したPH６以下で初めて重合し不溶分が析
出するが、本発明により濃縮した液では、フオト
レジスト成分がリツチになつているため高アルカ
リ性領域でも、水を含んだままで容易に重合する
性質を有し、何ら酸等の薬剤を添加することなく
太陽光などの電磁波または熱エネルギーの付与に
よつて容易に重合固化することが可能である。重
合・固化は、濃縮液の含水率が50〜60重量％付近
から生起し、含有水も含めて重合固化ができるた
めに従来法に見られるような固液分離の処理も必
要ないものである。
本発明によるフオトレジスト成分濃縮廃液が、
太陽光などの電磁波または熱エネルギー照射だけ
で容易に重合され、フオトレジスト含有廃液を簡
便に経済的に処理できるためには以下の条件を満
たすものでなければならない。
濃縮廃液は、アルカリ成分などの他の成分の含
有レベルが低く、主にフオトレジスト成分を含有
しているものでなければならない。そして、本発
明により利用する限外濾過膜は、次のようなもの
でなければならない。
第１に限外濾過膜のモジユールは、処理すべき
フオトレジスト廃液がアルカリ性であるので、耐
アルカリ性でなければならない。
第２に、アルカリ性の廃液に溶解された無機質
を透過し、フオトレジスト成分を除くために、限
外濾過膜の分画分子量は、好適には5000〜100000
の範囲である。
これは、本発明方法によるフオトレジスト廃液
の処理法を、実際のフオトレジストの現像廃液及
び剥離廃液の特性を考慮して、この範囲が定めら
れた。即ち、限外濾過膜は一般に、ある一定の分
子量範囲の溶質を除去する分子量分画特性を有す
るが、この特性に基づくフオトレジストの現像廃
液及び剥離廃液中に含まれるフオトレジストに対
する除去性能がすぐれたものでなければならな
い。ここで除去性能とは、膜処理の供給原液成分
濃度に対する膜透過液成分濃度の低減率に相当
し、換言すれば、膜を透過しない成分濃度の比率
である。
フオトレジスト成分を大部分濃縮でき、消泡剤
及びアルカリ成分をじゆうに透過できる範囲は、
実用的には、分画分子量が、5000〜100000の範囲
にあればよい。このような特性を有する限外濾過
膜を用いることによつてフオトレジスト処理の現
像廃液及び剥離廃液中の有効成分たる消泡剤及び
アルカリ成分を経済的に回収することができる。
一方、フオトレジスト成分は処理しやすい固形分
として取り出すことができる。
従つて、本発明により適合利用できる限外濾過
膜モジユールは、膜素材として金属酸化物の無機
材例えば、二酸化ジルコニウム系、及び合成高分
子材の中で、例えば、ポリスルホン系、ポリイミ
ド系、アクリルニトリル系等が良好である。
プリント基板製造に用いるフオトレジストの感
光の後に、それを現像するため、即ち、フオトレ
ジストを除去するための現像工程で使用される現
像液、処理すべき現像廃液、限外濾過された液の
性質及び、プリント基板製造で導体板等をエツチ
ングした後、光重合したフオトレジストを剥離す
るための剥離液、その剥離廃液、限外濾過された
液等の特性を第１表に示す。
[Industrial Field of Application] The present invention is applicable to printed circuit board manufacturing processes, printing industry,
This invention relates to a method for treating waste liquid discharged from the semiconductor manufacturing industry, etc. In particular, the present invention relates to a pretreatment method for concentrating a waste liquid containing a photoresist component and a disposal method for solidifying the waste liquid by electromagnetic waves or thermal energy irradiation. [Conventional technology] Conventional waste liquid treatment technology for printed circuit board manufacturing
As shown in Figure 1, the waste liquid containing water-soluble photoresist is treated with an alkaline agent after which the pH is lowered by adding acid to insolubilize the dissolved resist and separated into solid and liquid.
After neutralizing the water and reducing the organic load with dilution water, biological treatment, filtration, and activated carbon adsorption were performed. This treatment method uses a large amount of acid and
In addition to consuming alkali, a large amount of dilution water and large unit processing equipment are required, so the cost of processing the waste liquid is extremely high. In addition, conventional methods for treating this photoresist-containing waste liquid include reverse osmosis, but this method has the following problems. Since the waste liquid discharged from printed circuit board manufacturing contains about 2% inorganic substances, a high concentration ratio cannot be secured. That is, the practical limit is a 5-fold concentration due to an increase in osmotic pressure. For this reason, about 1/5 of the concentrated liquid remains to be treated. On the other hand, there is a method in which light energy or heat is applied to a photoresist-containing waste liquid to separate solid-liquid insoluble components, and there is also a method in which the polymer photoresist component is decomposed and rendered harmless using electromagnetic energy. However, these methods require the addition of polymerization accelerators, photodecomposition accelerators, etc., which, together with the need for applied energy, has the problem of increasing processing costs. The present inventors have filed a patent application (Japanese Patent Application No. 171,894/1982) for a method of recovering and reusing waste liquid shown in FIG. 3, which enables a significant reduction in the amount of waste liquid and treatment cost. In this treatment method, an acid is added to the concentrated solution concentrated using an ultrafiltration membrane to insolubilize the photoresist components, and after solid-liquid separation, reverse osmosis or ultraviolet decomposition and activated carbon adsorption or biological treatment are applied. Although this concentrated liquid processing method does not lead to high processing costs because the amount of concentrated liquid is significantly reduced, it has been desired to further simplify the processing. [Problems to be Solved by the Invention] The developing waste liquid and stripping waste liquid discharged in printed circuit board manufacturing are alkaline waste liquids in which water-soluble photoresist resin, antifoaming agent, etc. are dissolved.
COD and BOD are high, and the waste liquid treatment cost is also high. The entire amount of waste liquid must be disposed of, and even a small volume reduction cannot solve the high cost. In contrast, an object of the present invention is to provide a waste liquid treatment method with reduced waste liquid treatment cost. Another object of the present invention is to provide a method for processing a photoresist component-containing waste solution very simply and inexpensively without adding any chemicals to the photoresist component-containing waste solution. [Structure of the Invention] [Means for Solving the Problems] The gist of the present invention is to provide a method for treating waste liquid containing a photoresist component, as long as only the photoresist component is removed from the waste liquid containing the photoresist component. A photoresist produced by concentrating the photoresist components using an outer filtration membrane, irradiating the resulting concentrated waste liquid with electromagnetic waves such as sunlight, or adding thermal energy to polymerize the photoresist components and processing them into a solid substance. This is a method for treating waste liquid containing waste water. In addition, the obtained solid substance can be combusted, and the concentrated waste liquid can be further evaporated by the combustion heat, thereby promoting polymerization by electromagnetic wave irradiation. [Function] In the conventional waste liquid treatment method, the entire amount of waste liquid is treated, but in the waste liquid treatment method according to the present invention, the waste liquid itself is concentrated to about 1/10 to 1/20 or more by ultrafiltration, and the concentrated liquid is Electromagnetic waves such as sunlight or thermal energy are applied to the photoresist component to polymerize organic substances such as photoresist components to form a solid content, which is self-combustible and can be easily disposed of. In the waste liquid treatment method using ultrafiltration, the developing and stripping waste liquids are each kept alkaline and filtered through an ultrafiltration membrane. Instead, it remains as a concentrated solution, and other active additives such as alkaline components and antifoaming agents freely pass through the ultrafiltration membrane, so the permeated solution can be returned and reused as a developer or stripping solution. Therefore, the concentrated waste liquid contains photoresist components at a high concentration and can be concentrated to about 1/10 to 1/20 of the amount of the original waste liquid. In the case of printed circuit board manufacturing, the water-soluble photoresist waste liquid contains 1 to 10% of Na 2 CO 3 , NaOH or KOH.
It is alkaline water soluble containing 2%. When this waste liquid is passed through an ultrafiltration membrane with a molecular weight cutoff of 5,000 to 100,000, the concentration of organic matter caused by the photoresist is reduced.
It is concentrated from about 1.5% by weight to 15-30% by weight. On the other hand, the inorganic alkali agent, which is a solvent component of photoresist and has a small molecular weight, is hardly concentrated and remains at a content of 1 to 2% in the obtained concentrated solution. Since the photoresist-containing waste liquid contains an alkali as a solvent for the photoresist, it polymerizes for the first time below the pH of 6, which is when the alkali is neutralized, and insoluble matter precipitates.However, in the liquid concentrated according to the present invention, the photoresist components are enriched. It has the property of easily polymerizing even in highly alkaline areas while containing water, and can be easily polymerized by applying electromagnetic waves such as sunlight or thermal energy without adding any chemicals such as acids. It is possible to solidify. Polymerization and solidification occur when the water content of the concentrated liquid is around 50 to 60% by weight, and since the water content can be polymerized and solidified, there is no need for solid-liquid separation as seen in conventional methods. . The photoresist component concentrated waste liquid according to the present invention is
In order for photoresist-containing waste liquid to be easily polymerized simply by irradiation with electromagnetic waves such as sunlight or thermal energy, and to be able to process photoresist-containing waste liquid simply and economically, it must satisfy the following conditions. The concentrated waste liquid must contain mainly photoresist components, with low levels of other components such as alkaline components. The ultrafiltration membrane used in the present invention must be as follows. First, the ultrafiltration membrane module must be alkaline resistant, since the photoresist waste liquid to be treated is alkaline. Second, in order to pass through the inorganic substances dissolved in the alkaline waste liquid and remove the photoresist components, the molecular weight cutoff of the ultrafiltration membrane is preferably 5,000 to 100,000.
is within the range of This range was determined by considering the method of treating photoresist waste liquid according to the method of the present invention and the characteristics of actual photoresist developing waste liquid and stripping waste liquid. That is, ultrafiltration membranes generally have molecular weight fractionation characteristics that remove solutes within a certain molecular weight range, and based on these characteristics, ultrafiltration membranes have excellent removal performance for photoresist contained in the photoresist development waste solution and stripping waste solution. It must be of the same type. Here, the removal performance corresponds to the reduction rate of the concentration of components in the membrane-permeated solution relative to the concentration of components in the stock solution supplied for membrane treatment, in other words, it is the ratio of the concentration of components that do not pass through the membrane. The range in which most of the photoresist components can be concentrated and the antifoaming agent and alkaline components can be permeated is as follows:
Practically speaking, the molecular weight cutoff may be in the range of 5,000 to 100,000. By using an ultrafiltration membrane having such characteristics, it is possible to economically recover the antifoaming agent and alkaline components, which are the active ingredients in the developing waste solution and stripping waste solution from photoresist processing.
On the other hand, the photoresist component can be extracted as a solid content that is easy to process. Therefore, the ultrafiltration membrane module that can be suitably used in accordance with the present invention uses metal oxide inorganic materials, such as zirconium dioxide, and synthetic polymer materials, such as polysulfone, polyimide, and acrylonitrile, as membrane materials. The system etc. are good. Characteristics of the developer used in the development step for developing the photoresist used in the manufacture of printed circuit boards after exposure, that is, for removing the photoresist, the developer waste to be treated, and the ultrafiltered solution. Table 1 shows the characteristics of the stripping solution used to strip off the photoresist that has been photopolymerized after etching conductor plates and the like in the manufacture of printed circuit boards, the stripping waste solution, and the ultrafiltered solution.
【表】
現像廃液を限外濾過により処理し、限外濾過膜
を通過した透過液を再び使用するためには、前の
現像処理でアルカリ成分が消費されて、PH値が低
下しているために、限外濾過膜通過液には、アル
カリ液を補給してPHの調整を行なう。亦、剥離液
においても、同様にPHの調整を行ない、限外濾過
膜通過液を剥離液として戻す。
再生現像液のPHの調整には、Na2CO3、NaOH
溶液を補給する。現像液中のNaイオンが増加す
ると、剥離工程で溶解すべきフオトレジストまで
が溶解する恐れがあるが、レジスト溶解前のPHに
達するまでNaOHを加えるとともに膜濃縮廃液
量に対応してNa2CO3の補給量を設定することで
Naイオンの蓄積を防止することができる。
再生剥離液の成分の調整は、NaOH或いは
KOH溶液でPHを14程度に調整することで十分で
ある。
本発明によるフオトレジスト成分含有廃液の処
理方法では、現像廃液及び剥離廃液の両方を処理
し、各々の系の限外濾過膜からでるフオトレジス
ト成分の濃縮された濃縮廃液を太陽光下に放置す
ることにより重合せしめ、濃縮廃液を固形化す
る。尚、太陽光線に限らず、人工光線によつても
重合せしめ得る。また、濃縮廃液に熱エネルギー
を加え、更に蒸発・濃縮することにより廃液を重
合・固化することができる。
本発明による廃液処理では、アルカリ調整、限
外濾過膜の種類及び数量の変更等により廃液に溶
解しているフオトレジスト成分、その濃度の変化
に対応する処理条件の選択が必要である。
この限外濾過膜によりフオトレジスト成分は、
10〜20倍に濃縮され、濃縮液のフオトレジストな
どの有機物濃度は、15〜30重量％に達することが
できる。本発明は、この濃縮液に薬剤を加えるこ
となく、極めて簡便且つ安価に廃液の処理を行な
うことができる。
以上のように、本発明で、フオトレジスト含有
廃液そのものを、自燃し得る固形物として固化す
るには、フオトレジストの溶剤成分例えば、アル
カリ成分及び重合に関与しない低分子有機物（フ
オトレジストの分解物など）の濃度を増加させな
いで、レジスト成分などの有機物濃度を10重量％
程度（当初の廃液濃度からは約10倍濃縮に相当す
る）以上に、濃縮しておくことが必要である。こ
の濃縮には高分子フオトレジスト成分のみを排除
即ち、濃縮できる限外濾過膜を用いる。
この濃縮液に太陽光線等の電磁波または熱エネ
ルギーを一定時間照射するのみで濃縮液自体が固
化する。照射すべき電磁波エネルギーは、通常太
陽光線でよく、波長200〜400nｍの紫外線を含む
ものが好適であり、フオトレジスト成分水溶液の
特性に適するものを用いる。バツト、プレートな
どにいれて濃縮液に太陽光線を当て放置すればよ
い。従つて、重合固化物は、プレート中に水を含
んで固化析出し、容易にとりだせる。その固化物
は、自燃するために、燃やしその燃焼熱を回収す
る手段を講じれば、更に、もとの濃縮液の蒸発、
固化を促進することができる。また、熱エネルギ
ーを加える場合はドラムトライヤーなどによる間
接加熱方式とし、重合固化物はスクレーパーで剥
ぎ取る方式が好適である。また、この場合前記し
た固化物の燃焼熱は加熱エネルギーの補助として
利用できる。このような本発明によるフオトレジ
スト成分含有廃液の処理システムを、第４図に示
す。
即ち、フオトレジスト成分含有廃液を限外濾過
にかけ、その膜透過液は回収しリサイクル使用或
いは無害化して処理し、透過せずに濃縮した液に
は太陽光線など電磁波または熱エネルギーを付与
し重合固化せしめ、フオトレジスト成分などを処
理する。固化したフオトレジスト成分などよりな
る固化物は自燃せしめ、その燃焼熱で更に処理を
経済的に効率化せしめる。
本発明による重合固化は、含水率50〜60重量％
付近で生じ、水分も含めて固化し、且つ容易に自
燃する固化物が得られる。従つて、従来法のよう
な固液分離等の処理を必要としない。
次に本発明の処理法の実施例による実証テスト
を述べるが、本発明は、これにより限定されるも
のではない。
実施例 １
プリント基板製造工程より排出する水溶性フオ
トレジスト現像廃液（１％Na2CO3添加し、PH
10.5に調整したもので、TOC6000mg／）を分
画分子量10000のポリスルホン膜で20倍に濃縮し
た液200mlを200mm×250mmのガラス製バツト中で
太陽光下に放置した。４時間で厚みが２mm程度の
固化物を得た。固化物は水分55重量％であつた。
この固化物の低位発熱量は4100kcal／Kgで容易に
自燃した。
実施例 ２
プリント基板製造工程より排出する水溶性フオ
トレジスト剥離廃液（２％KOHを添加し、PH
13.5に調整したもので、TOC11000mg／）を実
施例１と同一の限外濾過膜で10倍濃縮した液200
mlを200mm×250mmのガラス製バツト中で太陽光下
に放置した。その結果3.5時間で実施例１と同様
の固化物を得た。固化物の水分量は、60重量％で
あつた。低位発熱量は3600kcal／Kgであつた。こ
の固化物は、実施例１と同様に自燃した。
比較例 １
実施例１と同じ現像廃液200mlを限外濾過での
濃縮を行なわずにそのままで200mm×250mmのガラ
スバツト中で太陽光下に放置した。その結果、12
時間放置したが含水率52重量％となつたが、固化
物は認められなかつた。更に天日蒸発を継続した
結果、13時間で乾固したが、殆ど白色の無機アル
カリ剤に起因する粉末状析出物しか残らなかつ
た。
比較例 ２
実施例１と同じ現像廃液を実施例１と同じ限外
濾過により５倍に濃縮した液200mlを200mm×250
mmのガラスバツト中で太陽光下に放置した。その
結果、９時間放置した含水率55重量％となつた
が、固化物は得られなかつた。更に天日蒸発を継
続した結果、10時間で乾固したが、殆ど白色の無
機アルカリ剤に起因する粉末状析出物しか残らな
かつた。
比較例 ３
実施例１と同じ現像廃液を実施例１と同じ限外
濾過で８倍に濃縮した液200mlを200mm×250mmの
ガラスバツト中で太陽光下に放置した。その結
果、７時間放置したが部分的に固化物が得られた
が、白色粉末が混在する固形物であり、固化が不
十分であつた。
実施例 ３
実施例１で用いた廃液と同一の現像廃液を限外
濾過により20倍に濃縮して濃縮液を得、その濃縮
液を遮光下で１時間含水率57重量％まで加熱蒸発
した。その結果実施例１と同様に固化し、自燃す
る固化物を得た。
［発明の効果］
本発明のフオトレジスト含有廃液の処理方法
は、高分子フオトレジストのみを排除する限外濾
過膜の濃縮液が重合できるために、
第１に、極めて簡便に安価にフオトレジスト廃
液を処理できる方法を提供できること、
第２に、光または熱エネルギーを用いる重合の
ために何等の薬剤を添加する必要がなく、廃液重
合固化ができること、
第３に、重合固化したものは、容易に自然にす
るために従来の処理法のような固液分離水の処理
を必要としないこと、
第４に、廃液を濃縮したものを更に含水率を下
げるために、この含有率の燃焼熱を利用して、効
率化が図かれること、
第４に、従つて、短時間に且つ極めて低コスト
で廃液を固化処理することができることなどの技
術的効果が得られた。[Table] In order to process the development waste liquid by ultrafiltration and reuse the permeate that has passed through the ultrafiltration membrane, the alkaline component has been consumed in the previous development process and the PH value has decreased. Next, the pH of the liquid passing through the ultrafiltration membrane is adjusted by replenishing it with an alkaline solution. In addition, the pH of the stripping solution is similarly adjusted, and the liquid passing through the ultrafiltration membrane is returned as the stripping solution. To adjust the pH of the regenerated developer, use Na 2 CO 3 or NaOH.
Replenish the solution. If the Na ions in the developer increase, there is a risk that the photoresist that should be dissolved in the stripping process will be dissolved, but NaOH is added until the pH reaches the level before the resist is dissolved, and Na 2 CO is added in proportion to the amount of membrane concentrated waste liquid. By setting the supply amount of 3
It can prevent the accumulation of Na ions. To adjust the components of the regenerated stripper, use NaOH or
It is sufficient to adjust the pH to around 14 with a KOH solution. In the method for treating a waste liquid containing a photoresist component according to the present invention, both the developing waste liquid and the stripping waste liquid are treated, and the concentrated waste liquid containing the photoresist component from the ultrafiltration membrane of each system is left under sunlight. This polymerizes and solidifies the concentrated waste liquid. Note that polymerization can be performed not only by sunlight but also by artificial light. Further, by applying thermal energy to the concentrated waste liquid and further evaporating and concentrating it, the waste liquid can be polymerized and solidified. In the waste liquid treatment according to the present invention, it is necessary to select treatment conditions corresponding to changes in the photoresist components dissolved in the waste liquid and their concentrations by adjusting the alkali, changing the type and quantity of ultrafiltration membranes, etc. This ultrafiltration membrane allows photoresist components to
It is concentrated 10-20 times, and the concentration of organic matter such as photoresist in the concentrated solution can reach 15-30% by weight. According to the present invention, waste liquid can be treated extremely simply and at low cost without adding any chemicals to this concentrated liquid. As described above, in the present invention, in order to solidify the photoresist-containing waste liquid itself as a solid substance that can self-combust, the photoresist's solvent components, such as alkaline components and low-molecular organic substances that do not participate in polymerization (decomposed products of the photoresist) etc.) without increasing the concentration of organic matter such as resist components by 10% by weight.
It is necessary to concentrate the waste liquid to a degree (equivalent to about 10 times the original concentration of waste liquid) or higher. For this concentration, an ultrafiltration membrane is used which can eliminate or concentrate only the polymer photoresist components. Simply by irradiating this concentrated liquid with electromagnetic waves such as sunlight or thermal energy for a certain period of time, the concentrated liquid itself solidifies. The electromagnetic wave energy to be irradiated may normally be sunlight, preferably one containing ultraviolet rays with a wavelength of 200 to 400 nm, and should be selected from those suitable for the characteristics of the photoresist component aqueous solution. All you have to do is put it in a vat, plate, etc. and leave it exposed to sunlight. Therefore, the polymerized solidified product is solidified and precipitated while containing water in the plate, and can be easily taken out. Since the solidified substance self-combustes, if a means is taken to burn it and recover the combustion heat, it will further reduce the evaporation of the original concentrated liquid.
It can promote solidification. In addition, when applying heat energy, it is preferable to use an indirect heating method using a drum trier or the like, and to strip off the polymerized solidified product with a scraper. Further, in this case, the heat of combustion of the solidified material described above can be used as supplementary heating energy. A system for treating waste liquid containing photoresist components according to the present invention is shown in FIG. That is, waste liquid containing photoresist components is subjected to ultrafiltration, the liquid that permeates through the membrane is collected and recycled or treated to make it harmless, and the concentrated liquid that does not permeate is subjected to electromagnetic waves such as sunlight or thermal energy to polymerize and solidify it. Processes photoresist components, etc. The solidified material, such as the solidified photoresist component, self-combusts, and the heat of combustion makes the process more economical and efficient. The polymerization solidification according to the present invention has a moisture content of 50 to 60% by weight.
A solidified product is obtained that forms near the fuel, solidifies together with moisture, and easily self-combustes. Therefore, treatments such as solid-liquid separation as in conventional methods are not required. Next, a demonstration test using an example of the treatment method of the present invention will be described, but the present invention is not limited thereto. Example 1 Water-soluble photoresist development waste liquid discharged from the printed circuit board manufacturing process (1% Na 2 CO 3 added, PH
10.5, 200 ml of TOC 6,000 mg/) was concentrated 20 times using a polysulfone membrane with a molecular weight cutoff of 10,000 and left in a 200 mm x 250 mm glass vat under sunlight. A solidified product with a thickness of about 2 mm was obtained in 4 hours. The solidified material had a water content of 55% by weight.
The lower calorific value of this solidified material was 4100kcal/Kg, and it easily combusted. Example 2 Water-soluble photoresist stripping waste liquid discharged from the printed circuit board manufacturing process (added 2% KOH, pH
It was adjusted to 13.5, and the TOC 11000mg/) was concentrated 10 times using the same ultrafiltration membrane as in Example 1.
ml was left in a 200 mm x 250 mm glass vat under sunlight. As a result, a solidified product similar to that in Example 1 was obtained in 3.5 hours. The moisture content of the solidified product was 60% by weight. The lower calorific value was 3600kcal/Kg. This solidified material self-combusted similarly to Example 1. Comparative Example 1 200 ml of the same developing waste solution as in Example 1 was left exposed to sunlight in a 200 mm x 250 mm glass vat without being concentrated by ultrafiltration. As a result, 12
After being left for a while, the water content reached 52% by weight, but no solidified material was observed. As a result of further continued solar evaporation, it was dried to solidity in 13 hours, but only an almost white powdery precipitate caused by the inorganic alkali agent remained. Comparative Example 2 200 ml of the same developer waste solution as in Example 1 was concentrated five times by the same ultrafiltration as in Example 1, and was placed in a 200 mm x 250
It was left under sunlight in a glass vat. As a result, the water content was 55% by weight after being left for 9 hours, but no solidified product was obtained. As a result of further continued solar evaporation, it was dried to solidity in 10 hours, but only an almost white powdery precipitate caused by the inorganic alkali agent remained. Comparative Example 3 200 ml of the same developer waste solution as in Example 1 was concentrated 8 times by the same ultrafiltration as in Example 1 and left in a 200 mm x 250 mm glass vat under sunlight. As a result, although a partially solidified product was obtained after being left for 7 hours, it was a solid containing white powder and was not sufficiently solidified. Example 3 A developer waste solution, which was the same as the waste solution used in Example 1, was concentrated 20 times by ultrafiltration to obtain a concentrated solution, and the concentrated solution was heated and evaporated to a water content of 57% by weight for 1 hour in the dark. As a result, a solidified product which solidified and self-combusted in the same manner as in Example 1 was obtained. [Effects of the Invention] The method for treating photoresist-containing waste liquid of the present invention is capable of polymerizing the concentrated liquid of an ultrafiltration membrane that excludes only polymeric photoresist. Second, there is no need to add any chemicals for polymerization using light or thermal energy, and the waste liquid can be polymerized and solidified. Thirdly, the polymerized and solidified material can be easily processed. In order to make it natural, there is no need to treat solid-liquid separated water as in conventional treatment methods.Fourthly, to further reduce the water content of concentrated waste liquid, the combustion heat of this content is used. Fourthly, technical effects such as the ability to solidify waste liquid in a short time and at extremely low cost were obtained.
第１図は、従来のプリント基板製造の廃液処理
のシステムを示すフローシートである。第２図
は、従来のプリント基板製造の廃液処理のシステ
ムを示すフローシートである。第３図は、先願の
発明によるプリント基板製造の現像廃液又は剥離
廃液を処理するシステムを示す説明図である。第
４図は、本発明によるフオトレジスト含有廃液の
処理システムの１例を示すフローシートである。
FIG. 1 is a flow sheet showing a conventional waste liquid treatment system for manufacturing printed circuit boards. FIG. 2 is a flow sheet showing a conventional waste liquid treatment system for manufacturing printed circuit boards. FIG. 3 is an explanatory diagram showing a system for treating developing waste liquid or stripping waste liquid from printed circuit board manufacturing according to the invention of the prior application. FIG. 4 is a flow sheet showing an example of a treatment system for photoresist-containing waste liquid according to the present invention.
Claims (1)
法おいて、 フオトレジスト成分含有廃液をフオトレジスト
成分のみを排除する限外濾過膜によりフオトレジ
スト成分を濃縮し、得られた濃縮廃液に、電磁波
を照射し、フオトレジスト成分を重合せしめ、固
形物にして処理することを特徴とするフオトレジ
スト含有廃液の処理方法。 ２ 得られた固形物を燃焼させて、その燃焼熱に
より該濃縮廃液を更に蒸発せしめ、電磁波エネル
ギー照射による重合を促進せしめる特許請求の範
囲第１項記載のフオトレジスト含有廃液の処理方
法。 ３ フオトレジスト成分を含有する廃液の処理方
法おいて、 フオトレジスト成分含有廃液をフオトレジスト
成分のみを排除する限外濾過膜によりフオトレジ
スト成分を濃縮し、得られた濃縮廃液に、熱エネ
ルギーを加え、固形物にして処理することを特徴
とするフオトレジスト含有廃液の処理方法。[Claims] 1. A method for treating a waste liquid containing a photoresist component, comprising: concentrating the photoresist component in the waste liquid containing the photoresist component using an ultrafiltration membrane that removes only the photoresist component; and a concentrated waste liquid obtained by concentrating the photoresist component. A method for treating a photoresist-containing waste liquid, which comprises irradiating electromagnetic waves to polymerize photoresist components and treating them as a solid. 2. A method for treating a photoresist-containing waste liquid according to claim 1, wherein the obtained solid substance is combusted, and the concentrated waste liquid is further evaporated by the heat of combustion, and polymerization by electromagnetic energy irradiation is promoted. 3. A method for treating waste liquid containing a photoresist component, in which the photoresist component is concentrated in the waste liquid containing the photoresist component using an ultrafiltration membrane that removes only the photoresist component, and thermal energy is added to the obtained concentrated waste liquid. , a method for treating photoresist-containing waste liquid, which comprises treating it as a solid substance.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62007449A JPS63178888A (en) | 1987-01-17 | 1987-01-17 | Treatment of photoresist-containing waste liquid |
| EP87306477A EP0254550B1 (en) | 1986-07-23 | 1987-07-22 | Treatment of photoresist materials containing waste solution |
| US07/076,372 US4786417A (en) | 1986-07-23 | 1987-07-22 | Management of photoresist materials containing waste solution |
| AT87306477T ATE81476T1 (en) | 1986-07-23 | 1987-07-22 | TREATMENT OF A WASTE SOLUTION CONTAINING PHOTORESIST MATERIALS. |
| DE8787306477T DE3782205T2 (en) | 1986-07-23 | 1987-07-22 | TREATING A WASTE SOLUTION CONTAINING PHOTORESIST MATERIALS. |
| KR1019870007965A KR950014323B1 (en) | 1986-07-23 | 1987-07-22 | Treatment method of photoresist waste liquid |
| CN87105308A CN1010555B (en) | 1986-07-23 | 1987-07-23 | Treatment of waste liquid containing photoresist |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62007449A JPS63178888A (en) | 1987-01-17 | 1987-01-17 | Treatment of photoresist-containing waste liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63178888A JPS63178888A (en) | 1988-07-22 |
| JPH0314518B2 true JPH0314518B2 (en) | 1991-02-26 |
Family
ID=11666146
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62007449A Granted JPS63178888A (en) | 1986-07-23 | 1987-01-17 | Treatment of photoresist-containing waste liquid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63178888A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5112491A (en) * | 1991-03-01 | 1992-05-12 | E. I. Du Pont De Nemours And Company | Management of waste solution containing photoresist materials |
| US5811224A (en) * | 1994-08-24 | 1998-09-22 | Bayer Corporation | Process for rejuvenating developer in printing plate development |
| KR20080018215A (en) * | 2005-06-22 | 2008-02-27 | 도아고세이가부시키가이샤 | Removal method and removal apparatus of organic film on gas surface |
| JP7084683B2 (en) * | 2015-02-23 | 2022-06-15 | 東京応化工業株式会社 | Liquid purification method, chemical or cleaning liquid manufacturing method, filter media, and filter device |
| JP7501075B2 (en) * | 2020-04-24 | 2024-06-18 | ニプロ株式会社 | Method and system for pre-treating wastewater |
-
1987
- 1987-01-17 JP JP62007449A patent/JPS63178888A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63178888A (en) | 1988-07-22 |
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