CN101407596B - Method for recycling epoxy resins and glass fibre from non-metal powder of waste printed circuit board - Google Patents

Method for recycling epoxy resins and glass fibre from non-metal powder of waste printed circuit board Download PDF

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Publication number
CN101407596B
CN101407596B CN2008102004105A CN200810200410A CN101407596B CN 101407596 B CN101407596 B CN 101407596B CN 2008102004105 A CN2008102004105 A CN 2008102004105A CN 200810200410 A CN200810200410 A CN 200810200410A CN 101407596 B CN101407596 B CN 101407596B
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metal powder
reaction
mineral acid
organic solvent
solid
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CN2008102004105A
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Chinese (zh)
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CN101407596A (en
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管传金
王景伟
周玉林
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上海第二工业大学
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J11/00Recovery or working-up of waste materials
    • C08J11/04Recovery or working-up of waste materials of polymers
    • C08J11/10Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/16Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with inorganic material
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J2363/00Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/582Recycling of unreacted starting or intermediate materials
    • Y02W30/705

Abstract

The invention discloses a method for recycling epoxide resin and glass fiber from non-metal powder in waste printed circuit boards, comprising the following steps of: (1) pretreatment, and dust removal by washing; (2) removing residue metal: inorganic acid is used for removing the residue metal in the non-metal powder, and the obtained powder can be used directly after being filtrated; (3) preliminary decomposition: the processed non-metal powder is added into inorganic acid, the obtained mixture is heated for reaction and then filtrated; the filtrated solid is added into organic solvent, stirred and filtrated and the obtained solid is the glass fiber; and the organic solvent in the filtrate is evaporated so as to obtain the solid epoxide resin; and (4) secondary decomposition: the obtained solid epoxide resin is added into inorganic acid, and heated for reaction; and then the organic solvent is used for extraction and then is evaporated so as to obtain low molecular weight epoxide resin. The invention realizes green recycling of the non-metal powder of the waste printed circuit boards under the moderate condition and has high recovery rate, thus not only being capable of reducing the emission of pollutants but also leading the resource to be fully utilized.

Description

From the non-metal powder of abandoned printed circuit board, reclaim the method for Resins, epoxy and glass fibre

Technical field

The present invention relates to from the non-metal powder of abandoned printed circuit board, reclaim the method for Resins, epoxy and glass fibre.

Background technology

Printed-wiring board (PWB) (Printed Circuit Boards, be called for short PCB) be requisite integral part in the electronic product, little of electronic watch, counter, general-purpose computer, big to computer, communication equipment, military weapons system, as long as electronic devices and components such as unicircuit are arranged, printed circuit board is just arranged.Printed circuit board ratio in electronic product is higher, can reach 20-30% (mass ratio) as containing ratio in computer.

Depleted PCB is mainly derived from two aspects: one is to derive from the various electric equipment products of scrapping, China's household electrical appliance have entered and have eliminated the peak period of scrapping at present, how to handle the printed circuit board in these waste electrical equipments, become the difficult problem that more current national government and environmental protection organization face; Waste electrical equipment has become world's public hazards.Contain metal, components and parts and substrate (being mainly glass fibre enhanced thermosetting epoxy resin, particularly IT industry) among the discarded PCB.After the components and parts dismounting remaining PCB is pulverized, reclaim metal; After metal was recovered utilization, remaining a large amount of non-metal powders became the secondary waste; Another source is a large amount of scrap stock and the underproof PCB that produces in the PCB production process, and scrap stock and substandard product account for 10~20% of production greatly, thereby will produce quantity huge secondary waste with regard to this every year.These powder are glass fibre enhanced thermosetting epoxy resins, and are insoluble not molten, are difficult to recycle with ordinary method.

Traditionally, the method for disposing these non-metal powders on a large scale is landfill and burning.Landfill not only takies valuable land resources, and pollutes the environment.Burn and can produce a large amount of toxic substance, particularly many bromos dibenzo Dioxins and PBDF, these materials are to produce in combustion processes owing to containing a large amount of bromines in the PCB base material.The content of brominated flame retardant in PCB is bigger, uses among the PCB as the desk-top computer of producing the nineties in 20th century, and bromine content accounts for 9% (weight percent).These methods are disabled at present.

The recovery of non-metallic part is the difficult point and the focus of electron wastes recycling among the discarded PCB.(DE 4337970 to the resource utilization result of study of non-metallic substrate among the discarded PCB many patent disclosures both at home and abroad, JP 2003301404, CN1814665, and WO 2002088277, JP 2003055498, JP 8085736, and WO 9616112, and EP 1437378, JP2005220198, CN 1520943, and JP 2005344058, CN 1792618A).The method of non-metallic substrate mainly contains following several among the discarded PCB of recycling in these disclosed patents: first, do filler with non-metal powder and prepare material of construction etc., as non-metal powder being cut with sand, wood fragments and tackiness agent mixes, prepare pavior, or prepare composite fiber plate as filler; The second, with the non-metallic part pyrolysis among the discarded PCB, reclaim pyrolysis product as industrial chemicals or fuel; The 3rd, additive method, as in the presence of phosphoric acid and organic solvent, under high temperature, decompose thermosetting epoxy resin in the non-metallic substrate with ultrasonic technology, thus the purpose that obtains reclaiming, the apparatus expensive that this method is required, the cost height need carry out in the presence of higher temperature and phosphoric acid, and phosphoric acid has higher corrodibility, thereby, make cost recovery increase to the having relatively high expectations of equipment; Or at high temperature remove halogen in the non-metallic substrate etc. with alkali.

Though the recycling of discarded PCB has caused extensive concern, the recycling of non-metal powder still is a difficult problem.The problem for preparing material of construction or other materials as filler with non-metal powder is that the amount of adding is limited, and the affiliation that adds of non-metal powder influences the performance of material, particularly also contains impurity such as a certain amount of metal-powder and dust in these non-metal powders.A difficult problem of recycling the non-metallic substrate among the discarded PCB with pyrolysis method is the use that is difficult to act as a fuel owing to calorific value is lower of the product after the pyrolysis, also can't be as other industrial chemicals uses, and pyrolysis product will become waste three times.Additive method such as supersonic method need special equipment and higher cost.

Summary of the invention

The present invention discloses a kind of method that realizes reclaiming Resins, epoxy and glass fibre under the condition of gentleness from the non-metal powder of abandoned printed circuit board (PCB), its purpose is to overcome prior art and disposes these non-metal powders employing landfills and burn the land resources that not only takies preciousness, and serious waste resource pollution environment; Prepare material of construction or other materials with non-metal powder as filler, add limited amount and can influence the performance of material; Recycle with pyrolysis method,, will become waste three times because the pyrolysis product calorific value is lower; Additive method such as supersonic method need problems such as special equipment and higher cost.Behind the impurity of the present invention in removing non-metal powder, method is decomposed these non-metal powders in two steps, separates with glass fibre with organic solvent dissolution and with Resins, epoxy then, to reach the purpose that reclaims Resins, epoxy and glass fibre respectively.All reagent in the whole recovery process comprise all recycling uses of mineral acid filtrate and organic solvent, so whole recovery process environment-friendly and green is pollution-free, and rate of recovery height, resource is fully used.

From the non-metal powder of discarded PCB, reclaim the method for Resins, epoxy and glass fibre, it is characterized in that this method may further comprise the steps:

(1) pre-treatment

Non-metal powder is washed with water to water limpid earlier, filter, the non-metal powder drying-free that obtains can directly enter next step;

(2) metallic impurity in the removal non-metal powder

Mineral acid is joined in the non-metal powder after previous step is handled, the concentration of mineral acid is 0.8~4mol/L, the volume ratio of non-metal powder and mineral acid is 10g/50~100mL, heated and stirred, reaction times is 0.5~4 hour, temperature of reaction is 35 ℃~55 ℃, and after-filtration is finished in reaction, and the non-metal powder that obtains need not washing and drying directly enters next step;

(3) decompose for the first time

Mineral acid is joined in the non-metal powder after top processing, the concentration of mineral acid is 5~8mol/L, and the volume ratio of non-metal powder and mineral acid is 10g/30~80mL, and the reaction times is 8~35 hours, temperature of reaction is 75 ℃~95 ℃, and after-filtration is finished in reaction; The solid particulate that leaches is joined in the organic solvent again, stir, filter, the solid that obtains is a glass fibre, boils off the organic solvent in the filtrate, obtains solid epoxy;

(4) decompose for the second time

The above-mentioned solid epoxy that obtains is joined in the mineral acid, the concentration of mineral acid is 4~7mol/L, the volume ratio of solid epoxy and mineral acid is 10g/30~60mL, and to add the organic solvent reaction times be 6~20 hours, and temperature of reaction is 55 ℃~85 ℃, tells organic layer after reaction is finished, use the organic solvent extraction water layer again, merge organic layer, boil off organic solvent, obtain low-molecular-weight Resins, epoxy.

Described mineral acid is nitric acid, sulfuric acid, hydrochloric acid, or the mixing of two kinds of acid.

Described organic solvent is ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, ethyl propionate, ethyl benzoate.

Discarded PCB non-metal powder of the present invention is meant powder residual after having reclaimed metal, contains impurity such as little metal and dust.

The mineral acid filtrate that produces among the present invention will reclaim and recycle, and organic solvent also reclaims and recycles, and is not discharged in the environment, does not increase burden to environment, realizes that the green of the non-metal powder of discarded PCB reclaims.

The advantage and the positively effect of the inventive method are: whole recovery process environment-friendly and green is pollution-free, and rate of recovery height, and resource is fully used.

Embodiment

Describe the present invention below in conjunction with embodiment, but present embodiment is not limited to the present invention, every employing similarity method of the present invention and similar variation thereof all should be listed protection scope of the present invention in.

Embodiment 1

In the 250mL flask that fills the discarded PCB non-metal powder of 30g, add the water of 150mL, stir after 4~5 minutes, the layer that anhydrates, the water washing of using equivalent again to water layer limpid till.Add 0.8mol/L sulfuric acid 150mL then,, filter the solid that obtains and directly add in the flask of 250mL, add 5mol/L nitric acid 300mL again, heat 35 hours after-filtration, filtrate recycling down at 95 ℃ in 55 ℃ of heating 4 hours.Solid washes with water to neutrality, pours in the round-bottomed flask of 250mL, adds the 150mL ethyl acetate, stirs, and filters, and to colourless, obtains glass fibre with identical organic solvent washing.The filtrate evaporate to dryness is obtained solid epoxy.

The above-mentioned solid epoxy that obtains is joined in the round-bottomed flask of 250mL, add 4mol/L nitric acid/sulfuric acid 180mL, under agitation be heated to 85 ℃, reacted 20 hours, and used ethyl acetate extraction water layer four times after reaction is finished, merge organic layer, be spin-dried for solvent, obtain low-molecular-weight epoxy resin.

Adopt the mineral acid of lower concentration in the present embodiment, higher temperature and solid-to-liquid ratio and long reaction times, though the concentration of mineral acid is low, the time is long.

Embodiment 2

In the 250mL flask that fills the discarded PCB non-metal powder of 30g, add the water of 150mL, stir after 4~5 minutes, the layer that anhydrates, the water washing of using equivalent again to water layer limpid till.Add 4mol/L sulfuric acid 300mL then,, filter the solid that obtains and directly add in the flask of 250mL, add 8mol/L nitric acid 90mL again, heat 8 hours after-filtration, filtrate recycling down at 75 ℃ in 35 ℃ of heating 0.5 hour.Solid washes with water to neutrality, pours in the round-bottomed flask of 250mL, adds the 100mL ethyl acetate, stirs, and filters, and to colourless, obtains glass fibre with identical organic solvent washing.The filtrate evaporate to dryness is obtained solid epoxy.

The above-mentioned solid epoxy that obtains is joined in the round-bottomed flask of 250mL, add 7mol/L nitric acid/sulfuric acid 90mL, under agitation be heated to 55 ℃, reacted 20 hours, and used ethyl acetate extraction water layer four times after reaction is finished, merge organic layer, be spin-dried for solvent, obtain low-molecular-weight epoxy resin.

The mineral acid of higher concentration and less consumption in the present embodiment, solid-to-liquid ratio and reaction times all reduce, but the concentration of acid is higher, is unfavorable for operation.

Embodiment 3

In the 250mL flask that fills the discarded PCB non-metal powder of 30g, add the water of 150mL, stir after 4~5 minutes, the layer that anhydrates, the water washing of using equivalent again to water layer limpid till.Add 1mol/ nitric acid 150mL then,, filter the solid that obtains and directly add in the flask of 250mL, add 6mol/L nitric acid 100mL again, heat 20 hours after-filtration, filtrate recycling down at 85 ℃ in 40 ℃ of heating 1.5 hours.Solid washes with water to neutrality, pours in the round-bottomed flask of 250mL, adds the 100mL ethyl acetate, stirs, and filters, and to colourless, obtains glass fibre with identical organic solvent washing.The filtrate evaporate to dryness is obtained solid epoxy.

The above-mentioned solid epoxy that obtains is joined in the round-bottomed flask of 250mL, add 5mol/L nitric acid/sulfuric acid 100mL, under agitation be heated to 80 ℃, reacted 10 hours, and used ethyl acetate extraction water layer four times after reaction is finished, merge organic layer, be spin-dried for solvent, obtain low-molecular-weight epoxy resin.

The add-on of mineral acid, concentration, reaction times are suitable in the present embodiment, and the productive rate that obtains is higher, also do not cause the waste of raw material.

Embodiment 4

In the 250mL flask that fills the discarded PCB non-metal powder of 30g, add the water of 150mL, stir after 4~5 minutes, the layer that anhydrates, the water washing of using equivalent again to water layer limpid till.Add 2mol/ nitric acid 150mL then,, filter the solid that obtains and directly add in the flask of 250mL, add 6.5mol/L nitric acid 110mL again, heat 14 hours after-filtration, filtrate recycling down at 85 ℃ in 45 ℃ of heating 0.5 hour.Solid washes with water to neutrality, pours in the round-bottomed flask of 250mL, adds the 100mL ethyl acetate, stirs, and filters, and to colourless, obtains glass fibre with identical organic solvent washing.The filtrate evaporate to dryness is obtained solid epoxy.

The above-mentioned solid epoxy that obtains is joined in the round-bottomed flask of 250mL, add 4mol/L nitric acid 100mL, under agitation be heated to 85 ℃, reacted 8 hours, and used ethyl acetate extraction water layer four times after reaction is finished, merge organic layer, be spin-dried for solvent, obtain low-molecular-weight epoxy resin.

The add-on of mineral acid, concentration, reaction times are suitable in the present embodiment, and the productive rate that obtains is higher, also do not cause the waste of raw material.

Embodiment 5

The discarded PCB non-metal powder of 12kg is poured in the porcelain enamel barrel of 50L, is added the water of 30L, stir the layer that anhydrates after 10 minutes, the water washing of using equivalent again to water layer limpid till, leach pressed powder at last.Then pressed powder is joined in the glass reaction still of 50L, add 2mol/L sulfuric acid, leach solid after 2 hours in 55 ℃ of heating.

Above-mentioned solid is joined the glass reaction still of 50L, add the nitric acid of 30L6.5mol/L, under agitation be heated to 87 ℃.React and after 20 hours solid and liquid are emitted, filter the filtrate recycling use.Solid washes with water to neutrality, adds the 12L ethyl acetate, stirs, and filters then, and to colourless, the solid that obtains is a glass fibre with the ethyl acetate washing, and the solvent that boils off in the filtrate obtains solid epoxy, collects organic solvent simultaneously, recycles.

The above-mentioned solid epoxy that obtains is joined in the nitric acid of 15L5mol/L,, use ethyl acetate extraction 4 times, merge organic layer, boil off solvent, obtain the less Resins, epoxy of molecular weight in 75 ℃ of heating 6 hours.Water layer is that inorganic acid solution can be recycled.

Claims (2)

1. from the non-metal powder of abandoned printed circuit board, reclaim the method for Resins, epoxy and glass fibre, it is characterized in that this method may further comprise the steps:
(1) pre-treatment
Non-metal powder is washed with water to water limpid earlier, filter, the non-metal powder drying-free that obtains directly uses;
(2) metal residue in the removal non-metal powder
Mineral acid is joined in the non-metal powder of handling through previous step, the concentration of mineral acid is 0.8~4mol/L, the volume ratio of non-metal powder and mineral acid is 10g/50~100mL, heated and stirred, reaction times is 0.5~4 hour, temperature of reaction is 35 ℃~55 ℃, filters then, and the non-metal powder that obtains need not washing and drying directly enters next step;
(3) decompose for the first time
Mineral acid is joined in the non-metal powder of handling through above-mentioned steps, the concentration of mineral acid is 5~8mol/L, the volume ratio of non-metal powder and mineral acid is 10g/30~80mL, reaction times is 8~35 hours, temperature of reaction is 75 ℃~95 ℃, after-filtration is finished in reaction, collects acidleach liquid and recycles; The solid particulate that leaches is joined in the organic solvent again, stir, filter, the solid that obtains is a glass fibre, boils off the organic solvent in organic filtrate, obtains solid epoxy;
(4) decompose for the second time
The above-mentioned solid epoxy that obtains is joined in the mineral acid, the concentration of mineral acid is 4~7mol/L, the volume ratio of solid epoxy and mineral acid is 10g/30~60mL, and adds organic solvent, and the reaction times is 6~20 hours, temperature of reaction is 55 ℃~85 ℃, tell organic layer after reaction is finished, use identical organic solvent extraction water layer again, merge organic layer, boil off organic solvent, obtain low-molecular-weight Resins, epoxy;
Described mineral acid is nitric acid, sulfuric acid, hydrochloric acid, or the mixing of two kinds of acid.
2. the method that reclaims Resins, epoxy and glass fibre from the non-metal powder of abandoned printed circuit board according to claim 1, it is characterized in that: organic solvent is ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, ethyl propionate, ethyl benzoate.
CN2008102004105A 2008-09-25 2008-09-25 Method for recycling epoxy resins and glass fibre from non-metal powder of waste printed circuit board CN101407596B (en)

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CN101787145B (en) * 2010-03-12 2011-09-21 中国科学院长春应用化学研究所 Method for recovering fiber from epoxy resin/fiber composite material
CN102240606B (en) * 2011-05-05 2013-06-19 广州有色金属研究院 Method for separating nonmetal materials from waste circuit boards by flotation
CN102294345A (en) * 2011-06-24 2011-12-28 清远市东江环保技术有限公司 Method for processing discarded PCBs (printed circuit boards) into composite municipal products
CN103084369B (en) * 2011-11-08 2015-09-02 江西格林美资源循环有限公司 A kind of harmless treatment of circuit board and the method for resource comprehensive utilization
CN102504491B (en) * 2011-11-14 2013-06-26 同济大学 Preparation method for waste circuit board non-metal powder modified epoxy glass fiber reinforced plastic composite material
CN104894696B (en) * 2015-06-29 2017-01-04 重庆再升科技股份有限公司 A kind of method from non-inductive windings filter paper trimming recycled fiber
US20170022636A1 (en) 2015-07-22 2017-01-26 Korea Institute Of Science And Technology Method and composition for depolymerization of cured epoxy resin materials
CN107082626A (en) * 2016-02-15 2017-08-22 山东理工大学 A kind of method for comprehensively utilizing carbon fibre reinforced composite and red mud discarded object
CN107399928B (en) * 2017-08-22 2020-03-17 上海第二工业大学 Glass fiber ball bundle and preparation method thereof
CN107400255A (en) * 2017-08-31 2017-11-28 江苏中信世纪新材料有限公司 Method of the organic salt as catalyst chemical degraded epoxy resin
CN107825615A (en) * 2017-11-18 2018-03-23 陈潇曼 Epoxy resin pre-processing device is used in a kind of LED manufacture

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003055498A (en) * 2001-08-20 2003-02-26 Chubu Electric Power Co Inc Method for decomposing thermosetting resin
CN1483754A (en) * 2003-07-30 2004-03-24 哈尔滨工业大学 Chenical recovery method for thermosetting epoxy compound material
EP1437378A1 (en) * 2003-01-09 2004-07-14 Electricité de France Process for the valorization of waste epoxy resin materials
CN1520943A (en) * 2003-02-11 2004-08-18 巫协森 Method and apparatus for processing waste containing bromination epoxy resin and glass fiber
JP2005220198A (en) * 2004-02-04 2005-08-18 Hitachi Chem Co Ltd Dehalogenation method of halogen-containing epoxy resin
JP2005344058A (en) * 2004-06-04 2005-12-15 Hitachi Chem Co Ltd Method for treating cured epoxy resin
CN101007313A (en) * 2006-01-20 2007-08-01 巫协森 Recovery method of discarded printed circuit boards

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003055498A (en) * 2001-08-20 2003-02-26 Chubu Electric Power Co Inc Method for decomposing thermosetting resin
EP1437378A1 (en) * 2003-01-09 2004-07-14 Electricité de France Process for the valorization of waste epoxy resin materials
CN1520943A (en) * 2003-02-11 2004-08-18 巫协森 Method and apparatus for processing waste containing bromination epoxy resin and glass fiber
CN1483754A (en) * 2003-07-30 2004-03-24 哈尔滨工业大学 Chenical recovery method for thermosetting epoxy compound material
JP2005220198A (en) * 2004-02-04 2005-08-18 Hitachi Chem Co Ltd Dehalogenation method of halogen-containing epoxy resin
JP2005344058A (en) * 2004-06-04 2005-12-15 Hitachi Chem Co Ltd Method for treating cured epoxy resin
CN101007313A (en) * 2006-01-20 2007-08-01 巫协森 Recovery method of discarded printed circuit boards

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JP平8-085736A 1996.04.02

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