CN102781640A

CN102781640A - Process for production of polycarbonate resin pellets

Info

Publication number: CN102781640A
Application number: CN2012800006399A
Authority: CN
Inventors: 田尻敏之; 吉国道生
Original assignee: Mitsubishi Engineering Plastics Corp
Current assignee: Mitsubishi Engineering Plastics Corp
Priority date: 2011-02-09
Filing date: 2012-01-19
Publication date: 2012-11-14
Anticipated expiration: 2032-01-19
Also published as: KR101201265B1; WO2012108245A1; JP4977786B1; JP2012162048A; CN102781640B; KR20120101665A

Abstract

The invention provides polycarbonate resin pellets which are characterized in that: the content of impurities such as chlorine compound, etc. is extremely small, resin deterioration happens few, the polycarbonate resin pellets will not yellowing and appearance thereof is good, and the polycarbonate resin pellets can be used without resin additives. The present invention is a process for producing polycarbonate resin pellets, characterized by comprising the steps of: 1) using a polycarbonate resin having a specific powdery or granular form; 2) moving the polycarbonate resin in an inert gas atmosphere having an oxygen concentration of 3 vol% or less by allowing the polycarbonate resin to fall in the inert gas atmosphere 50 cm or more; 3) injecting a specified amount of water having an electrical conductivity of 30 [mu]S/cm or less in a kneading zone of an extruder; 4) sucking an vent inlet so as to render the vent inlet in a pressure-reduced state and, at the same time, adjusting the water content in the resin to 10-200 ppm; 5) introducing a strand-shaped molten resin that is extruded through a die into water having an electrical conductivity of 30 [mu]S/cm or less to thereby cool the molten resin; 6) cutting the strand at 70-130 DEG C to produce pellets each containing 10-200 ppm of water; and 7) allowing the pellets each having a water content of 10-200 ppm thus produced to further absorb water in a wet atmosphere, thereby adjusting the water content of the pellets to a value greater than the initial water content of the pellets and equal to or lower than 1300 ppm.

Description

The manufacturing approach of polycarbonate resin pellet

Technical field

The present invention relates to the manufacturing approach of polycarbonate resin pellet; Relate more specifically to make the method for polycarbonate resin pellet; Impurity contents such as the chlorine compound of this polycarbonate resin pellet are few, and the resin deterioration is few, and yellowing does not take place; The pellet outward appearance is good, can under the situation of no resin additive, use.

Background technology

Polycarbonate resin is as general engineering plastic; Excellences such as the transparency, resistance to impact, hear resistance, dimensional stability; Because characteristic that should excellence is used in wide spectrums such as electric, electronics, business automation equipment parts, mechanical part, vehicle part.

In electric/electronic device, as parts use silicon wafer, optic disc base board, storage with hard disk, optical storage CD, IC chip, LCD with various electrical and electronic equipment parts such as high function substrate glass.In the manufacturing of electric/electronic device, for these component-assembled and supply with production line, need transportation, pass on these parts, therefore use to transport and use case, as its material, use various thermoplastic resins such as polycarbonate resin so far.

In recent years; Electrical and electronic equipment part is along with the miniaturization for high performance, densification, highly integrated; In manufacturing environment, keeping and the polluter that produces, contacts in moving to yield rate, quality, the very big influence of reliability generation of electric/electronic device goods; Along with miniaturization, densification and the highly integrated progress of electrical and electronic equipment part, need higher cleannes.

Polycarbonate resin; Especially contain carrene and other chlorine compounds in the polycarbonate resin that the so-called interfacial polymerization that utilizes aromatic dihydroxy compound and phosgene in carrene (being METHYLENE CHLORIDE) solvent, to react obtains; Though be a small amount of; In addition, these chlorine compounds decompose when fusion, produce acidic materials.Through from polycarbonate resin, removing these pollution sources materials, expection can improve the reliability with case of transporting of using it.

In order to solve this type of problem relevant with polycarbonate resin, known have when melt extruding, add water to remove the method (for example with reference to patent documentation 1) of impurity, in addition, proposed to make the method for the water foaming of interpolation in the patent documentation 2.Yet, only utilize these methods, require high-caliber transporting in its cleannes with in the case etc., cleannes do not claim it is fully, the method for the polycarbonate resin molding material with high-level cleannes is effectively made in expectation in addition.

The prior art document

Patent documentation

Patent documentation 1: the special fair 5-48162 communique of Japan

Patent documentation 2: No. 3776746 communique of japanese

Summary of the invention

The problem that invention will solve

The objective of the invention is provides a kind of method of making polycarbonate resin pellet in view of above-mentioned prior art problems; Impurity contents such as the chlorine compound of this pellet are few, and the resin deterioration is few, and yellowing does not take place; The pellet outward appearance is good, can under the situation of no resin additive, use.

The scheme that is used to deal with problems

The inventor is in order to reach above-mentioned problem; Further investigation repeatedly; The result finds, uses the specific specific area and the polycarbonate resin of particle diameter, through the non-active gas treatment process that each is specific, water injection process, decompression suction operation, refrigerating work procedure, cutting action, curing step combination; The polycarbonate resin pellet of the utmost point levels of impurities content that can obtain can not to reach so far, thus the present invention accomplished.

Promptly; According to first invention of the present invention, a kind of manufacturing approach of polycarbonate resin pellet is provided, it is characterized in that; Its polycarbonate resin of containing micro-carrene of serving as reasons is made the method for the polycarbonate resin pellet that carrene content reduced, and comprises following operation:

1) as the Merlon that contains micro-carrene, use specific area to be 0.008m ²/ g is above and have the polycarbonate resin of powder shape of the particle diameter of 200 ~ 2000 μ m more than the 50 quality %;

2) make in the non-active gas atmosphere of polycarbonate resin below oxygen concentration is 3 volume % of powder shape fall, the non-active gas treatment process more than the mobile 50cm;

The polycarbonate resin that 3) will pass through the powder shape that non-active gas handles supplies in the vented extruder; In mixing district, injecting with respect to 100 mass parts polycarbonate resins is that the electrical conductivity of 0.1 ~ 2 weight portion is the operation of the water below the 30 μ S/cm;

4) exhaust ports in the downstream through making the water injection portion that is arranged at extruder is aspirated in decompression state; Thereby from the resin of molten condition, carrene is aspirated removal with above-mentioned water, and the moisture concentration in the resin is adjusted to the operation of 10 ~ 200ppm;

It is the operation of cooling off the water below the 30 μ S/cm that the molten resin of the line material shape that 5) will extrude from extruder die head imports to electrical conductivity;

6) at 70 ℃ ~ 130 ℃ scope line of cut material, acquisition contains the operation of the pellet of 10 ~ 200ppm moisture;

7) make it further moisture through the pellet that contains 10 ~ 200ppm moisture in moistening atmosphere held, moisture content is adjusted to above original moisture content of pellet and the curing step below the 1300ppm gained.

In addition,, a kind of manufacturing approach of polycarbonate resin pellet is provided, has it is characterized in that, in the 1st invention, further carried out the pellet of the saturation state that obtains through curing step is carried out dry drying process according to the 2nd invention of the present invention.

In addition; According to the 3rd invention of the present invention, a kind of manufacturing approach of polycarbonate resin pellet is provided, it is characterized in that; In the 1st invention; When handling the polycarbonate resin of powder shape, supply with the powder body with full state with non-active gas, from the below being that the mode of adverse current is supplied with non-active gas with respect to the powder body.

In addition, according to the 4th invention of the present invention, a kind of manufacturing approach of polycarbonate resin pellet is provided, has it is characterized in that, in the 1st invention, making the oxygen concentration in the machine barrel of vented extruder is below the 3 volume %.

In addition, according to the 5th invention of the present invention, a kind of manufacturing approach of polycarbonate resin pellet is provided, has it is characterized in that in the 1st invention, the mixing district of injecting water is the zone that is full of of resin, resin pressure is the scope of 0.5 ~ 10MPa.

In addition; According to the 6th invention of the present invention, a kind of manufacturing approach of polycarbonate resin pellet is provided, it is characterized in that; In the 1st invention, the resin fullness rate is that the length in the zone of 5 ~ 30 volume % is more than the 8.0D (D is the machine barrel internal diameter of extruder) in the relief portion of extruder.

In addition, according to the 7th invention of the present invention, a kind of manufacturing approach of polycarbonate resin pellet is provided, has it is characterized in that, in the 1st invention, the temperature that is used to cool off the water of line material is 30 ~ 90 ℃.

In addition, according to the 8th invention of the present invention, a kind of polycarbonate resin pellet is provided, it is through the manufacturing approach manufacturing of the 1st invention.

In addition, according to the 9th invention of the present invention, provide a kind of electrical and electronic equipment part to transport and used case, it uses the polycarbonate resin pellet of the 8th invention.

The effect of invention

Manufacturing approach according to thermoplastic resin composition's formed body of the present invention; Can make polycarbonate resin pellet, impurity contents such as its chlorine compound are few, and the resin deterioration is few; Yellowing does not take place; The pellet outward appearance is good, is particularly suitable for electrical and electronic equipment part and transports with case etc., can under the situation of no resin additive, use.

Description of drawings

Shown in Figure 1 for can be applicable to the formation example of supply machine-hopper of the present invention-extruder.

Fig. 2 (a) and (b) be the explanation figure that falls the definition of distance of the present invention, (c) be depicted as be used to polycarbonate resin is fallen stage by stage and magazine chute (hopper chute) in the figure of examples of members of setting.

Screw rod pie graph for the extruder that uses in the embodiment of the invention shown in Figure 3.

The specific embodiment

Embodiment is shown below and the illustration thing specifies the present invention, waits and make an explanation but the present invention is not limited to this embodiment and illustration thing.

Wherein, in this manual, unless otherwise prescribed, " ~ " uses as the implication of lower limit and higher limit to comprise the numerical value of putting down in writing before and after it.In addition, " ppm " is meant quality ppm.

The invention is characterized in that it is a method of being made the polycarbonate resin pellet that carrene content reduced by the polycarbonate resin that contains micro-carrene, it comprises:

The polycarbonate resin that 3) will pass through the powder shape that non-active gas handles supplies in the vented extruder, and in mixing district, injecting with respect to 100 mass parts polycarbonate resins is that 0.1 ~ 2 weight portion electrical conductivity is the operation of the water below 30 μ S/cm;

4) aspirate in decompression state through the exhaust ports that makes the water injection portion downstream that is arranged at extruder, from the resin of molten condition, carrene is aspirated removal with above-mentioned water, and the moisture concentration in the resin is adjusted to the operation of 10 ~ 200ppm;

It is the water below the 30 μ S/cm and the operation of cooling that the molten resin of the line material shape that 5) will extrude from extruder die head imports to electrical conductivity;

As the polycarbonate resin that uses among the present invention (A); Can enumerate out aromatic polycarbonate resin, aliphatic polycarbonate resin, aromatic-aliphatic polycarbonate resin; Aromatic polycarbonate resin preferably; Particularly, can use thermoplasticity aromatic polycarbonate polymers or the copolymer that obtains through the diester reaction that makes aromatic dihydroxy compound and phosgene or carbonic acid.

As aromatic dihydroxy compound, can enumerate out 2, two (4-hydroxyphenyl) propane (bisphenol-A) of 2-, tetramethyl bisphenol-A, α, α '-two (4-hydroxyphenyl)-to diisopropyl benzene, hydroquinones, resorcinol, 4,4 '-dihydroxybiphenyl etc.In addition; Bonding on the above-mentioned aromatic dihydroxy compound has been used in combination compound or the polymer that contains two terminal phenolic hydroxyl groups or the oligomer etc. with siloxane structure of 1 above sulfonic acid Si Wan Ji Phosphonium during as dihydroxy compounds a part of can obtain the high polycarbonate resin of anti-flammability.

As the preferred example of the polycarbonate resin that uses among the present invention, can enumerate out combination and use 2, two (4-hydroxyphenyl) propane or 2 of 2-, two (4-hydroxyphenyl) propane of 2-and other aromatic dihydroxy compounds are as the polycarbonate resin of dihydroxy compounds.

To the not special restriction of the manufacturing approach of polycarbonate resin, usually, can use the method for interfacial polymerization (phosgenation) or fusion method (ester-interchange method) to make.

Polymerisation in the interfacial polymerization is described below: to reaction for inactive organic solvent, aqueous alkali in the presence of; Usually pH is remained on more than 9; Use aromatic dihydroxy compound and molecular weight regulator as required (terminal terminator) and the anti-oxidant that is used to prevent the aromatic dihydroxy compound oxidation, make it with phosgene reaction after, polymerization catalysts such as interpolation tertiary amine or quaternary ammonium salt; Carry out interfacial polymerization, thereby obtain polycarbonate resin.The interpolation of molecular weight regulator so long as beginning to polymerisation during from phosgenation during get final product, to its not special restriction.Wherein, reaction temperature for example is 0 ~ 40 ℃, and the reaction time for example is several minutes (for example 10 minutes) ~ several hours (for example 6 hours).

Herein, as being inactive organic solvent, can enumerate out carrene, 1, chlorinated hydrocabons such as 2-dichloroethanes, chloroform, monochloro-benzene, dichloro-benzenes etc. to reaction.In addition, as the alkali cpd that uses in the aqueous alkali, can enumerate out alkali-metal hydroxide such as NaOH, potassium hydroxide.

As molecular weight regulator, can enumerate out the compound of phenolic hydroxyl group with monovalence, preferably can enumerate out m-methyl phenol, p-methyl phenol, a propylphenol, n-propyl phenol, p-t-butyl phenol and to chain alkyl fortified phenol etc.The consumption of molecular weight regulator is preferably 50 ~ 0.5 moles with respect to 100 moles of aromatic dihydroxy compounds, more preferably 30 ~ 1 moles.

As polymerization catalyst, can enumerate out tertiary amines such as trimethylamine, triethylamine, tri-n-butylamine, tripropyl amine (TPA), three hexyl amines, pyridine, quaternary ammonium salts such as trimethyl benzyl ammonia chloride, tetramethyl ammonium chloride, triethyl benzyl ammonia chloride etc.

Fusion method is described, and the polymerisation in this manufacturing approach for example is the ester exchange reaction of carbonic diester and aromatic dihydroxy compound.As carbonic diester, can enumerate out dialkyl carbonate ester compounds such as dimethyl carbonate, diethyl carbonate, dimethyl dicarbonate butyl ester, diphenyl carbonate and carbonic acid two (toluene) ester etc. replace diphenyl carbonate etc.Carbonic diester is diphenyl carbonate or replacement diphenyl carbonate preferably, is more preferably diphenyl carbonate.

In melting state transesterification reaction, usually, the decompression degree when blending ratio, the ester exchange reaction of regulating carbonic diester and aromatic dihydroxy compound can obtain to regulate the aromatic polycarbonate resin of desired molecule amount and terminal hydroxyl amount.Usually, in the melting state transesterification reaction,, use the above carbonic diester of equimolar amounts, especially preferably use 1.001 ~ 1.3 moles, especially preferably use 1.01 ~ 1.2 moles with respect to 1 mole of aromatic dihydroxy compound.In addition,, the method for when reaction, adding terminal terminator in addition can be enumerated out,, monobasic phenols, monocarboxylic acid class, carbonic diester class can be enumerated out as the terminal terminator of this moment as more positive control method.

The polycarbonate resin that uses among the present invention can use any of above-mentioned interfacial polymerization and melt phase polycondensation to make.Yet; As stated; Contain many carrene that is derived from polymer solvent, catalyst, catalytic deactivation agent and byproduct of reaction etc. in the polycarbonate resin through the interfacial polymerization manufactured and contain chlorine compounds such as compound, preferably as object of the present invention as the chloro-carbonic acid ester group of unreacted residue.Therefore, method of the present invention is fit to use the polycarbonate resin through the interfacial polymerization manufactured.

According to the viscosity average molecular weigh meter that converts by the solution viscosity that uses carrene under 25 ℃ temperature, to measure as solvent; The molecular weight of polycarbonate resin is generally 10000 ~ 50000 scope; Be preferably 15000 ~ 30000 scope, more preferably 17500 ~ 27000 scope.Viscosity average molecular weigh is lower than at 10000 o'clock, and mechanical strength is inferior, and surpasses at 50000 o'clock, and processing and forming property is inferior, and is therefore not preferred.

The polycarbonate resin that uses among the present invention is object with the resin that contains micro-carrene, and herein, trace is meant, is converted into the chlorine atomic weight, contains the chlorine-containing compound below the 200ppm.The polycarbonate resin that obtains with interfacial polymerization contains the above chlorine-containing compound of 20ppm when polymerization system takes out usually.The common content of the carrene in the raw material polycarbonate resin is 10 ~ 100ppm.In addition, contain the polycarbonate resin that significantly surpasses the 200ppm chlorine-containing compound,, also be difficult to the content of carrene is reduced to below the 3ppm of purpose according to the invention even use method of the present invention for being converted into the chlorine atomic weight.

In the present invention, polycarbonate resin uses the resin with powder shape.

Particularly, polycarbonate resin is that above the distribution according to the particle diameter of measuring according to the method for JISK0069 (sieve test method) of its 50 quality % counted 200 ~ 2000 μ m, is preferably 300 ~ 2000 μ m, further is preferably the powder body of 400 ~ 2000 mu m ranges.Contain surpass 50 quality % have less than 200 μ m or when surpassing the resin of particle diameter of 2,000 μ m, the composition that has less than the particle diameter of 200 μ m flies upward easily, is difficult to supply to extruder quantitatively from feeder.In addition, for the composition with the particle diameter that surpasses 2,000 μ m, the follow-up processing that utilizes non-active gas lacks effect.

In addition, the specific area of polycarbonate resin is 0.008m ²More than/the g, be preferably 0.01m ²More than/the g, 0.012m more preferably ²More than/the g.Specific area is less than 0.008m ²During/g, be difficult to show the effect of the processing of later use non-active gas.Herein, the specific area of polycarbonate resin is the value of obtaining through the BET multipoint method.

Need to prove that powder shape of the present invention is meant, get final product,, be meant so-called powder, fine pellet equigranular thing, granular substance, tablet etc. its not special restriction so long as have the particulate of above-mentioned fine particle size distribution.

In addition; When polycarbonate resin is used for semiconductor substrate and especially requires the few purposes of semiconductor polluters such as chlorine with container etc.; Additive that might become polluter etc. does not add as far as possible; Use down so-called " additive-free ", but, can contain additives such as heat stabilizer, anti-oxidant, releasing agent, ultra-violet absorber, fluorescent whitening agent, pigment, dyestuff, other polymer, fire retardant, shock-resistant modifying agent, antistatic additive, plasticizer, compatilizer according to purposes.

These additives can cooperate one or more.In the middle of these, especially preferably use heat stabilizer and anti-oxidant.

To the not special restriction of heat stabilizer, for example preferably enumerate out phosphorus series compound.As phosphorus series compound, can use known any phosphorus series compound.As object lesson; Can enumerate out the oxyacid of phosphorus such as phosphoric acid, phosphonic acids, phosphorous acid, phosphinic acids, polyphosphoric acids; Acid pyrophosphoric acid slaines such as SAPP, acid potassium pyrophosphate, acid calcium pyrophosphate, the phosphate of potassium phosphate, sodium phosphate, phosphoric acid caesium, trbasic zinc phosphate grade in an imperial examination 1 family or the 10th family's metal, organophosphorus compounds; The organic phosphorous acid ester compounds, organic phosphinate compound etc.

Wherein, Triphenyl phosphite, tricresyl phosphite (single nonyl phenyl) ester, tricresyl phosphite (single nonyl/dinonyl-phenyl) ester, tricresyl phosphite (2; The 4-di-tert-butyl-phenyl) ester, phosphorous acid list octyl group diphenyl, phosphorous acid dioctyl list phenylester, phosphorous acid list decyl diphenyl, phosphorous acid didecyl list phenylester, tridecyl phosphite, trilauryl phosphite, tricresyl phosphite stearyl ester, phosphorous acid 2; Organic phosphites such as 2-di-2-ethylhexylphosphine oxide (4, the 6-di-tert-butyl-phenyl) monooctyl ester are preferred.

The content of heat stabilizer is generally more than 0.001 mass parts with respect to 100 mass parts polycarbonate resins, is preferably more than 0.01 mass parts, more preferably more than 0.03 mass parts; In addition; Be generally below 1 mass parts, be preferably below 0.7 mass parts, more preferably below 0.5 mass parts.When heat stabilizer was very few, it is insufficient that thermostable effect might become, and when heat stabilizer was too much, effect culminated, and it is uneconomical to become.

In addition, as anti-oxidant, for example, can preferentially enumerate out hindered phenol is anti-oxidant.As its object lesson, can enumerate out pentaerythrite four [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester, sulfo-di ethylene bis [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester], N; N '-1, the 6-hexylidene two [3-(3,5-di-t-butyl-4-hydroxyphenyl propionamide), 2, [[3,5-two (1 for 4-dimethyl-6-(1-methyl pentadecyl) phenol, diethyl; The 1-dimethyl ethyl)-and the 4-hydroxyphenyl] methyl] phosphate, 3,3 ', 3 ", 5,5 '; 5 "-six tert-butyl groups-a, a ', a "-(mesitylene-2,4; 6-three bases) three-paracresol, 4, two (hot sulfenyl the methyl)-orthoresols of 6-, ethylenebis (oxidation ethylidene) two [3-(a 5-tertiary butyl-4-hydroxy-tolyl) propionic esters], hexa-methylene two [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester], 1,3; 5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-1,3,5-triazines-2; 4,6 (1H, 3H, 5H)-and triketone, 2; 6-di-t-butyl-4-(4, two (hot the sulfenyl)-1,3,5-triazines of 6--2-base is amino) phenol etc.

Wherein, pentaerythrite four [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester are preferred.As this phenol is anti-oxidant; Particularly; For example; Can enumerate out " Irganox 1010 " (registration mark, down together), " Irganox1076 " that Ciba Specialty Chemicals Inc. makes, " the ADK STAB AO-50 " that ADEKA Corporation makes, " ADK STAB AO-60 " etc.

Wherein, anti-oxidant can contain a kind of, also can contain two or more with combination in any and ratio.

The content of anti-oxidant is generally more than 0.001 mass parts with respect to 100 mass parts polycarbonate resins, is preferably more than 0.01 mass parts, in addition, is generally below 1 mass parts, is preferably below 0.5 mass parts.The content of anti-oxidant might become insufficient as the effect of anti-oxidant when the lower limit of above-mentioned scope is following, when the content of anti-oxidant surpassed the higher limit of above-mentioned scope, effect culminated, and it is uneconomical to become.

In addition; Polycarbonate resin of the present invention not only can not use the raw material of (virgin); Also can use by the polycarbonate resin of the goods regeneration of using, the polycarbonate resin of so-called material regeneration; In addition, can also use defective work, geat cold burden (sprue), the pulverizing article of runner cold burden acquisitions such as (runner) or the powder body that their fusions are obtained etc. by goods.The polycarbonate resin of regeneration mixes the back to be used with the polycarbonate resin that is not the powder shape of regenerate; As combined amount; Preferably below the 80 quality % of whole polycarbonate resin compositions, more preferably below the 50 quality %, be preferably especially below the 30 quality %.

The polycarbonate resin of powder shape is at first handled with non-active gas.

Using the processing of non-active gas is to carry out under specific shape and the condition that is in specific state at polycarbonate resin.Particularly, as the Merlon that contains micro-carrene, the preparation specific area is 0.008m ²/ g is above and have the polycarbonate resin of the powder shape of 200 ~ 2000 μ m particle diameters more than the 50 quality %, through fall in the non-active gas atmosphere of polycarbonate resin below oxygen concentration is 3 volume % that makes this powder shape, move 50cm with on carry out.

Making polycarbonate resin is that the reason of this special shape is the area (surface) that contacts with non-active gas in order to have increased; Remove the residual oxygen in powder surface effectively through non-active gas; In addition, making it fall mobile is to improve treatment effeciency for the powder body is moved in non-active gas with flow regime.

Carry one in passing, the polycarbonate resin of powder shape is accommodated in the container, obtained to be difficult to abundant process result with the mode of the atmosphere in the non-active gas displacement container.

Fall and move: flow through the tubular part that vertically carries the polycarbonate resin that is equipped with the powder shape from the below through making non-active gas so long as get final product as follows; Supply with the polycarbonate resin of powder shape from the top with weight feed machine etc., it is moved with full state in non-active gas.

Particularly, supply with the polycarbonate resin of powder shape from the hopper (hopper of extruder) of the height more than 50cm top, make it to fall, the mode of supplying with non-active gas from the root of hopper can be used as easy mode and enumerates out.

Below use the description of drawings object lesson.

The polycarbonate resin of this powder shape is housed in the raw material supplying machine, supplies in the magazine chute that is arranged on the extruder from this through feeder (weight feed machine).

The figure of the formation example for the supply machine-hopper-extruder that can use in the present invention shown in Figure 1.The bottom of magazine chute is connected with the supply port of extruder, and polycarbonate resin supplies in the extruder via magazine chute successively, and melting mixing in extruder forms resin molding materials such as pellet.

When other compositions that cooperate except polycarbonate resin, this mixing can cooperate in any stage before putting into extruder.For example, can after cooperating whole compositions, put in the magazine chute via feeder as required, supply to extruder with rotary drum, Henschel mixer, blending machine.Extruder can use single screw extrusion machine, double screw extruder etc.In addition, can supply in the magazine chute via the path different with polycarbonate resin.

At first, in the present invention, the inner atmosphere of magazine chute that material is supplied to extruder is replaced with non-active gas.In the present invention, non-active gas is not limited to rare gas, is meant that the powder body with respect to employed polycarbonate resin is inactive gas.As non-active gas, for example can use nitrogen, carbon dioxide, rare gas etc., especially preferably use nitrogen.

In the present invention, in order to replace the atmosphere in the magazine chute, the non-active gas of supplying with to magazine chute is preferably drying regime and purity is more than the 99 volume %.In addition, shown in the dotted line of Fig. 1, non-active gas can be supplied with near the extruder supply port of magazine chute or from the top of magazine chute, and preferably (foot) supplied with near supply port.This be because, it is desirable to, the limit falls polycarbonate resin, the limit is the non-active gas of atmosphere with the air displacement in the resin, on this basis, it is higher to keep non-active gas shared concentration in the atmosphere of magazine chute bottom.

Preferably, it is higher and can the air of displacement be discharged to the air-tightness of outside degree that magazine chute has the non-active gas concentration of keeping in the internal atmosphere.Non-active gas is so that the flow sustainable supply of the lower state of the oxygen concentration of internal atmosphere is discharged and kept to the air of replacing in the magazine chute.Concrete flow can suitably confirm according to the size and the air-tightness of magazine chute.

In addition, in the present invention, preferably, when handling the polycarbonate resin of powder shape, supply with the powder body with full state with non-active gas, from the below being that the mode of adverse current is supplied with non-active gas with respect to the powder body.

In the present invention, preferred so that the oxygen concentration in the atmosphere is below the 3 volume % in the magazine chute, be preferably below the 1 volume %, more preferably 0.5 volume % mode following, that most preferably be below the 0.1 volume % is supplied with non-active gas.Oxygen concentration for example can nearby be measured at the supply port of magazine chute bottom, extruder.When oxygen concentration surpasses 3 volume %, the removal effect of the inhibition effect of the yellowing that can not fully obtain to cause, chloride etc. because of oxidative degradation etc.

Need to prove that non-active gas not only can supply in the magazine chute, and can supply in the machine barrel of extruder.

Need to prove that as stated, when in polycarbonate resin, cooperating other compositions, polycarbonate resin supplies to extruder with dispersity afterwards through non-active gas atmosphere.Particularly, supply to extruder after polycarbonate resin falls in the magazine chute that internal atmosphere was replaced with non-active gas.

As stated, in the present invention, preferably, supply with the polycarbonate resin of powder shape with the mode that under the state that disperses, in magazine chute, falls.Herein; " state of dispersion " be meant each resin particle the surface can with the abundant state of contact of atmosphere; Do not need special supply method; Can supply with the polycarbonate resin of powder shape of the present invention from hopper top continuously through using screw type weigh feeder (or intermittently), thereby under dispersity, fall.For dispersity but situation intensive or that fall is not preferred with becoming piece.

Yet; For the air that contains in the pit on the surface of fully replacing polycarbonate resin with non-active gas etc., the polycarbonate resin of powder shape in non-active gas atmosphere by vertical range fall more than the 50cm, the mode that arrives the extruder supply port after more than the preferred 80cm supplies with.

For example, as shown in Figure 1, use feeder that polycarbonate resin is supplied under the situation in the magazine chute, shown in Fig. 2 (a), making the vertical range h of the height of feeder outlet and the material supply port of extruder (magazine chute bottom) is more than the 50cm.Wherein, shown in Fig. 2 (b), when the material of melting mixing was piled up in magazine chute, making the vertical range h on summit of material of height and the accumulation of feeder outlet was more than the 50cm.

For example; Use double screw extruder as extruder etc. carry out with material supply to bit by bit in the machine barrel of extruder, when being referred to as hungry material and supplying with the hunger of method and supply with (hungry charging); State for Fig. 2 (a); In addition, use single screw extrusion machine etc. not carry out being the state of Fig. 2 (b) under the hungry situation about supplying with.Therefore, confirm whether the adopting of kind or hungry charging, the extruded velocity of extruder, the quantity delivered of material, make the polycarbonate resin of powder shape in magazine chute, fall more than the 50cm.Through being set at hungry charging, affirmation can stably be extruded.

In addition, in the present invention, the polycarbonate resin of powder shape is as long as the vertical range by essence falls more than the 50cm in non-active gas atmosphere, to the not special restriction of the process that falls.Not once to fall more than the 50cm can yet.In addition; For example, shown in Fig. 2 (c), also can on the inner surface of magazine chute, divide several sections the tabular parts (deflection plate) that more than one front end tilts downwards are set; Make the powder shape polycarbonate resin stage by stage (in a zigzag) fall, arrive the material supply port of extruder.In magazine chute, being provided with under the situation such as deflection plate, can be that the total distance (distance in a zigzag) that repeatedly falls stage by stage is for more than the 50cm.In addition, fall and be not limited to freely fall, get final product so long as move downwards.Therefore, the distance that descends on landing limit, deflection plate top is also contained in and falls in the distance.

According to thinking, the powder body is not to grow with the state of piling up but with the time that the state that disperses contacts with atmosphere (non-active gas), and then the contained air of resin and the displacement of non-active gas are further carried out.When deflection plate is set, compare with situation about falling more than the 50cm by free-falling mode once, owing in magazine chute, slowly fall, therefore, the raising of the displacement efficiency of air and non-active gas.

Yet, as the polycarbonate resin of object of the present invention owing to be the little powder shape of particle diameter, with the shape of pellet and so on relatively, air drag is big, free-falling speed is little, therefore, can be non-active gas with air displacement just through freely falling only.

The polycarbonate resin that has passed through the powder shape of non-active gas processing like this can supply in the extruder of exhaust.And the limit is injected in this mixing district and is added water, and the limit outgases from exhaust outlet, and the limit melt extrudes polycarbonate resin.

As the water that injects, using electrical conductivity is the water below the 30 μ S/cm.When electrical conductivity surpassed 30 μ S/cm, the cleannes of gained polycarbonate resin pellet worsened.Electrical conductivity remains not clear to the mechanism of the influence of the cleannes of gained polycarbonate resin pellet, but is that interaction because of ion component and Merlon or impurity causes by inference.

The preferred electrical conductivity of water is below the 20 μ S/cm, more preferably below the 10 μ S/cm, further is preferably below the 5 μ S/cm, is preferably especially below the 3 μ S/cm, most preferably is below the 1 μ S/cm.

Wherein, the mensuration of electrical conductivity uses conductivity meter to carry out measuring under 25 ℃ of the temperature.

In addition, the injection rate of water is 0.1 ~ 2 mass parts with respect to 100 mass parts polycarbonate resins.When the injection rate of water is less than 0.1 mass parts; Can not show water and inject the effect of adding; Chlorine compound in the polycarbonate resin is difficult to reach by below the chlorine atom 3ppm, in addition, and during more than 2 mass parts; The degassing in the exhaust portion becomes insufficient, polycarbonate resin is produced harmful effects such as hydrolysis.In addition, owing to produce a large amount of steams, cause the ejection (vent-up) of resin.The preferred injection rate of water is 0.15 ~ 1.8 mass parts with respect to 100 mass parts polycarbonate resins, and more preferably 0.2 ~ 1.5 mass parts further is preferably 0.3 ~ 1.2 mass parts, is preferably 0.4 ~ 1.0 mass parts especially.

As the extruder that has exhaust outlet that uses among the present invention, can be single screw extrusion machine, also can be double screw extruder, preferred double screw extruder.In addition, the number of exhaust outlet can be 1 place, also can be more than 2 places, is preferably 2～6 places.Injecting the position of adding water can be for more than 2 place.

L/D as the screw rod of extruder is preferably 10 ~ 80, and more preferably 15 ~ 70, more preferably 20 ~ 60.When too short, the degassing is not enough easily, when long, and the easy variation of tone.

The mixing district of injecting water is the position that is full of of melt polycarbonate resin (preferably be full of the zone carry out) preferably fullly.Be full of the zone and (be meant fullness rate with respect to the ratio of the spatial volume of a spacing of the screw rod in mixing district with the amount (based on the volume of real density) of resin; Unit: when volume %) representing is more than the 95 volume %; Be preferably more than the 98 volume %; More preferably more than the 99 volume %, especially be preferably being full of fully of 100 volume %.

The resin pressure (the machine barrel internal pressure of kneading part) of the injection part of water is preferably 0.5 ~ 10MPa, more preferably 1 ~ 8MPa, more preferably 2 ~ 7MPa.The pressure that improves polycarbonate resin disperses water in the melt polycarbonate resin.When resin pressure was too small, the removal effect of carrene was little, when excessive, and the resin deterioration, tone worsens easily.

Preferably, the upstream side of the injection point in mixing district is provided with the high zone of resin pressure, in the downstream in the high zone of pressure injection point is set.Particularly, the screw rod of extruder constitute to be recommended as follows: 1) after upstream side is provided with the position of sealing ring, be right after injection point is set; Perhaps, 2) from upstream side the forward kneading member is set in order, reverse kneading member then is set, water filling after reverse kneading member.

Method 1) in, sealing ring is the sealing ring with the chimeric ring-type of screw rod, and about 70 ~ 90% inaccessible with stream is detained resin flow, thus, can improve the pressure of resin, and the downstream after being right after sealing ring is provided with injection point.

In addition; Method 2) be provided with when rotation with resin transfer to the forward kneading member in downstream, then the reverse kneading member that resin is turned back to upstream side is set in the downstream of forward kneading member when rotating; Thereby the raising resin pressure, the method for carrying out water filling in the back of reverse kneading member.

In addition, the oxygen concentration in the machine barrel of vented extruder (barrel) is preferably below the 3 volume %.Through being below the 3 volume %, prevent the yellowing of gained polycarbonate resin pellet easily.

In order to make the oxygen concentration in the machine barrel is below the 3 volume %, can inject non-active gas from the hopper side (root of screw rod) of extruder.Owing to think the oxygen concentration and its difference significantly not of hopper bottom, therefore, if the oxygen concentration in the machine barrel is difficult to direct mensuration, then with the oxygen concentration replacement of hopper bottom.

Injecting in the above-mentioned mixing district after the water, is that near the leading section of extruder exhaust ports is aspirated in decompression state through making the downstream that is arranged at extruder, and volatile ingredients such as carrene are aspirated removal with water from the resin of molten condition.Through this suction, the non-zone that is full of that is full of the zone to screw front end after the kneading part that is full of resin divides becomes decompression state (relief portion).

Exhaust outlet is connected with not shown vacuum extractor, carries out decompression exhaust.In exhaust portion; Before operation in be dispersed with the water that disperses in the polycarbonate resin of high-temperature high-pressure state of water because the expansion of gasifying of sharply reducing pressure; Foaming enlarges the surface area of polycarbonate resin, and volatile ingredients such as carrene volatilize from the surface with water.

The decompression degree of exhaust outlet is-below the 0.05MPa, more preferably-below the 0.07MPa, more preferably-below the 0.09MPa.

For the moisture concentration in the polycarbonate resin of molten condition,, therefore replace with the moisture concentration in the following pellet owing to can not directly measure the molten resin in the extruder.Because, according to thinking in the die head between the moisture concentration in the molten resin and the moisture concentration in the pellet less than difference significantly.

The length of relief portion preferably is the length more than the 8.0D (D is the machine barrel internal diameter of extruder) on the screw rod direction, more preferably more than the 12D.In addition, the fullness rate of the resin of this relief portion 5 ~ 30 volume % preferably.This is because preferably the filling rate of melt polycarbonate resin is fully reduced, and the degassing is fully carried out.Preferred resin fullness rate is 8 ~ 25 volume %, more preferably 10 ~ 20 volume %.When the resin fullness rate was lower than 5 volume %, the amount of resin that can handle reduced, so productivity ratio descends.

And the moisture concentration in the polycarbonate resin of (just having extruded the back) after will extruding is adjusted to 10 ~ 200ppm.Making moisture concentration is that this scope is in order to remove carrene etc. well and do not make the polycarbonate resin deterioration; Mixing and exhaust is until moisture concentration during less than 10ppm, the easy deterioration of polycarbonate resin, and be when surpassing the amount of 200ppm, carrene etc. are residual.In addition, through being the moisture of this scope, expection has the plasticization effect through water to make the stable effect of line material cutting.

Moisture concentration in the polycarbonate resin is preferably 15 ~ 150ppm, more preferably 20 ~ 100ppm.The mensuration of the moisture rate in the Merlon after just having extruded can be carried out as follows: online material cools off, cuts afterwards 3 minutes and puts in the vacuum drier with interior; At room temperature dry about 5 minutes; Thereby only the adsorbed water of desiccated surface is measured with the determination of trace water device.

Then, polycarbonate resin is extruded from extruder die head and is line material shape, imports in the water and cooling.To the not special restriction of the shape of extrusion die, can use known shape.The diameter of die head of nozzle of spuing depends on the size of extrusion pressure, required pellet, is generally about 2 ~ 5mm.The temperature of the polycarbonate resin after just having extruded is generally about 300 ℃.

The line material is transported in the water that accumulates in the cooling bath through the carry-over pinch rolls traction.Cool off.In order to reduce the deterioration of resin, the line material is preferably shorter to the time of putting into the water after die head is extruded.Usually, can, die head put into the water in 1 second after extruding.

In the present invention, at this moment, importing to electrical conductivity is in the water below the 30 μ S/cm.When employed electrical conductivity of water surpasses 30 μ S/cm, the cleannes variation of gained polycarbonate resin pellet.The preferred electrical conductivity of water is below the 20 μ S/cm, more preferably below the 10 μ S/cm, further is preferably below the 5 μ S/cm, is preferably especially below the 3 μ S/cm, most preferably is below the 1 μ S/cm.

The water that accumulates in the cooling bath through the time deterioration, electrical conductivity raises, but through often supplying with cooling water, water overflow from groove is gone out, and can electrical conductivity be remained on the scope (below the 30 μ S/cm) of regulation.In addition, the temperature of tank changes according to the position, and the place that common line material is put in the tank is a maximum temperature, and along with cooling, the temperature of tank descends.If the temperature of tank is low excessively, then the line material is by sub-cooled, if the temperature of tank is too high, then the excessive temperature of line material raises.Be 30 ℃ ~ 90 ℃ in the preferable range of the temperature of tank, preferred scope is 40 ℃ ~ 70 ℃.

The line material of cooling is transported in the comminutor through carry-over pinch rolls like this, cuts, and forms pellet.Cutting online material temperature is in 70 ~ 130 ℃, carries out during preferred 75 ~ 125 ℃ scope.Obtained to contain 10 ~ 200ppm, the moisture pellet of preferred 15 ~ 150ppm moisture.Therefore significantly molecular weight reduction or hydrolysis, do not take place owing to do not experience the surplus shearing course that extruder brings in the moisture pellet of gained, form the high pellet of cleannes.

When line material temperature was lower than 70 ℃, the line material became really up to the mark, break easily when cutting with comminutor, breach, and when surpassing 130 ℃, it is soft that the line material becomes, and produces whiskers (whisker), pellet easy deformation at cut surface.

Need to prove that the line material temperature of this moment can be measured through contactless thermometer, easily, can accommodate by in the bag of the pellet of cutting machine cutting or the pellet in the container and measure and replace through thermometer is inserted into.

In addition, preferably, will pack in paper bag, bucket made of paper, the canister etc., contact slaking with moistening air by the pellet of cutting machine cutting.Pellet by the cutting machine cutting directly has static, easily the dust in the absorbed air and the dust on floor.In order to reduce this static, usefully remove the method that electrical equipment (for example IONAIZER SJ-M02:KEYENCE CORPORATION makes) removes electricity energetically, simply, can contact with wet air and reduce static through pellet being put in the canister etc.According to thinking that reason is, through contacting with wet air, the adsorption moisture of pellet increases, and the electric conductivity on pellet surface improves, and what electric charge leaked speeds up; Perhaps through the volumetric moisture absorption of pellet, the whole electric conductivity of pellet improves.According to thinking, be set at metal through container with pellet, can bring into play the bigger electric effect of removing.

In a word, through this curing step, can obtain dust, dust adheres to few pellet.

As wet air, particularly, the air of relative humidity more than 40% is preferred, and more preferably relative humidity is more than 50%, is preferably the air more than 60% especially.

Through this curing step is set at for a long time, moisture content increases, and electric charge takes place leak, and the carried charge of pellet reduces, and can obtain dust, dust adheres to few pellet.

This long ageing method is, in also do not accommodated water vapour permeability bigger poly bag etc. before pollution such as dust with the pellet of cutting machine cutting, be unit with the sky, with the moon be unit in indoor placement, make it the method for slaking.Temperature during this long time treatment, humidity can be normal temperature, normal wet, preferably in the environment of temperature adjustment and damping, regulate fate, time certainly, the control moisture content.

Yet there are limit in the time of curing step or moisture amount of moisture, it is desirable to, and the moisture content after the slaking is below the 1300ppm.When containing the water that surpasses 1300ppm, when using the required moulding article of this moisture pellet moulding, the problem of moulding article intensity reduction takes place in the easy hydrolysis of resin.In addition, even dry before the pellet moulding, drying needs the time, and productivity ratio descends.Preferred moisture content is below the 1000ppm.More preferably below the 700ppm.Contain water in the pellet and prevent chargedly through making, the object tape electric weight is preferably below the 10kV, more preferably below the 8kV.

Then, further carry out the pellet of the saturation state that obtains via curing step is carried out dry drying process.The purpose of moisture operation is to remove electricity suppressing the absorption of dust, when the pellet moulding is obtained the moulding article, water content for a long time, the Merlon hydrolysis becomes the reason of yellowing etc.Therefore, before with the moulding of moulding article, regulate the water content in the pellet once more.

Above-mentioned moisture pellet is implemented dried, moisture content is adjusted to 50 ~ 200ppm.Dried about 100 ~ 130 ℃ of temperature, was carried out preferred 3 ~ 7 hours scope with hot-air drier common 2 ~ 10 hours in preferred 105 ~ 125 ℃ scope.

The polycarbonate resin pellet (pellet after the dried) that is obtained by the present invention is shaped to shape arbitrarily, uses as formed body.To not restriction such as the shape of formed body, pattern, color, size, can at random set according to the purposes of this formed body.

To the not special restriction of the manufacturing approach of formed body, the method for forming that can adopt poly carbonate resin composition to adopt usually arbitrarily.For instance, can enumerate out hollow molding method, the method for forming of using heat insulating mold, the method for forming of using rapidly heating moulds, foaming (comprising supercritical fluid), the inserts method of forming, IMC (coated and molded in the mould) method of forming, extrusion moulding, the sheet method of forming, hot-forming method, rotoforming, the range upon range of method of forming, shaping method to suppress etc. such as injection moulding, ultrahigh speed injection moulding, injection compression molding method, the two look methods of forming, gas be auxiliary.In addition, can also adopt the method for forming of using hot flow path (hot runner).

Especially, polycarbonate resin pellet of the present invention is because impurity contents such as chlorine compound are few, and the deterioration of resin is few; Yellowing does not take place; Can under the situation of no resin additive, use, therefore, utilize these specialities; Can in requiring the high electric/electronic device of formed body cleannes etc., be widely used, especially can be used for electrical and electronic equipment part and transport and use case.

Transport and use case in order to make electrical and electronic equipment part, through resin granular material injection moulding being shaped to the case of required form with known method.Transport with case and comprise various magazines (magazine), pallet, box, container etc.

Wherein, the not special restriction of the electrical and electronic equipment part here for example, is meant the parts that silicon wafer, hard disk, various optic disc base board, IC chip, LCD use with various electric/electronic devices such as high function substrate glass.

Embodiment

Below provide embodiment and come more specifically to explain the present invention.Yet the present invention is defined in following examples to explain.

Among the following embodiment and comparative example, as polycarbonate resin, the polycarbonate resin (PC-1) ~ (PC-3) below using.

PC-1：

(manufacturing of polycarbonate resin (PC-1))

In the caustic soda aqueous solution that is dissolved with sodium dithionite (hydrosulfite), dissolve bisphenol-A down at 35 ℃; Be cooled to 25 ℃ then, form the aqueous solution, this aqueous solution and the carrene that is cooled to 5 ℃ are supplied in the stainless steel tubulation of internal diameter 6mm continuously; Mix; Mixed liquor through in the homogeneous blender, is carried out emulsification, preparation emulsion.The quantity delivered that Xiang Guanzhong supplies with is following: bisphenol-A 16.31kg/hr, caustic soda 5.93kg/hr, water 101.1kg/hr, sodium dithionite 0.018kg/hr, and carrene 68.0kg/hr.

Flow in the polyflon tubulation formula reactor of internal diameter 6mm, length 34m behind the pipe of the emulsion that generates through internal diameter 6mm.Simultaneously in tubular reactor, supply with the liquefaction phosgene that is cooled to 0 ℃, make it reaction, generate oligomer with the speed of 7.5kg/hr.The flow velocity of tubular reactor is 1.7m/ second.

Wherein, in tubular reactor, temperature rises to 60 ℃, and through external refrigeration, outlet is 35 ℃.Reaction mixture sat is separated, be separated into water and oil phase.The chloro-formate concentration of gained oligomer is 0.47N, and the terminal concentration of OH is 0.23N, and oligomer concentrations is 27.7%.Obtain 40kg from the gained oil phase, join in the reactive tank that has three leaf swept-back (Pfaudler) blades of 200 liters of internal volumes.Then; Add 25kg carrene, the 5.75kg25% caustic soda aqueous solution, 41kg water and 0.87g (0.020mol% therein; With respect to bisphenol-A) the pyridine hydrochloride catalyst, under nitrogen atmosphere, stirring 60 minutes under 360rpm under 10 ℃; Carry out polymerisation, generate terminal (the OH ends concentration: polycarbonate resin 60 μ eq/g) of full OH.

Then; In this reaction mixture, add 175g (3.92 moles of % are with respect to bisphenol-A) (terminal terminator) p-t-butyl phenol, the 105g 25 weight % caustic soda aqueous solution, 218g (is 0.10 mole of % with respect to bisphenol-A) 2 weight % triethylamine aqueous solutions and further under 1 hour, the stirring of 360rpm, continue reaction.After this, add 30kg carrene and 7kg water, at room temperature stir and left standstill afterwards in 20 minutes, be separated into water and organic facies.Carry out following washing operation repeatedly 3 times: in this organic facies, add the 0.1 centinormal 1 sodium hydrate aqueous solution of 20kg, after stirring 15 minutes, leave standstill, be separated into water and organic facies.Add 20kg 0.1 centinormal 1 hydrochloric acid in the organic facies behind the neutralizing treatment, after stirring 15 minutes, leave standstill, be separated into water and organic facies.Carry out 3 following operations repeatedly: in this organic facies, add the 20kg pure water, after stirring 15 minutes, leave standstill, be separated into the washing operation of water and oil phase, the result does not detect chlorion at aqueous phase, therefore, ends washing operation.From organic facies,,, obtain polycarbonate resin (PC-1) with the gained powder for drying with kneader evaporation, removal carrene.

PC-2：

The comminutor " HB 189 " that uses FURUKAWA Industrial Machinery Systems Co. to make is pulverized above-mentioned PC-1 and the material of acquisition at 650rpm.

PC-3：

(Japan Steel Works, the TEX30 α that Inc.) makes extrudes above-mentioned PC-1 under discharge-amount 50kg/hr, screw speed 200rpm, in tank, cools off line of cut material and the shot-like particle that obtains with company of JSW.

Wherein, The specific area of polycarbonate resin is obtained as follows: with test portion (below about 1.3Pa) decompression heat treated 3 hours under 110 ℃, vacuum; Then; The powder measurement appearance AUTO SORB 1MP that makes with Quantachrome Instruments is determined at the adsorption isotherm (adsorbed gas: krypton), use the gained adsorption isotherm, obtain specific area through the BET multipoint method under the liquid nitrogen temperature.

In addition, particle diameter is obtained as follows.

Use the sieve of the above sieve mesh of 1mm; Obtain the above size distribution of 1mm; The LMS-2000e that makes through laser diffraction and scattering formula sedimentograph (Seishin Enterprise Co) below the 1mm obtains size distribution (damp process), obtains volume average particle size thus.

In addition, viscosity average molecular weigh is obtained with following formula through using the inherent viscosity [η] under 20 ℃ of the determination of ubbelohde viscometer:

[η]=1.23×10 ^-4×(Mv) ^0.83。

In addition, carry out the mensuration of quantity of dichloromethane through following method.

The quantity of dichloromethane of polycarbonate resin PC-1 ~ PC-3, particle diameter, viscosity average molecular weigh are shown in the table 1.

[table 1]

(embodiment 1)

Use engagement type parallel dual-screw vented extruder (the TEX30 α of JSW's manufactured, barrel length 52.5D (D is the machine barrel internal diameter)), use the screw rod of Fig. 3 to constitute A.

As shown in Figure 3, in order to explain, be divided into the equal length of C 1 ~ C 15 to the die head direction from the hopper side of extruder.

Screw rod constitutes A and in each district as shown in Figure 3, constitutes by following mode.

A) melting zone: be connected with length 31.5D, the forward screw rod of helical pitch (lead) 1.5D.

B) mixing district: length 4.0D

Along throughput direction, comprise forward kneading member 1D, reverse kneading member 0.5D and forward kneading member 1.0D, quadrature kneading member 1.0D, counterscrew 0.5D.Wherein, in C 10 machine barrels fluid injection plug is installed, adds water with plunger displacement pump.

C) depressor area: the forward screw rod that is connected with length 17.0D, helical pitch 1.5D.This 17.0D is the length of relief portion.

In C 14 machine barrels decompression exhaust mouth is set, makes the decompression degree be-0.090MPa.

In formation shown in Figure 1; Making the distance (highly) from the material supply port of quantitative feeder (the belt weigh feeder (Weighing Feeder) that KUBOTA Corporation makes, Wide Range B-WF) to the material supply port of double screw extruder is 85cm.Use has roughly bubble-tight magazine chute, from upwards supplying with nitrogen (purity 99.9 volume %) with 35 liters/minute flow near the material supply port of double screw extruder, forms adverse current with polycarbonate resin powder body.Through near the material supply port that is arranged on double screw extruder, the locational oxymeter corresponding (the zirconia formula oxymeter LC-750L that Toray Industries Inc. makes) with the supply port of nitrogen; Measure the oxygen concentration of (hopper bottom) in the magazine chute, confirm that oxygen concentration is 0.3 volume %.

Through quantitative feeder above-mentioned polycarbonate resin powder body (PC-1) is supplied in the magazine chute that nitrogen replacement crosses.Polycarbonate resin supplies in the extruder with the mode of starvation with 50kg/hr via the percentage feeder that is arranged at the hopper bottom.

The machine barrel design temperature of extruder is set at 270 ℃; Screw speed is set at 400rpm; In mixing district, using plunger displacement pump to constitute from the screw rod of Fig. 3 that the fluid injection plug that is provided with C 10 machine barrels of A injects with respect to 100 mass parts polycarbonate resins is that the electrical conductivity of 0.5 mass parts is the ion exchange water of being made by 23 tower pure water devices of 1.5 μ S/cm.Wherein, electrical conductivity is used conductivity meter mensuration under 25 ℃ that DKK-TOA Corporation makes.

The resin fullness rate of depressor area is 1.3 volume %, and the resin fullness rate in mixing district is 99 volume %.

Wherein, the fullness rate of resin is obtained through following formula.

Discharge-amount (kg/ hour) ÷ the length * screw speed of the proportion of resin * (sectional area of the sectional area of machine barrel-2 screw rod) * helical pitch (/ hour)

In addition, with the resin pressure of this water filling part of resin pressure sensor determination, the result is 2.0MPa.

Then,, make that the decompression degree reaches-0.09MPa, remove water and volatile ingredient, the moisture concentration in the resin is adjusted to 38ppm through suction with the exhaust outlet suction of vavuum pump from C 14 machine barrels.

Then, extrude the line material of the circular cross-section of diameter 4mm from the extrusion nozzle of the front end of extruder.Line material temperature after just having extruded is 310 ℃.

The line material extruded is imported in the tank of ion exchange water that the electrical conductivity of having accommodated by 23 tower pure water device manufacturings is 1.5 μ S/cm, cool off.Tank through making the water overflow with adjustment in 40 ℃ ~ 70 ℃ scope.

The line material is cooled to 103 ℃, is inserted in the comminutor, cutting.When line material temperature surpassed 130 ℃, it was wound on the cutting machine, can not obtain good pellet.Also seen whiskers on the cut surface.In addition, when being lower than 70 ℃, during cutting, it is unfavorable that pellet has taken place to break etc., and aesthetic property reduces.Cut surface at 103 ℃ of pellets that cut down is good-looking and good shape.Cut in back 3 minutes, pellet is put in the vacuum drier of room temperature and at room temperature placed 5 minutes, remove the water that adheres on the pellet surface, measure the moisture rate of pellet.

Then, this pellet of 3kg is put into the stainless steel cylindrical can (10L volume, model ST-24: science Co., Ltd. buys from south, Hunan), uncap contacts 3 hours with the wet air of humidity 50%, makes it slaking.Measure the moisture rate and the carried charge of the pellet that takes out after 3 hours.The result is shown in the table 3.

Wherein, moisture rate is measured and is used determination of trace water device (CA-100 that Mitsubishi Chemical Ind (Mitsubishi Chemical Corp.) makes) to carry out.

Carried charge is measured with Handy Sensor SK-030 (KEYENCE Corporation manufacturing).

In addition, the carrene content of gained pellet and stripping cl concn are measured with following method.

(assay method of carrene)

Under 70ml/ minute nitrogen circulation; In being set in 300 ℃ the heating furnace of gasification installation (UA-21 of MCI manufactured); Place the above pellet of 4g, importing is incorporated with in the absorption tube (being cooled to 13 ± 1 ℃) of marking (chloroform is a 0.08mg/ml De dioxane solution) in 20ml diox and the 5ml and reaches 60 minutes with nitrogen with the gas that produces.(GC-14A that company of Shimadzu Seisakusho Ltd. (SHIMADZU Corp.) makes measures (internal standard method) with the gas chromatograph that has flame ionization detector (Flame Ionization Detector) with the gained absorption liquid.

Condition determination is described below:

Post:

SUS post 3mm φ * 2m

Filler: silicone DC-550 25%80/100 order

Celite?545sk?DMCS

60 ℃ of column temperature

250 ℃ of injection temperatures

Detector temperature: 250 ℃

Gas air 0.60kg/cm ²

Hydrogen 0.60kg/cm ²

Carrier gas (helium) 1.15kg/cm ²

Test portion injection rate 3 μ L

(assay method of stripping cl concn)

Adding 50g pellet and 100g pure water with pure water in the washed polypropylene container made that has a lid; After in 50 ℃ cleaning oven, keeping 3 hours; Be separated into pellet and water; Use possesses the ion chromatograph (the ion chromatograph DX-AQ of Japan DIONEX manufactured) of concentrated module (test portion of Japan DIONEX manufactured concentrates module SPU-300), measures the chlorion composition (absolute standard curve method) in the liquid phase.Condition determination is described below:

The analytical column AS12A of post Japan DIONEX manufactured

The guard column AG12A of Japan DIONEX manufactured

The evaporating column AG4A-SC of Japan DIONEX manufactured

The Suppressor ASRS3004mm of TVS Japan DIONEX manufactured

Eluent 2.7mM sodium carbonate+0.3mM sodium acid carbonate

Eluent flow 1.5ml/ minute

Test portion injection rate (enrichment facility imposes a condition) circulated in evaporating column with 1.5ml/ minute, concentrates 4 minutes

Detection sensitivity RANGE:3 μ S, temperature correction: 1.7/ ℃

TVS current value 50mA

In addition; With the gained pellet 120 ℃ of following heat dryings 5 hours; The injection (mo(u)lding) machine SH100 that uses Sumitomo heavy-duty machine tool company (Sumitomo Heavy Ind.) to make; Under the condition of 290 ℃ of barrel zone temperatures, 80 ℃ of mold temperatures, mold the flat moulding article of 100mm * 100mm * 3mm.The good moulding article of silver bar (silver) or bubble have been obtained not produce.

Use gained tabular moulding article, carry out the mensuration of tone (yellow colour index (YI value)).

Yellow colour index (YI value) is according to JIS K-7105, and is as test film, fixed with the SE2000 type beam splitting type color instrumentation that Japanese electric look industrial group (NIPPON DENSHOKU Ind.) makes with the thick flat board of above-mentioned 3mm.

Above evaluation result is shown in the table 3.

(embodiment 2)

Except using PC-2 to replace the PC-1, with embodiment 1 likewise, make pellet.The result is shown in the table 3.

(embodiment 3)

Except increasing the quantity delivered of nitrogen, making the oxygen concentration in the magazine chute is beyond the 0.1 volume %, with embodiment 1 likewise, make pellet.The result is shown in the table 3.

(embodiment 4)

Except reducing the quantity delivered of nitrogen, making the oxygen concentration in the magazine chute is beyond the 2.1 volume %, with embodiment 1 likewise, make pellet.The result is shown in the table 3.

(embodiment 5)

Except the distance (highly) from the material supply port of quantitative feeder to the material supply port of double screw extruder is set at the 60cm, with embodiment 1 likewise, make pellet.The result is shown in the table 3.

(embodiment 6)

Except making water injection rate is 0.2 mass parts, with embodiment 1 likewise, make pellet.The result is shown in the table 4.

(embodiment 7)

Except making water injection rate is 1.5 mass parts, with embodiment 1 likewise, make pellet.The result is shown in the table 4.

(embodiment 8)

Except an electrical conductivity of inject to use mixing the manufacturing of bed formula pure water device is the pure water of 0.5 μ S/cm, with embodiment 1 likewise, make pellet.The result is shown in the table 4.

(embodiment 9)

Except injecting pure water that is produced by two three tower pure water devices and the electrical conductivity that running water mixes is the water of 9 μ S/cm, with embodiment 1 likewise, the manufacturing pellet.The result is shown in the table 4.

(embodiment 10)

Except injecting pure water that is produced by two three tower pure water devices and the electrical conductivity that running water mixes is the water of 17 μ S/cm, with embodiment 1 likewise, the manufacturing pellet.The result is shown in the table 4.

(embodiment 11)

In tank, fill with a pure water that mixes the electrical conductivity 0.5 μ S/cm that bed formula pure water device makes, with the cooling of line material, in addition, with embodiment 1 likewise, make pellet.The result is shown in the table 5.

(embodiment 12)

In tank, filling the electrical conductivity that pure water and running water by the manufacturing of two three tower pure water devices mix is the water of 9 μ S/cm, with the cooling of line material, in addition, with embodiment 1 likewise, make pellet.The result is shown in the table 5.

(embodiment 13)

In tank, filling the electrical conductivity that pure water and running water by the manufacturing of two three tower pure water devices mix is the water of 17 μ S/cm, with the cooling of line material, in addition, with embodiment 1 likewise, make pellet.The result is shown in the table 5.

(embodiment 14)

Shorten tank cooling distance, the line material temperature during with cutting is increased to 118 ℃, in addition, with embodiment 1 likewise, make pellet.The result is shown in the table 5.

(embodiment 15)

Prolong tank cooling distance, the line material temperature during with cutting is reduced to 79 ℃, in addition, with embodiment 1 likewise, make pellet.The result is shown in the table 5.

(embodiment 16)

Except curing step being set at 7 hours, with embodiment 1 likewise, make pellet.The result is shown in the table 5.

Need to prove, in each table below table 3, " pellet shape " and " overall merit " hurdle zero with * according to the judgement of the benchmark of below table 2.

[table 2]

[table 3]

[table 4]

[table 5]

(comparative example 1)

Except using PC-3 to replace the PC-1, with embodiment 1 likewise, make pellet.The result is shown in the table 6.

(comparative example 2)

Except reducing the quantity delivered of nitrogen, making the oxygen concentration in the magazine chute is beyond the 4.0 volume %, with embodiment 1 likewise, make pellet.The result is shown in the table 6.

(comparative example 3)

Except the supply that stops nitrogen, to make the oxygen concentration in the magazine chute be the 21 volume %, with embodiment 1 likewise, make pellet.The result is shown in the table 6.

(comparative example 4)

Except making distance (vertical height) for the 40cm from the material supply port of quantitative feeder to the material supply port of double screw extruder, with embodiment 1 likewise, make pellet.The result is shown in the table 6.

(comparative example 5)

Except injecting pure water that is produced by two three tower pure water devices and the electrical conductivity that running water mixes is the water of 33 μ S/cm, with embodiment 1 likewise, the manufacturing pellet.The result is shown in the table 7.

(comparative example 6)

In tank, filling the electrical conductivity that pure water and running water by the manufacturing of two three tower pure water devices mix is the water of 33 μ S/cm, with the cooling of line material, in addition, with embodiment 1 likewise, make pellet.The result is shown in the table 7.

(comparative example 7)

Except the cancellation water filling, with embodiment 1 likewise, make pellet.The result is shown in the table 7.

(comparative example 8)

Except making water injection rate is 0.05 mass parts, with embodiment 1 likewise, make pellet.The result is shown in the table 7.

(comparative example 9)

Except making water injection rate is 2.5 mass parts, with embodiment 1 likewise, make pellet.The result is shown in the table 7.

Extrude when opening exhaust outlet when finishing resin come up (ejection might be that vacuum system is inaccessible by resin in long-time continuous is produced, and is judged as and is not suitable for steady production).

(comparative example 10)

Except screw speed is set at the 900rpm, with embodiment 1 likewise, make pellet.The result is shown in the table 8.

(comparative example 11)

Shorten tank cooling distance, the line material temperature during with cutting is increased to 132 ℃, in addition, with embodiment 1 likewise, make pellet.The result is shown in the table 8.

(comparative example 12)

Prolong tank cooling distance, the line material temperature during with cutting is reduced to 65 ℃, in addition, with embodiment 1 likewise, make pellet.The result is shown in the table 8.

(comparative example 13)

In embodiment 1,, measure the carried charge of pellet without curing step.Carried charge is 10.2kV, easily the dust in the absorbed air.The result is shown in the table 8.

[table 6]

[table 7]

[table 8]

(embodiment 17)

Except screw speed is set at the 700rpm, with embodiment 1 likewise, make pellet.The result is shown in the table 9.

(embodiment 18)

Except discharge-amount being set at 70kg/hr, screw speed being set at the 300rpm, likewise make pellet with embodiment 1.The result is shown in the table 9.

(embodiment 19)

Constitute the B except screw rod being constituted the screw rod that is set at Fig. 3, likewise make pellet with embodiment 18.It is that the helical pitch of the screw rod of the screw rod depressor area that constitutes A is the formation of 1.0D that screw rod constitutes B.The result is shown in the table 9.

(embodiment 20)

Constitute the C except screw rod being constituted the screw rod be set at Fig. 3, with embodiment 1 likewise, make pellet.

Screw rod constitutes C and has following formation:

A) melting zone: the forward screw rod that is connected with length 31.5D, helical pitch 1.5D.

B) mixing district: length 4.5D

Along throughput direction, comprise forward kneading member 1.0D, reverse kneading member 0.5D and forward kneading member 1.0D, quadrature kneading member 1.0D, reverse kneading member 1.0D.

C) depressor area: the forward screw rod that is connected with length 16.5D, helical pitch 1.5D.

The result is shown in the table 9.

(embodiment 21)

Constitute the D except screw rod being constituted the screw rod be set at Fig. 3, with embodiment 1 likewise, make pellet.

A) melting zone: the forward screw rod that is connected with length 41.5D, helical pitch 1.5D.

B) mixing district: length 4.0D

Along throughput direction, comprise forward kneading member 1D, reverse kneading member 0.5D and forward kneading member 1.0D, quadrature kneading member 1.0D, counterscrew 0.5D.Wherein, in C 13 machine barrels fluid injection plug is installed, adds water with plunger displacement pump.

C) depressor area: the forward screw rod that is connected with length 17.0D, helical pitch 1.5D.This resin transfer district is the length of relief portion.

The result is shown in the table 9.

[table 9]

(embodiment 22)

In embodiment 1, do not carry out the pellet drying, the injection (mo(u)lding) machine SH 100 that uses Sumitomo Juki Corporation to make under the condition of 290 ℃ of barrel zone temperatures, 80 ℃ of mold temperatures, molds the flat moulding article of 100mm * 100mm * 3mm.Seen the silver bar (silver streak) of minute quantity, but in no problem scope.

Utilizability on the industry

Manufacturing method according to the invention can be made polycarbonate resin pellet, and impurity contents such as its chlorine compound are few; The resin deterioration is few, and yellowing does not take place, and the pellet outward appearance is good; Can under the situation of no resin additive, use, can obtain the high high-quality moulding article of cleannes, therefore; Can be applied to wide spectrums such as electrical and electronic parts, the usability on the industry is very high.

Claims

1. the manufacturing approach of a polycarbonate resin pellet is characterized in that, its polycarbonate resin of containing micro-carrene of serving as reasons is made the method for the polycarbonate resin pellet that carrene content reduced, and comprises following operation:

The polycarbonate resin that 3) will pass through the powder shape that non-active gas handles supplies in the vented extruder; In mixing district, injecting with respect to 100 mass parts polycarbonate resins is that the electrical conductivity of 0.1 ~ 2 mass parts is the operation of the water below the 30 μ S/cm;

4) exhaust ports in the downstream through making the water injection portion that is arranged at extruder is aspirated in decompression state; Thereby from the resin of molten condition, carrene and above-mentioned water are aspirated removal together, and the moisture concentration in the resin is adjusted to the operation of 10 ~ 200ppm;

2. the manufacturing approach of polycarbonate resin pellet according to claim 1 is characterized in that, it further carries out the pellet of the saturation state that obtains through curing step is carried out dry drying process.

3. the manufacturing approach of polycarbonate resin pellet according to claim 1; It is characterized in that; When handling the polycarbonate resin of powder shape, supply with the powder body with full state with non-active gas, from the below being that the mode of adverse current is supplied with non-active gas with respect to the powder body.

4. the manufacturing approach of polycarbonate resin pellet according to claim 1 is characterized in that, making the oxygen concentration in the machine barrel of vented extruder is below the 3 volume %.

5. the manufacturing approach of polycarbonate resin pellet according to claim 1 is characterized in that, the mixing district of injecting water is the zone that is full of of resin, and resin pressure is the scope of 0.5 ~ 10MPa.

6. the manufacturing approach of polycarbonate resin pellet according to claim 1 is characterized in that, the resin fullness rate is that the length in the zone of 5 ~ 30 volume % is more than the 8.0D in the relief portion of extruder, and wherein D is the machine barrel internal diameter of extruder.

7. the manufacturing approach of polycarbonate resin pellet according to claim 1 is characterized in that, the temperature that is used to cool off the water of line material is 30 ~ 90 ℃.

8. polycarbonate resin pellet, it is through the described manufacturing approach manufacturing of claim 1.

9. an electrical and electronic equipment part transports and uses case, and it uses the described polycarbonate resin pellet of claim 8.