CN101434112B

CN101434112B - Method for separating resin

Info

Publication number: CN101434112B
Application number: CN2008102157168A
Authority: CN
Inventors: 宫坂将稔; 小岛环生; 矶见晃; 田端大助; 中裕之; 酒井弥彦
Original assignee: Matsushita Electric Industrial Co Ltd
Current assignee: Panasonic Holdings Corp
Priority date: 2007-11-14
Filing date: 2008-09-02
Publication date: 2011-05-04
Anticipated expiration: 2028-09-02
Also published as: CN101434112A; JP2009137273A; ATE529198T1; JP4439571B2

Abstract

To provide a high purity separation method of resin materials, which method does not produce waste water and is not affected by the specific gravities and dielectric characteristics of resin materials, in recycling of resin materials as resources. A separation object including at least two types of resins with different glass transition temperatures (glass transition temperature of a first resin 1 < glass transition temperature of a second resin 2) is placed on a separating member 3. Next, primary heating is applied at a temperature between the glass transition temperatures of the first resin 1 and the second resin 2, and pressurization is additionally performed to cause the first resin 1 to adhere to the separating member 3. Subsequently, a heat history of secondary heating at a temperature higher than the primary heating temperature is applied to detach and recover the second resin 2 by restoring the shape of the second resin 2, while the first resin 1 adhering to and retained by the separating member 3 is detached by a blade 5 and the like for recovery.

Description

Method for separating resin

Technical field

The present invention relates to be used for the renewable resources of waste household appliances goods, the technology of separation resin from the separate object thing that is mixed with resin sheet.

Background technology

In recent years a large amount of productions, a large amount of economic activity of consuming, discarding in a large number type have caused global environment problem such as greenhouse effects and resource exhaustion.Under these circumstances, be to make up circular form society, self-balancing becomes rise in April, 13 to have implemented household electrical appliances and utilizes method again, and the utilization again of waste air-conditioner (air conditioner), television picture tube, refrigerator ice cabinet, washing machine is decided to be obligation.

In the past, useless tame electrical article was in after electricity utilizes factory's fragmentation again, utilized magnetic force, wind-force, vibration etc. that different materials is separated and reclaimed, and carried out renewable resources.Especially metal material, by using gravity separation device or magnetic force sorting unit, but high-purity reclaims different materials such as iron, copper, aluminium, realizes high renewable resources rate.

On the other hand, in the resin material, the polypropylene (following note is made PP) of light proportion can separate with the height ratio weight by wet separation by specific gravity, reclaims with higher degree.Yet, in the wet separation by specific gravity, a large amount of drainings polystyrene close with proportion (following note is made PS) and acrylonitrile-butadiene-styrene (following note is made ABS) take place can't separate etc. and all to have become big problem.In addition in recent years, the demand of hyperbaric filler filling polypropylene composite material is also enlarging, and this is to use proportion separation in the past to be difficult to tackle.

In following patent documentation 1, patent documentation 2, proposed to have considered the separation method of the problems referred to above relevant with the resin material renewable resources.

Patent documentation 1 has proposed to have utilized the separation method as the melt temperature difference of 2 kinds of resins of separate object, this method heats the medium temperature of melt temperature that a pair of heat-resisting steel plane of rotation makes it to reach 2 kinds of resins of separate object, with 2 kinds of resins of separate object gap by the plane of rotation of above-mentioned heating, the low resin of melt temperature is attached on the plane of rotation of above-mentioned heating, separates 2 kinds of resins by this.

In addition, patent documentation 2 has proposed to have utilized the different separation method of dielectric loss between resin material.This method to the separate object thing that is mixed with resin more than 2 kinds in addition electromagnetic wave wait and impose the medium heating, the melting characteristic difference of utilizing the heat generation characteristic difference of different resins material to be caused is separated, utilize these methods, draining neither takes place, also be not subjected to the influence of resin material proportion.

Patent documentation 1: Japan Patent is opened flat 4-126822 communique in fact

Patent documentation 2: the Japan Patent spy opens the 2002-234031 communique

Summary of the invention

Yet in patent documentation 1, for low polar molecule materials low with the adhesiveness of other material such as PP and PS, it is unstable that the adhesive strength of molten resin becomes, and can't do highly purified separation.In addition, if low melting point resin and high melting point resin simultaneously by the gap of the sliding surface that heats, then can occur in fusion low melting point resin on be attached with the high melting point resin of not fusion, the problem that can't separate.

In addition, in patent documentation 2, owing to can't carry out the separation of the resin material of dielectric loss characteristic close, therefore highly purified recovery is very difficult.

The present invention is the invention that solves above-mentioned existing problem, and its objective is provides the method for separating resin that draining does not take place, be not subjected to resin material proportion and dielectric loss properties influence.

The method for separating resin of claim 1 record of the present invention is characterised in that, on separating component, carry out the 1st heating with being mixed with the different separate object thing mounting of resin more than 2 kinds of vitrification point and yield stress, pressurization simultaneously, the temperature that at this moment the 1st time heated is set at the vitrification point that is lower than the resin more than a kind in the above-mentioned resin, and the temperature that is higher than the vitrification point of the resin more than a kind, plus-pressure at this moment is set in vitrification point to be lower than in the resin of the 1st heating-up temperature, more than the compressive yield stress of the resin that compressive yield stress is the highest, at least the resin that makes vitrification point be lower than the 1st heating-up temperature is attached on the above-mentioned separating component, the resin or the little resin of adhesive force that are not attached on the above-mentioned separating component are separated from above-mentioned separating component, further the above-mentioned separating component that has adhered to resin is carried out the 2nd heating, the temperature of the 2nd heating of this moment is set at and is higher than heating-up temperature the 1st time, and be lower than the temperature of the melting point of the resin that melting point is minimum in the above-mentioned separate object thing, the resin that only makes vitrification point be lower than the 1st heating-up temperature is attached to above-mentioned separating component, the resin that is attached on the above-mentioned separating component is separated from above-mentioned separating component, separate.

The method for separating resin of claim 2 record of the present invention according to claim 1, it is characterized in that, with the temperature of the 1st heating be set in above-mentioned vitrification point and yield stress different more than 2 kinds in the resin, the temperature between the vitrification point of the low resin that is only second to this resin of the vitrification point of the resin that vitrification point is minimum and vitrification point.

The method for separating resin of claim 3 record of the present invention according to claim 1, it is characterized in that, with the temperature of the 1st heating be set in above-mentioned vitrification point and yield stress different more than 2 kinds in the resin, the height of the vitrification point of the resin that vitrification point is the highest and vitrification point is only second to the temperature between the vitrification point of resin of this resin.

The method for separating resin of claim 4 of the present invention record is characterized in that according to claim 1, and above-mentioned plus-pressure is the plus-pressure more than 1.2 times of the compressive yield stress of the resin that reclaims of desire.

The method for separating resin of claim 5 of the present invention record is characterized in that according to claim 1, with separate object thing mounting on the compression aspect of the resin on the separating component minimum thickness and the difference of maximum ga(u)ge in 5.5mm.

The method for separating resin of claim 6 of the present invention record is characterized in that according to claim 1, with separate object thing mounting in the scope of the thickness on the compression aspect of the resin on the separating component below the above 6.0mm of 0.5mm.

The method for separating resin of claim 7 of the present invention record is characterized in that according to claim 1, with separate object thing mounting in the scope of the thickness on the compression aspect of the resin on the separating component below the above 6.0mm of 1.0mm.

The method for separating resin of claim 8 of the present invention record is characterized in that according to claim 1, with separate object thing mounting in the scope of the thickness on the compression aspect of the resin on the separating component below the above 3.0mm of 1.0mm.

The method for separating resin of claim 9 record of the present invention according to claim 1, it is characterized in that, add at the 2nd time and to pine for, vitrification point is lower than the programming rate of the resin of the 1st heating-up temperature, is higher than the programming rate of the resin of the 1st heating-up temperature less than vitrification point.

The method for separating resin of claim 10 record of the present invention according to claim 1, it is characterized in that, add at the 2nd time and to pine for, the programming rate that is higher than the resin of the 1st heating-up temperature by the programming rate that makes vitrification point be lower than the resin of the 1st heating-up temperature less than vitrification point, the resin that makes above-mentioned vitrification point be lower than the 1st heating-up temperature is short more than 5 seconds at the resin that the more above-mentioned vitrification point of heat treated time under the intensification limiting temperature is higher than the 1st heating-up temperature, and above-mentioned vitrification point is lower than heating-up time of resin of the 1st heating-up temperature below 60 seconds.

The method for separating resin of claim 11 record of the present invention according to claim 1, it is characterized in that the separate object thing comprises wantonly at least a kind in polypropylene, polyethylene, PLA, polyvinyl chloride, polystyrene, acrylonitrile-styrene, acrylonitrile-butadiene-styrene, the Merlon.

The method for separating resin of claim 12 of the present invention record is characterized in that according to claim 1, the separate object thing by polypropylene, and polystyrene or acrylonitrile-butadiene-styrene at least a kind form.

The method for separating resin of claim 13 record of the present invention according to claim 1, it is characterized in that, the separate object thing by polypropylene, and polystyrene or acrylonitrile-butadiene-styrene at least a kind form, and be set at the temperature of the 1st heating more than 15 ℃ and be lower than the temperature of the vitrification point of separate object resin kinds whole except that polypropylene, the temperature of the 2nd heating is set at more than 70 ℃ below 155 ℃, and is higher than the temperature of the 1st heating.

The method for separating resin of claim 14 record of the present invention according to claim 1, it is characterized in that, the separate object thing by polypropylene, and polystyrene or acrylonitrile-butadiene-styrene at least a kind form, and be set at the temperature of the 1st heating more than 15 ℃ and be lower than beyond the polypropylene all temperature of the vitrification point of the resin kind of separate object things, the temperature of the 2nd heating is set at more than 100 ℃ below 155 ℃, and is higher than the temperature of the 1st heating.

According to this formation, by with the separate object thing mounting of the resin of thickness in setting range on separating component, and heat pressurization with the temperature between the vitrification point of above-mentioned separate object resin, can be situated between with separating component, the resin isolation that vitrification point is higher than the resin of heating-up temperature and is lower than heating-up temperature is opened.Thus, can from the above-mentioned separate object thing that can't separate, separate desired resin in high-purity ground with prior art.

Description of drawings

Fig. 1 is the operation sectional view of the method for separating resin of expression embodiments of the present invention 1.

Fig. 2 is the key diagram of the temperature variant measurement result of compressive yield stress of each resin in the same embodiment.

Fig. 3 is the plus-pressure of PP in the same embodiment and the graph of a relation of the rate of recovery.

Fig. 4 is to the 1st heating of separate object thing and the graph of a relation of the PP rate of recovery in the same embodiment.

Fig. 5 is for PP, PS separate object thing, the graph of a relation of the 1st heating and PP purity.

Fig. 6 is for PP, ABS separate object thing, the graph of a relation of the 1st heating and the PP rate of recovery.

Fig. 7 is for PP, ABS separate object thing, the graph of a relation of the 1st heating and PP purity.

Fig. 8 is for PP, PS separate object thing, the graph of a relation of the 2nd heating and PP and PS purity.

Fig. 9 is for PP, PS separate object thing, the graph of a relation of the 2nd heating and the PP rate of recovery.

Figure 10 is the 2nd heat time heating time that contains in the separation of separate object thing of PP and PS, with the graph of a relation of the adhesion strength of PP and PS and separating component.

Figure 11 is the infrared absorption character figure of PP.

Figure 12 is the infrared absorption character figure of PS.

Figure 13 is the performance plot of the 2nd heating means.

Figure 14 is the graph of a relation of the purity of the difference of PS and the heat time heating time of PP under the intensification limiting temperature and PP and PS.

Figure 15 is the operation sectional view of the method for separating resin of expression embodiments of the present invention 2.

Figure 16 is for PP, PS, ABS separate object thing, the graph of a relation of the 1st heating and the PP rate of recovery.

Figure 17 is for PP, PS, ABS separate object thing, the graph of a relation of the 1st heating and PP purity.

Figure 18 is the operation sectional view of the method for separating resin of expression embodiments of the present invention 3.

The specific embodiment

Embodiment 1

Fig. 1～Figure 14 represents embodiments of the present invention 1.

Fig. 1 (a)～Fig. 1 (f) represents from the separate object thing that is mixed with the 1st kind of different resin 1 of vitrification point and yield stress and 2 two kinds of resins of the 2nd kind of resin, the operation of separation resin.

Among Fig. 1 (a), on separating component 3 mounting above-mentioned separate object thing.Here, the vitrification point of the 1st kind of resin 1 is lower than the vitrification point of the 2nd kind of resin 2.

Among Fig. 1 (b), carry out the 1st heating.The heating-up temperature of this moment is the temperature between the vitrification point of the 1st kind of resin 1 and the 2nd kind of resin 2.

At this moment, by dull and stereotyped 4 the 1st kind of resin 1 and the 2nd kind of resin 2 are pressed on the separating component 3.The compressive yield stress of this stressed size and the 1st kind of resin 1 is identical or on it, by under this state to the 1st kind of resin 1 and the 2nd kind of resin 2 heating pressurizations, the 1st kind of resin 1 is attached on the separating component 3.In other words, the 1st kind of resin 1 of this moment owing to in the heating of the condition more than the vitrification point and more than compressive yield stress pressurization, therefore plastic deformation takes place, is attached on the separating component 3.In addition, though when the plus-pressure of above-mentioned heating pressurization when the compressive yield stress of the 2nd kind of resin 2 is above, warpage also can take place in the 2nd kind of resin 2, be attached on the separating component 3, but because machining deformation carries out being lower than under the temperature of vitrification point, if therefore be higher than the thermal process of the 1st heating-up temperature after pressure discharges, then shape returns to the preceding state of pressurization, breaks away from from separating component 3.In addition, when the plus-pressure of above-mentioned heating pressurization during less than the compressive yield stress of the 2nd kind of resin 2, the 2nd kind of resin 2 is not attached on the separating component 3.In addition, if separating component 3 uses surfaces such as wire netting or punch metal that the sheet material of concaveconvex shape is arranged, then can obtain good adhesion strength.

Then as Fig. 1 (c) shown in, by discharging above-mentioned moulding pressure, make separating component 3 inclinations or make the method for separating component 3 little vibrations etc., separablely be attached to the resin on the separating component 3 and be not attached to resin on the separating component 3.Here, the 2nd kind of resin 2b that is not attached on the separating component 3 breaks away from from separating component 3.The 2nd kind of resin 2 usefulness 2a that are attached on the separating component 3 represent.

In addition, when containing the material (metal, paper, wood chip, thermosetting resin etc.) that under the heating pressurized conditions of Fig. 1 (b), is not attached on the separating component 3 in the separate object thing, can with the 2nd kind of the same conduct of resin 2b bur not, separate and remove with the 1st kind of resin 1, the 2nd kind of resin 2a on being attached to separating component 3.

Then in Fig. 1 (d), be higher than the 1st heating-up temperature and be lower than the 1st kind of resin 1 and the 2nd kind of resin 2 in the temperature of melting point of the lower resin of melting point carry out the 2nd heating.Thus, the recovery of shape that always is attached to the 2nd kind of resin 2a on the separating component 3 is to the preceding state of pressurization, become the state that breaks away from from separating component 3 or with the significantly reduced state of the adhesive strength of separating component 3, therefore, by separating component 3 being tilted or making the method for separating component 3 little vibrations etc., can be shown in Fig. 1 (e), separate with the 1st kind of resin 1 on being attached to separating component 3.

In addition, above-mentioned the 1st heating and the 2nd heating both can be implemented by separating component 3 is contacted with hot plate, also can adopt radiation mode or hot blast mode etc. without particular limitation.

Then in Fig. 1 (f), can reclaim the 1st kind of resin 1 that is attached on the separating component 3 by the mode that scrapes with blade 5 grades.At this moment, if by the 1st kind of resin 1 being carried out the 3rd heating the elastic modelling quantity of the 1st kind of resin 1 is descended, then the branch defection of the 1st kind of resin 1 and separating component 3 becomes easy.

General, when the heating resin material, exist from low temperature hard, the state that do not have flowability down, the temperature that rigidity reduces rapidly, flowability increases sharply in certain narrow temperature range.The temperature that causes such change in physical is called vitrification point.

Following table 1 is to use differential scanning calorimetry (differentialScanning the Calorimeter) (model: the DSC220) result of the vitrification point of mensuration PP, PE, PLA, PVC, PS, AS, ABS and PC of Seiko Electronics Co., Ltd system.Confirmed the notable difference of the vitrification point that the difference by each resin causes.

Table 1

In addition, the SP2 in the table is Scientific Polymer Products.Inc. (U.S.), and UMG is UMGABS limited company (UMG ABS.Ltd.).

Resin material is exerted pressure, and when this plus-pressure was risen, if reach the above scope of elastic limit of resin material, the then corresponding stressed a little increase of arrival, displacement (strain) promptly began the rapid point (yield point) that increases.Plus-pressure when arriving this is defined as compressive yield stress.

The compression stress analyzer (model: TCM10000 (compressive load speed 1mm/ branch)) that Fig. 2 is to use the Tokyo impact machine to make institute (TOKYO SEIZOSHO Ltd.) system is measured the temperature variant result of compressive yield stress of each resin material in the table 1.

All compressive yield stress reduces each resin material with the rising of temperature, when reaching vitrification point when above, reaches below the determination limit.This is because the impatient sharp increase of resin flow adds when vitrification point is above, and when vitrification point was above, each resin all under low plus-pressure compression took place easily as can be known.

Embodiment 1

The method of separating desired resin from the separate object thing that contains PP and PS is described.

The 1st kind of resin 1 here is PP, and the 2nd kind of resin 2 is PS.

Separating component 3 and separate object thing are loaded on the increased pressure board of platen-press, for reaching the backing plate (spacer) that specific thickness accompanies 3.0mm, pressurizeed 60 seconds, further remove the following resin of 1.0mm, make thickness homogenization on the compression aspect by this to the scope below the above 3.0mm of 1.0mm.

In addition, also can be with the compress mode of roll squeezer replacement platen-press with the resin homogenization to desired thickness.When using roll squeezer, no matter vertical, the horizontal thickness homogenization continuously that all can make resin, can effectively implement the homogenization of resin thickness by optimization, optimization nip (roll gap), pressure roller footpath, pressure roller rotation number, pressure roller number this moment.

Separating component 3 uses the stainless steel wire mesh of mesh 0.28mm, line footpath 0.23mm, big or small 150mm * 150mm.

Then in 45～55% the ratio that is equivalent to separating component 3 gross areas, under the condition of non-overlapping copies between the resin with above-mentioned separate object thing mounting on separating component 3, this separating component 3 is loaded on the hot plate of hot press, carry out the 1st time in 70 ℃ and heat, carry out 30 seconds heating pressurization with plus-pressure 20000kgf.

Then mounting is had the above-mentioned separating component 3 of the separate object thing that has applied the heating pressurization to be loaded on the electric hot plate, when carry out 20 seconds with 150 ℃ the 2nd time was heated, inclination separating component 3 also separated and reclaims the 2nd kind of resin 2.

The separating component 3 of then separation having been removed the 2nd kind of resin 2 is loaded on the above-mentioned electric hot plate, with 150 ℃ of the 3rd heating carrying out 30 seconds, and on above-mentioned electric hot plate, utilize the stainless steel blade of thickness 1mm, the 1st kind of resin 1 that sticks on the above-mentioned separating component 3 scraped, peel off recovery.

Utilize infrared absorption spectrometric apparatus that the 2nd time is heated and add the resin of pining for separating for the 3rd time and implement qualitative analysis, confirm the quality of resin isolation.As a result, the resin that breaks away from by the 2nd heating is the PS of purity 100%, and the resin that scrapes with blade by the 3rd heating is the PP of purity 100%.

In addition, preferably in homogenization to the specific thickness, with the particle footpath homogenization of sieve with the separate object thing.At first remove thick thing in the separate object thing, then remove and mix sheet and powder for a short time in the separate object thing with the sieve of mesh 1.0mm with the sieve of mesh 8.5mm, by this can with the particle of separate object thing directly homogenization to certain limit.

In addition, visible the 1st heating-up temperature is high more, and the adhesion strength of resin is big more, and the 2nd, the 3rd heating-up temperature is high more in addition, resin peel off easy more tendency.Yet, if heat, can cause the fusion of resin with the temperature more than the resin melting point in the separate object thing, therefore adhere to and peel off and can't fully carry out, can't separate efficiently.Therefore, heating-up temperature can not surpass the melting point of the resin that melting point is minimum in the above-mentioned separate object thing.

Below, the plus-pressure, the 1st during the heating pressurization that just quality of above-mentioned resin isolation impacted, temperature, the thickness of resin and the influence of impurity of the 2nd heating describe successively.

Stressed influence during-heating pressurization-

Fig. 3 be expression when containing heating pressurization in the separation of separate object thing of PP and PS plus-pressure and the relation of the PP rate of recovery.Transverse axis is with respect to the compressive yield stress of PP under the temperature of the 1st heating, under the temperature of the 1st heating to the stressed ratio of separate object thing.The PP rate of recovery (%) of the longitudinal axis is with respect to PP total amount contained in the separate object thing, the percentage (%) of the PP amount by the 3rd heating recovery.

As shown in Figure 3, if find to increase plus-pressure, then the rate of recovery of PP improves.By plus-pressure being brought up to more than the compressive yield stress of PP, can make PP keep sticking on the separating component, can from the separate object thing, reclaim PP.Found the compressive yield stress with respect to PP in addition, the rate of recovery of the preferred PP of plus-pressure of PP reaches 100% o'clock more than 1.2 times.

Also carried out same checking with the resin beyond the PP that exemplifies in the table 1, the result can both reclaim with the condition more than the yield pressure stress under compression any resin, and the condition more than 1.2 times with the yield pressure stress under compression can obtain high-recovery in addition.

In addition, owing to the undue conference of plus-pressure produces the breakage of separating component, the load increase to equipment, the problems such as destruction of resin, therefore need according to separating component and specification of equipment capping value.

The influence of one the 1st heating-up temperature-

Fig. 4 is that expression contains the 1st heating-up temperature in the separation of separate object thing of PP and PS and the relation of the PP rate of recovery.Fig. 5 is that expression contains the 1st heating-up temperature in the separation of separate object thing of PP and PS and the relation of PP purity.The PP purity (%) of the longitudinal axis of Fig. 5 is with respect to the resin total amount by the 3rd heating recovery, the percentage (%) of the PP amount by the 3rd heating recovery.

The solid line of Fig. 4 is 30 seconds gained curves of heating pressurization under plus-pressure 20000kgf.When the 1st heating-up temperature below 40 ℃ the time because PP is not attached on the separating component 3, therefore PP is remained on the separating component 3, can't separate recovery.When the 1st heating-up temperature from more than 60 ℃ to 90 ℃ interval the time, the adhesive strength of PP increases, and by the 2nd heating and the operation of heating for the 3rd time, can make the purity of PP and the rate of recovery reach 100%.

In addition, the dotted line of Fig. 4 is 30 seconds gained curves of heating pressurization under plus-pressure 40000kgf, owing to increase in the adhesive strength of PP more than 15 ℃, therefore can make the purity of PP and the rate of recovery reach 100%.Under the so high condition of plus-pressure, can separate PP in low temperature region.But, if pressure is increased to the destruction that is higher than 40000kgf then separating component can take place.

In addition as shown in Figure 5, if the temperature of the 1st heating is increased to more than 100 ℃, then since this temperature not only than the vitrification point of PP, also than the vitrification point height of PS, therefore can't make the recovery of shape of PS by the 2nd heating, the purity of PP descends.

Found that by above,, must carry out the 1st heating, more preferably carrying out the 1st heating with the temperature below 90 ℃ more than 60 ℃ under the plus-pressure 20000kgf with the temperature below 90 ℃ more than 15 ℃ for the separate object thing that contains PP and PS.

Fig. 6 is illustrated in the 1st heating-up temperature in the separation of the separate object thing that contains PP and ABS and the relation of the PP rate of recovery.Fig. 7 is illustrated in the 1st heating-up temperature in the separation of the separate object thing that contains PP and ABS and the relation of PP purity.

As shown in Figure 6 and Figure 7, can confirm the identical tendency of separating with the separate object thing that contains PP and PS.As shown in Figure 6, when the temperature of the 1st heating below 40 ℃ the time, PP is adhered to remain on the separating component 3, can't separate recovery.When the temperature of the 1st heating in 60 ℃ to 110 ℃ scope the time, the adhesive strength of PP increases, the operation by the 2nd heating and the 3rd heating can make the purity of PP and the rate of recovery reach 100%.In addition, the dotted line of Fig. 6 is 30 seconds gained curves of heating pressurization under plus-pressure 40000kgf condition, owing to increase in the adhesive strength of PP more than 15 ℃, therefore can make the purity of PP and the rate of recovery reach 100%.

In addition as shown in Figure 7, if the temperature of the 1st heating is increased to more than 120 ℃, then since this temperature not only than PP, also than the vitrification point height of ABS, therefore can't make the recovery of shape of ABS by the 2nd heating, the purity of PP descends.

Found that by above,, must carry out the 1st heating, more preferably carrying out the 1st heating with the temperature below 110 ℃ more than 60 ℃ under the plus-pressure 20000kgf with the temperature below 110 ℃ more than 15 ℃ for the separate object thing that contains PP and ABS.

The influence of-the 2 heating-up temperature-

Fig. 8 is that expression contains the 2nd heating-up temperature in the separation of separate object thing of PP and PS and the relation of PP and PS purity.Fig. 9 is that expression contains the 2nd heating-up temperature in the separation of separate object thing of PP and PS and the relation of the PP rate of recovery.

The PS purity (%) of the longitudinal axis of Fig. 8 is with respect to breaking away from the resin total amount that reclaims by the 2nd heating, breaking away from the percentage (%) of the PS amount that reclaims by the 2nd heating.On the other hand, the PP purity (%) of the longitudinal axis of Fig. 8 is for after carrying out the 2nd heating with the temperature of setting, with respect to adding the resin total amount that thermal release is reclaimed by the 3rd time, and the percentage of the PP amount by the 3rd heating recovery.

As shown in Figure 8, in the temperature of the 2nd heating when being lower than 70 ℃, because the temperature of the 2nd heating is low than the 1st heating, the shape of PS can not restored the shape to the pressurization, so PS can't separate PP and PS effectively from separating component 3 disengagings.If the temperature of the 2nd heating is increased to more than 70 ℃, then because the shape of PS begins to restore, so PS breaks away from from separating component, can carry out separating of PP and PS.

Temperature the 2nd heating heats in the scope from 100 ℃ to 155 ℃ under 20 seconds the situation, can make the purity of PP reach 100%.In addition as shown in Figure 9, if the temperature of the 2nd heating is increased to more than 155 ℃, then because PP fusion and being fused on the separating component 3, the rate of recovery of PP descends.

Also carried out same checking with the resin beyond the PP that exemplifies in the table 1, the 2nd heating (Japanese: 2 times add Hot, based on context should be meant the 2nd heating) as a result must the resin that melting point is minimum in being lower than the separate object thing melting point and being higher than under the temperature of the 1st heating-up temperature carry out.

Found that by above, for the separate object thing that contains PP and PS, the separate object thing that contains the separate object thing of PP and ABS and contain PP, PS and ABS, the temperature that temperature must be set at more than 70 ℃ below 155 ℃ and be higher than the 1st heating-up temperature is carried out the 2nd heating, preferably temperature is set at more than 100 ℃ below 155 ℃ and the temperature that is higher than the 1st heating-up temperature is carried out the 2nd heating.

The influence of-resin thickness-

Because under the bigger situation of the form variations of separate object thing, can take place during pressurization pressure deviation, can't obtain good attachment phenomenon, therefore preferably the thickness of separate object thing is done homogenization in advance.If find resin maximum ga(u)ge in the thickness on the compression aspect with respect to the difference of minimum thickness in 5.5mm, then pressure apply basic homogeneous, can obtain good attachment phenomenon.

Be the influence of research thickness, use backing plate to implement the adjustment of thickness by platen-press.Following table two is with respect to the thickness range of separate object thing on compression aspect, the purity of PP and PS and the measurement result of the rate of recovery.

Table 2

Separating component 3 and separate object thing are loaded on the increased pressure board of platen-press, for reaching the backing plate that specific thickness accompanies 6.0mm, pressurizeed 60 seconds, further remove the resin of not enough 0.5mm, make thickness homogenization on the compression aspect by this to the scope below the above 6.0mm of 0.5mm, and maximum ga(u)ge is adjusted in the 5.5mm with respect to the difference of minimum thickness.At this moment, the purity of PS reaches more than 90%, can by with the combination of other method for separating resin, carry out regeneration of resin by most of resin material manufacturer, so this method is preferable.

Same, if by the thickness adjustment of carrying out with backing plate etc., the thickness homogenization that makes above-mentioned resin is to the scope below the above 6.0mm of 1.0mm, then PS purity reaches more than 98%, reaching can be directly as utilizing material again, the purity of regenerating by resin material manufacturer, so this method is better.

Further, if with the thickness homogenization of above-mentioned resin to the scope below the above 3.0mm of 1.0mm, then the purity of PP and PS and the rate of recovery reach 100%, so this method is better.

Carried out same checking with other resin that exemplifies in the table 1, results verification on other resin, also have and PP and the identical phenomenon of PS resin.

The influence of the programming rate of-the 2 heating-

Figure 10 is that expression contains the 2nd heat time heating time in the separation of separate object thing of PP and PS, with the relation of the adhesion strength of PP and PS and separating component.The separate object thing is afterwards using the thickness homogenization on the compression aspect in the scope below the above 6.0mm to 0.5mm.The adhesion strength of PP and PS measure for the force gauge FGP-20 that uses the refreshing step company of Nidec (NIDEC-SHIMPO CORPORATION) system and separating component between the value of shear stress of horizontal direction.In addition, for tilt and little vibration etc. with separate object thing desorption from the separating component simply, adhesion strength with zero be good.In addition, be attached on the separating component for the separate object thing is stably kept, adhesion strength is being good more than the 2N.That is to say that in the separation of the separate object thing that contains PP and PS, the adhesion strength of the 2nd heating back PS is that the adhesion strength of zero and PP is more than the 2N, then can obtain good separating resulting.

As shown in figure 10, as can be known along with the increase of the 2nd heat time heating time, the adhesion strength of PS descends, and the time of the 2nd heating adhesion strength of PS more than 20 seconds the time is zero.About the adhesion strength of PP, confirm that the adhesion strength of the PP of thickness more than 1mm does not descend.Yet, for the PP of thickness, as can be known along with the increase of the 2nd heat time heating time less than 1mm, adhesion strength descends, if then there be the PP of adhesion strength less than 2N in the time of the 2nd heating more than 20 seconds, become the low reason of the rate of recovery of the low and PP of the purity of PS.

Therefore, thickness is studied less than the low inhibition method of the adhesion strength of the PP of 1mm, found that, add the programming rate of the programming rate of the PP that pines for by making the 2nd time less than PS, substantially shortened the 2nd heat time heating time of PP, is to add the low inhibition method of adhesion strength of pining for PP the 2nd time.

The control of the programming rate of PP and PS can utilize the difference of the infrared absorption character of resin to implement easily.Figure 11 and Figure 12 are the infrared ray absorbing curve of PP and PS, if 500～1200cm that irradiation PP does not absorb, has only PS to absorb ^-1The infrared ray of wave number band, then PS preferentially is heated.In addition, in fact, utilize that the germanium of characteristic shown in Figure 13 is arranged is that infrared filter and near infrared ray panel heater heat PP and PS simultaneously, the result has confirmed programming rate with respect to PS with good repeatability, and the programming rate of PP is less.

Table 3 is that to utilize above-mentioned germanium be infrared filter and implements to contain the 2nd heating in the separating of separate object thing of PP and PS with the near infrared ray panel heater, the programming rate of PP is reduced, the actual heat time heating time under intensification limiting temperature (150 ℃) is with respect to PP and the purity of PS and the measurement result of the rate of recovery in short 5 seconds of the PS, and for having put down in writing the result who utilizes electric hot plate to carry out the 2nd heating more in the lump.Can confirm according to table 3,, can improve the purity and the rate of recovery of PP and PS by shortening the heat time heating time of PP.

Table 3

Figure 14 is the difference of expression PS and the heat time heating time of PP under the intensification limiting temperature and the relation of PP and PS purity.Discovery is by shortening the heat time heating time with PP more than 5 seconds, and the purity of PS resin reaches more than 98%, reach can be directly as utilizing material again, the purity of regenerating by resin material manufacturer.Yet if PP reaches the time of intensification limiting temperature, promptly the heating-up time surpasses 60 seconds, begins to occur the PP of adhesion strength below 2N after the heating the 2nd time, the heat time heating time of therefore preferred PP with respect to PS short more than 5 seconds and the heating-up time below 60 seconds.

Embodiment 2

Figure 15～Figure 17 represents embodiments of the present invention 2.

Figure 15 (a)～Figure 15 (f) represents from the separate object thing that is mixed with the 1st kind of different resin 6 of vitrification point and yield stress, the 2nd kind of resin 7 and 8 three kinds of resins of the 3rd kind of resin, the operation of separation resin.

Among Figure 15 (a), on separating component 3 mounting the separate object thing.Here, the vitrification point of the 1st kind of resin 6 is lower than the vitrification point of the 2nd kind of resin 7.The vitrification point of the 2nd kind of resin 7 is lower than the vitrification point of the 3rd kind of resin 8.

Among Figure 15 (b), carry out the 1st heating.The heating-up temperature of this moment is that the vitrification point of the 1st kind of resin 6 is above and be lower than the temperature of the vitrification point of the 2nd kind of resin 7 and the 3rd kind of resin 8.

At this moment, by dull and stereotyped 4 the 1st kind of resin 6 and the 2nd kind of resin 7 and the 3rd kind of resin 8 are pressed on the separating component 3.The compressive yield stress of this stressed size and the 1st kind of resin 6 is identical or on it, by under this state to the 1st kind of resin 6, the 2nd kind of resin 7 and the 3rd kind of resin 8 heating pressurizations, the 1st kind of resin 6 is attached on the separating component 3.

In addition, for the 2nd kind of resin 7 and the 3rd kind of resin 8, though when the plus-pressure of above-mentioned heating pressurization when the 2nd kind of resin 7 and the 3rd kind of resin 8 compressive yield stress separately are above, warpage will take place in each, be attached on the separating component 3, but since machining deformation carry out being lower than under the temperature of vitrification point, if therefore after pressure discharges, be higher than the thermal process of the 1st heating-up temperature, then shape returns to the preceding state of pressurization, breaks away from from separating component 3.

When the plus-pressure of above-mentioned heating pressurization during less than compressive yield stress, the 2nd kind of resin 7 and the 3rd kind of resin 8 are not attached on the separating component 3.

Then shown in Figure 15 (c), if discharge above-mentioned moulding pressure, then when the 2nd kind of resin 7 and the 3rd kind of resin 8 are not attached on the separating component 3, according to the reason same with embodiment 1, by separating component 3 being tilted or making the method for separating component 3 little vibrations etc., can separate with the 1st kind of resin 6 on being attached to separating component 3.

In Figure 15 (d), by be higher than the 1st heating-up temperature and be lower than the 1st kind of resin 6, the 2nd kind of resin 7 and the 3rd kind of resin 8 in the temperature of melting point of the lower resin of melting point carry out the 2nd heating, the recovery of shape of the 2nd kind of resin 7 and the 3rd kind of resin 8 is to the preceding state of pressurization, become the state or the significantly reduced state of adhesive strength that are not attached on the separating component 3, therefore, by making methods such as separating component 3 inclinations or little vibration, can shown in Figure 15 (e), separate with the 1st kind of resin 6.

The 1st kind of resin 6 that keeps being attached on the separating component 3 can reclaim in the mode that scrapes with blade 5 grades shown in Figure 15 (f).At this moment, if the elastic modelling quantity of the 1st kind of resin 6 is descended by the 1st kind of resin 6 being carried out the 3rd heating, the 1st kind of resin 6 and will become easy separating of separating component 3 then.

Under the situation that 3 kinds of resins that discovery has nothing in common with each other in this vitrification point and yield stress mix, preferably begin to make it successively to keep adhering on the separating component 3, make it the method for high-purityization from the lower resin of vitrification point.In addition, the 2nd kind of resin 7 and the 3rd kind of resin 8 from separating component 3 separates can separate by carrying out same operation repeatedly.

Figure 16 is illustrated in the separation of the resin compound that contains PP, PS, ABS, the relation of the 1st heating-up temperature and the PP rate of recovery.Figure 17 is illustrated in the separation of the resin compound that contains PP, PS, ABS, the relation of the purity of the 1st heating-up temperature and PP.

As shown in figure 16, when the temperature of the 1st heating below 40 ℃ the time because PP is not attached on the separating component 3, therefore can't make PP keep adhering on the separating component 3, can't separate recovery.When the temperature of the 1st heating heated in the interval below 90 ℃ more than 60 ℃, the operation by carrying out the 2nd heating subsequently and heating for the 3rd time can make the purity of PP and the rate of recovery reach 100%.In addition, the dotted line of Figure 16 is 30 seconds gained curves of heating pressurization under plus-pressure 40000kgf, owing to increase in the adhesive strength of PP more than 15 ℃, therefore can make the purity of PP and the rate of recovery reach 100%.

In addition as shown in figure 17, if the temperature of the 1st heating is increased to more than 100 ℃, then since this temperature not only than the vitrification point of PP, also than the vitrification point height of PS, therefore can't make the recovery of shape of PS by the 2nd heating, can't peel off.

Found that by above,, must carry out the 1st heating, more preferably carrying out the 1st heating with the temperature below 90 ℃ more than 60 ℃ under the plus-pressure 20000kgf with the temperature below 90 ℃ more than 15 ℃ for the separate object thing that contains PP, PS and ABS.

Embodiment 3

Figure 18 represents embodiments of the present invention 3.

Figure 18 (a)～Figure 18 (f) is identical with embodiment 2, represents from the separate object thing that is mixed with the 1st kind of different resin 6 of vitrification point and yield stress, the 2nd kind of resin 7 and 8 three kinds of resins of the 3rd kind of resin the operation of separation resin.

Among Figure 18 (a), on separating component 3 mounting the separate object thing.Here, the vitrification point of the 1st kind of resin 6 is lower than the vitrification point of the 2nd kind of resin 7.The vitrification point of the 2nd kind of resin 7 is lower than the vitrification point of the 3rd kind of resin 8.

Among Figure 18 (b), carry out the 1st heating.The heating-up temperature of this moment is that the vitrification point of the 1st kind of resin 6 and the 2nd kind of resin 7 is above and be lower than the temperature of the vitrification point of the 3rd kind of resin 8.

At this moment, by dull and stereotyped 4 the 1st kind of resin 6 and the 2nd kind of resin 7 and the 3rd kind of resin 8 are pressed on the separating component 3.This stressed size, identical with the compressive yield stress of the higher resin of compressive yield stress in the 1st kind of resin 6 and the 2nd kind of resin 7 or on it, by under this state, the 1st kind of resin 6, the 2nd kind of resin 7 and the 3rd kind of resin 8 heating being pressurizeed, the 1st kind of resin 6 and the 2nd kind of resin 7 are attached on the separating component 3.In other words, the 1st kind of resin 6 and the 2nd kind of resin 7 of this moment, because to pressurize more than the vitrification point of the 1st kind of resin 6 and the 2nd kind of resin 7 and at the 1st kind of resin 6 and the heating of the condition more than the 2nd kind of resin 7 compressive yield stress separately, therefore plastic deformation taking place, is attached on the separating component 3.

Though when the plus-pressure of above-mentioned heating pressurization when the compressive yield stress of the 3rd kind of resin 8 is above, warpage also can take place in the 3rd kind of resin 8, be attached on the above-mentioned separating component 3, but because machining deformation carries out being lower than under the temperature of vitrification point, if therefore after pressure discharges, be higher than the thermal process of the 1st heating-up temperature, then shape returns to the preceding state of pressurization, breaks away from from separating component 3.

When the plus-pressure of above-mentioned heating pressurization during less than the compressive yield stress of the 3rd kind of resin 8, the 3rd kind of resin 8 is not attached on the separating component 3.

Then as Figure 18 (c) shown in, if discharge above-mentioned moulding pressure, then when the 3rd kind of resin 8 is not attached on the separating component 3, according to the reason same with embodiment 1, by methods such as inclination or little vibrations, can with the resin isolation that is attached on the separating component 3.

Then in Figure 18 (d), carry out the 2nd heating.The temperature of this moment, be higher than the 1st heating-up temperature and be lower than the 1st kind of resin 6, the 2nd kind of resin 7 and the 3rd kind of resin 8 in the temperature of melting point of the minimum resin of melting point.Thus, the recovery of shape of the 3rd kind of resin 8 is to the preceding state of pressurization, become the state or the significantly reduced state of adhesive strength that are not attached on the separating component 3, therefore, by making methods such as separating component 3 inclinations or little vibration, can shown in Figure 18 (e), separate with the 1st kind of resin 6 and the 2nd kind of resin 7.

The 1st kind of resin 6 and the 2nd kind of resin 7 of keeping being attached on the separating component 3 can reclaim in the mode that scrapes with blade 5 grades shown in Figure 18 (f).At this moment, if the elastic modelling quantity of the 1st kind of resin 6 and the 2nd kind of resin 7 is descended by the 1st kind of resin 6 and the 2nd kind of resin 7 are carried out the 3rd heating, then the 1st kind of resin 6 and the 2nd kind of resin 7 and will become easy separating of separating component 3.

Under the situation that 3 kinds of resins that discovery has nothing in common with each other in this vitrification point and yield stress mix, preferably begin to break away from separating component 3 successively, make the method for its high-purityization from the higher resin of vitrification point.In addition, the 1st kind of resin 6 and the 2nd kind of resin 7 from separating component 3 separates can separate by carrying out same operation repeatedly.

The existence of-impurity-

Even in the separate object thing, contain under the situation of the impurity beyond the desired resin, can utilize the difference of vitrification point and yield stress from the separate object thing, to separate desired resin too.

When in the composition of impurity, containing rubber, adhesive tape, low melting point resin, in the above-mentioned impurity that adheres to by the heating pressurization, exist in the 2nd time and add the impurity of pining for not breaking away from, the part of above-mentioned impurity sneak into blade scrape and peel off recovery want in the resin, the purity of the resin of descends.In addition, when in the composition of impurity, containing the impurity that the 1st vitrification point more than the heating-up temperature arranged, heat owing to passing through the 2nd time, the recovery of shape of the part of above-mentioned impurity is the preceding state of pressurization extremely, so passes through to heat for the 2nd time the purity decline of the resin that breaks away from recovery.In addition, in the composition of impurity, contain metal.When timber, paper etc.,, therefore can separate desired resin because above-mentioned impurity does not stick on the separating component.

In this separate object thing, contain under the situation of impurity, though different according to the kind of impurity and content can cause that the purity of the resin of wanting changes also separable desired resin.Therefore, even in operation of the present invention, sneak into some impurity, also separable desired resin.

The shredded plastic separate object thing of useless household electrical appliances that will contain PP, PS, ABS and impurity carries out the confirmatory experiment of the high purity separation of PP of the present invention as sample.Above-mentioned sample is the refrigerator to the waste household appliances goods, at first remove compressor and contain the case inner part of high-purity resin component by hand-sorting, afterwards, pulverize with pulverizer, further remove the fragmentation bits of the largest particles footpath about 10.0mm of gained such as metal by operations such as pneumatic separating, magnetic force sorting, electrostatic separation.

Take out the part of above-mentioned sample in advance, utilize PP and impurity content in the above-mentioned samples of analysis such as well-known infrared absorptiometric analysis, densimetric analysis, range estimation and palpation, implement the separation of PP afterwards.Containing ratio (%), the containing ratio (%) of the impurity in the above-mentioned sample and the measurement result of peeling off the purity (%) of the PP of recovery of PP in the following above-mentioned sample of table 4 expression.

Table 4

The containing ratio of PP (%)	Impurity (%)	The purity of PP (%)
			38.6	2.3	99.1
38.6	1.1	99.6
			38.6	0.5	99.9

By table 4,, still can keep can be used as the purity of utilizing material to regenerate again even verified under the situation of having sneaked into impurity.

This shows that much more especially the present invention effective especially to the separation of content PP, PS, ABS in the discarded household electrical appliances.For the filler potting resin that can't separate with gravity separation etc. in the past with the PLA that increases of demand etc. is also very effective in the future.

The separation method that utilizes the separate object thing of vitrification point difference of the present invention can be used as that contained resin mixes in the sheet from useless household electrical appliances or general discarded object, with the separation method of specific resin material renewable resources, is used for the resources circulation of resin.

Claims

1. method for separating resin, it is characterized in that, on separating component, carry out the 1st heating with being mixed with the different separate object thing mounting of resin more than 2 kinds of vitrification point and yield stress, pressurization simultaneously, the temperature that at this moment the 1st time heated is set at the vitrification point that is lower than the resin more than a kind in the described resin, and the temperature that is higher than the vitrification point of the resin more than a kind, plus-pressure at this moment is set in vitrification point to be lower than in the resin of the 1st heating-up temperature, more than the compressive yield stress of the resin that compressive yield stress is the highest, at least the resin that makes vitrification point be lower than the 1st heating-up temperature is attached on the described separating component, the resin or the little resin of adhesive force that are not attached on the described separating component are separated from described separating component, further the described separating component that has adhered to resin is carried out the 2nd heating, the temperature of the 2nd heating of this moment is set at and is higher than heating-up temperature the 1st time, and be lower than the temperature of the fusing point of the resin that fusing point is minimum in the described separate object thing, the resin that only makes vitrification point be lower than the 1st heating-up temperature is attached to described separating component, the resin that is attached on the described separating component is separated from described separating component, separate;

Above-mentioned separate object thing comprises wantonly at least a kind in polypropylene, polyethylene, PLA, polyvinyl chloride, polystyrene, acrylonitrile-styrene, acrylonitrile-butadiene-styrene (ABS), the Merlon.

2. method for separating resin as claimed in claim 1, it is characterized in that, with the temperature of the 1st heating be set in described vitrification point and yield stress different more than 2 kinds in the resin, the temperature between the vitrification point of the low resin that is only second to this resin of the vitrification point of the resin that vitrification point is minimum and vitrification point.

3. method for separating resin as claimed in claim 1, it is characterized in that, with the temperature of the 1st heating be set in described vitrification point and yield stress different more than 2 kinds in the resin, the height of the vitrification point of the resin that vitrification point is the highest and vitrification point is only second to the temperature between the vitrification point of resin of this resin.

4. method for separating resin as claimed in claim 1 is characterized in that, described plus-pressure is the plus-pressure more than 1.2 times of the compressive yield stress of the resin that reclaims of desire.

5. method for separating resin as claimed in claim 1 is characterized in that, with separate object thing mounting on the compression aspect of the resin on the separating component minimum thickness and the difference of maximum ga(u)ge in 5.5mm.

6. method for separating resin as claimed in claim 1 is characterized in that, with separate object thing mounting in the scope of the thickness on the compression aspect of the resin on the separating component below the above 6.0mm of 0.5mm.

7. method for separating resin as claimed in claim 1 is characterized in that, with separate object thing mounting in the scope of the thickness on the compression aspect of the resin on the separating component below the above 6.0mm of 1.0mm.

8. method for separating resin as claimed in claim 1 is characterized in that, with separate object thing mounting in the scope of the thickness on the compression aspect of the resin on the separating component below the above 3.0mm of 1.0mm.

9. method for separating resin as claimed in claim 1 is characterized in that, adds at the 2nd time and pines for, and vitrification point is lower than the programming rate of the resin of the 1st heating-up temperature, is higher than the programming rate of the resin of the 1st heating-up temperature less than vitrification point.

10. method for separating resin as claimed in claim 1, it is characterized in that, add at the 2nd time and to pine for, the programming rate that is higher than the resin of the 1st heating-up temperature by the programming rate that makes vitrification point be lower than the resin of the 1st heating-up temperature less than vitrification point, the resin that makes described vitrification point be lower than the 1st heating-up temperature is short more than 5 seconds at the resin that the more described vitrification point of heat treated time under the intensification limiting temperature is higher than the 1st heating-up temperature, and described vitrification point is lower than heating-up time of resin of the 1st heating-up temperature below 60 seconds.

11. method for separating resin as claimed in claim 1 is characterized in that, the separate object thing by polypropylene, and polystyrene or acrylonitrile-butadiene-styrene (ABS) at least a kind form.

12. method for separating resin as claimed in claim 1, it is characterized in that, the separate object thing by polypropylene, and polystyrene or acrylonitrile-butadiene-styrene (ABS) at least a kind form, and be set at the temperature of the 1st heating more than 15 ℃ and be lower than the temperature of the vitrification point of separate object resin kinds whole except that polypropylene, the temperature of the 2nd heating is set at more than 70 ℃ below 155 ℃, and is higher than the temperature of the 1st heating.

13. method for separating resin as claimed in claim 1, it is characterized in that, the separate object thing by polypropylene, and polystyrene or acrylonitrile-butadiene-styrene (ABS) at least a kind form, and be set at the temperature of the 1st heating more than 15 ℃ and be lower than the temperature of the vitrification point of separate object resin kinds whole except that polypropylene, the temperature of the 2nd heating is set at more than 100 ℃ below 155 ℃, and is higher than the temperature of the 1st heating.