CN101516941A - Non-thermofusible granular phenol resin, method for producing the same, thermosetting resin composition, sealing material for semiconductor, and adhesive for semiconductor - Google Patents

Non-thermofusible granular phenol resin, method for producing the same, thermosetting resin composition, sealing material for semiconductor, and adhesive for semiconductor Download PDF

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CN101516941A
CN101516941A CNA2007800348520A CN200780034852A CN101516941A CN 101516941 A CN101516941 A CN 101516941A CN A2007800348520 A CNA2007800348520 A CN A2007800348520A CN 200780034852 A CN200780034852 A CN 200780034852A CN 101516941 A CN101516941 A CN 101516941A
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phenol resin
granular phenol
thermofusible
granular
weight
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CN101516941B (en
Inventor
吉永直人
若山善治
茨木敏
下村淳
村外荣己
盐见仁郎
小谷善信
池田孝臣
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Air Water Inc
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Air Water Inc
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Priority claimed from JP2007174033A external-priority patent/JP2009013224A/en
Priority claimed from JP2007214781A external-priority patent/JP4949971B2/en
Priority claimed from JP2007251605A external-priority patent/JP5496448B2/en
Application filed by Air Water Inc filed Critical Air Water Inc
Priority claimed from PCT/JP2007/069927 external-priority patent/WO2008047700A1/en
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

Disclosed is a non-thermofusible phenol resin powder having an average particle diameter of not more than 20 [mu]m and a single particle ratio of not less than 0.7. This non-thermofusible phenol resin powder preferably has a chlorine content of not more than 500 ppm. This non-thermofusible phenol resin powder is useful as an organic filler for sealing materials for semiconductors and adhesives for semiconductors. The non-thermofusible phenol resin powder is also useful as a precursor of functional carbon materials such as a molecular sieve carbon and a carbon electrode material.

Description

Non-thermofusible granular phenol resin and manufacture method thereof and compositions of thermosetting resin, sealing material for semiconductor and adhesive for semiconductor
Technical field
The present invention relates to a kind of non-thermofusible granular phenol resin and manufacture method thereof.More specifically, the present invention relates to be used as organic filler, the perhaps precursor of functional carbon material such as molecular-sieve carbon, carbon electrode material etc., safe non-thermofusible granular phenol resin and the manufacture method thereof can be well used as the additive of the material in the various industrial circles such as formed material, coating, refractory materials, papermaking, high-abrasive material, whetstone, tackiness agent.In addition, sealing material for semiconductor and the adhesive for semiconductor that the invention still further relates to the compositions of thermosetting resin that contains this non-thermofusible granular phenol resin and use this compositions of thermosetting resin.
Background technology
Resol is the outstanding material of the balance of thermotolerance, mechanical property and electrical characteristic and cost, is used to various industrial circles.Especially the granular or pulverous resol of discovered in recent years or its cured article go for various fields, and as multi-purpose material, existing several goods are sold.
For example, open the spy and to disclose the granular or Powdered phenolic resin curing thing that the condenses by phenols and formaldehyde forms in the clear 57-177011 communique (patent documentation 1), it is sold as trade(brand)name " Bellpearl (registered trademark) R type " (Air Water Inc.'s system).This phenolic resin curing thing for example can be used as to be given thermotolerance or improves the organic filler of sliding properties or use as the filler that is used to reduce the gas volume that produces when uncured resol etc. is solidified.In addition, the resin that resol is high carbon residue rate owing to its chemical structure is so for example can be used as activated carbon or the precursor that burns till of the powder formed carbon material that is suitable for using as carbon electrode material uses.And then the granular or Powdered phenolic resin curing thing of record does not contain deleterious phenol monomer or low molecule condensation composition in patent documentation 1, has safe characteristics.
At this, under the situation as the precursor of organic filler or powder formed carbon material with aforesaid granulous resol or its cured article, in order to bring into play performance, must suitably control the shape and the form of this particle as the precursor needs of organic filler or powder formed carbon material.Promptly, for be implemented in high fillibility in the goods, high specific area during as the powder formed carbon material and the low viscosity during as the water-based slip etc., preferably the median size of (i) particle is enough little, and (ii) must almost not have 2 agglutinators producing owing to the aggegation between the progenitor.In addition, except described (i) and (ii), more preferably (iii) the size-grade distribution of particle shape enough narrow and/or (iv) particle approaches spherical shape.And then if consider the security of the goods that are suitable for this granular phenol resin or the security when making, then best (v) the remaining quantity of the phenol monomer (free phenol) in the granular phenol resin still less.At this, described enough little particle diameter is meant if consider granular phenol resin or its cured article being suitable in various industrial uses, then must be at least below the 20 μ m, more preferably below the 10 μ m.
But, for granulous resol or its cured article, although carried out a lot of researchs at present, present situation is granular phenol resin or the unknown still of its cured article that possesses described characteristic, and the mass-produced manufacture method that is suitable for such granular phenol resin or its cured article is also unknown.
For example, synthesis conditions such as amount ratio by rationalizing the formaldehyde, phenol, hydrochloric acid and the aqueous medium that use, temperature condition in described patent documentation 1, have been put down in writing, thereby obtain granular or pulverous non-thermofusible resol, but the non-thermofusible resol that obtains have (i) initial size more greatly, (ii) because 2 agglutinators that the aggegation of progenitor forms are more, (iii) size-grade distribution wide, (iv) contain the point that the particle etc. of the shape beyond the more sphere remains to be improved.
In addition, open in the 2000-239335 communique (patent documentation 2) the spy and to disclose, make after phenol and the formaldehyde reaction, be cured reaction with acid catalyst, the spherical phenolic resin curing thing that obtains thus with alkaline catalysts by in the presence of suspension agent.But the median size of concrete record is 100～800 μ m in an embodiment.
Open in the presence of at least a and catalyzer of having put down in writing in the clear 50-98537 communique (patent documentation 3) in an acidic catalyst and basic catalyst that contains compound nitrogen series the spy, make the reaction of phenols and aldehydes, in the initial stage condenses that obtains, add cellulose-based compound, further continue reaction, spheroidizing thus, dehydrate afterwards, obtain the granular phenol resin of non-thermofusible.But the median size of this granular phenol resin is about 700 μ m.In addition, also contain the free phenol of the 6000ppm that has an appointment, so, room for improvement is arranged from the viewpoint of security.
Open in the 2001-114852 communique (patent documentation 4) the spy and to have put down in writing in the presence of condensation catalyst and emulsifying dispersant, at temperature more than 105 ℃ below 200 ℃, pressure 1.3kg/cm 2Above 15kg/cm 2Under the following condition, make phenols and aldehydes carry out condensation reaction, obtain spherical resol thus.As shown in embodiment, this spherical resol has the median size about 2～about 200 μ m.But the problem of existence is, with numerous and diverse program of using pressure kettle (autoclave) to react and so on, because stirring means or stirring velocity difference and particle diameter greatly changes.And then think that reactive mode is identical with described patent documentation 3 in itself, the chemical structure of the resol that obtains is also identical, so think and contain more free phenol.
Open in the clear 59-6208 communique (patent documentation 5) in the presence of water-soluble high-molecular compound the spy, use the nitrogenous compound catalyzer, make the reaction of phenols and aldehydes, utilize an acidic catalyst, make the dispersion of the spherical resol of solvable type that obtains take place solidify the spherical resol that forms and put down in writing.But the median size of utilizing the spherical resol that this method obtains is greatly to 350～520 μ m.
Open the manufacture method that discloses a kind of spherical resin fine particles in the 2002-226534 communique (patent documentation 6) the spy, it is the method from Resorcinol and aldehydes manufacturing spherical resin fine particles, it is characterized in that, making the Resorcinol and the ratio (weight ratio) of water is 1: 5～1: 100, and the pH regulator of reaction system is become 5～7.As shown in the Examples, this spherical resin fine particles has the median size of 500nm～2 μ m.But existence can only be used the problem of Resorcinol as the phenol source, thereby, think and compare that the carbon residue rate of the resol that obtains is low with the situation of using other phenols such as phenol.
Open the manufacture method of having put down in writing a kind of spherical phenolic resin curing thing in the flat 10-338728 communique (patent documentation 7) the spy, wherein, from the intimate mixing liquid that contains resol and derivatived cellulose and solvent, remove and desolvate, resol and derivatived cellulose are separated, make phenolic resin curing, remove derivatived cellulose from the complex body of phenolic resin curing thing and derivatived cellulose then.Utilize such method, can obtain having 28nm～the spherical phenolic resin curing thing of the median size of 5 μ m.But present method has to use the organic solvent to the security presence problem of environment or human body.And then, owing to utilize the reaction that is separated in the solid phase, thus the generation of particle extract need 21 hours～114 hours so for a long time.
Open the spy and to disclose in the flat 7-18043 communique (patent documentation 8) in the mixed solvent of the water of specified quantitative or water/water Combination organic solvent, in the presence of acid catalyst, the limit concentrates this solvent limit and makes oxybenzene compound and formaldehyde reaction, utilize reaction with solidifying agent, the phenolic varnish spherical particle of separating out is solidified, thereby make the method that spherical P-F is a resin.If utilize this method, then can obtain the spherical resol of the particle diameter about 9 μ m for example or 15 μ m.But this spherical resol that utilizes present method to obtain can not satisfy size-grade distribution fully.And then, think that reactive mode is identical with described patent documentation 3 in itself, the chemical structure of the resol that obtains is also identical, so think and contain more free phenol.
So, though the past is as the gimmick that obtains the particulate of resol, propose to use additive such as suspension agent or emulsifying dispersant or the polymerizing condition of resol etc. rationalized and waited the whole bag of tricks, but not have to propose to have resol particle and the manufacture method thereof that median size is below the 20 μ m, is preferably the nominal particle size below 10 μ m and does not almost have the content of 2 agglutinators, monomer phenols considerably less, have high security.And then, granular phenol resin and manufacture method thereof that the size distribution that is shaped as spherical shape, particle of this particle is enough narrow are not proposed except these characteristics yet.
Even under the situation of polymerizing condition that for example rationalizes resol etc., polymerizing condition self when making phenols with the aldehydes polymerization and normally used polymerizing condition become and contain in the resol that obtains and the high monomer phenols of past same degree in itself under the identical situation.In addition, low whipping speed influences in the manufacture method of granular phenol resin of particle diameter and so on, owing to can not continue equably in the stirring reaction container, size distribution must broaden.
Usually integrated circuit (IC) apparatus such as IC (unicircuit (Integrated Circuit)), storer are made of semiconductor element, insulativity supporting substrate, lead frame and lead-in wire etc., for their sealings and joint, use sealing material or tackiness agent.The main flow in past is to use the resin combination of mineral fillers such as containing spherical silicon dioxide, Resins, epoxy and solidifying agent as such sealing material or tackiness agent.
But, in recent years, for 1) and the electronic component that guarantees of high temperature actions such as the rising of the soldering temperature that causes to the transfer of no lead welding of reply and essential vehicle mounted electronic component suitable, require sealing material or tackiness agent to have thermotolerance.And then the further miniaturization for the internal wiring of tackling unicircuit needs the miniaturization of the filler in sealing material or the tackiness agent or the lowering viscousity of sealing material and tackiness agent, and in cooperation in the past, is difficult to satisfy this two new demand characteristics.
Promptly, as organic Resins, epoxy and as the spherical silicon dioxide (fused silica) of inorganics because linear expansivity has very big difference, so when following the manufacturing of soldering operation etc. or the heating and cooling in when use, stress takes place in the interface at Resins, epoxy and spherical silicon dioxide, thereby the deterioration of generation crackle etc. becomes problem.
The spy open put down in writing in the flat 11-172077 communique (patent documentation 9) for the mechanical characteristics that improves cured article encapsulating semiconductor with composition in mating reaction be silane coupling agent in the amino of silica sphere.But,, lower so the thermotolerance of sealing material also depends on the thermotolerance of silane coupling agent because the thermotolerance of silane coupling agent self is low.
As being used to eliminate described interface at Resins, epoxy and spherical silicon dioxide one of means of stress taking place, has considered mineral fillers such as replacement spherical silicon dioxide, and used as organic organic filler.This is because by using organic filler, diminishes with the difference of the linear expansivity of Resins, epoxy.For example, opening 2000-269247 communique (patent documentation 10), spy the spy opens 2002-226824 communique (patent documentation 11) and spy and opens to have put down in writing in the 2004-168848 communique (patent documentation 12) and can use organic filler as sealing material for semiconductor or adhesive for semiconductor.But, do not mention and possess the described concrete organic filler that requires characteristic.
At this, resol is the outstanding material of thermotolerance, mechanical property and electrical characteristic, is used as electronic material and various Industrial materials such as uses.If the cured article of resol can be used as organic filler, then can give the good characteristic that this resol has to sealing material for semiconductor or tackiness agent.
But, propose at present to have high heat resistance as yet and realized the miniaturization of resin particle simultaneously and become sealing material or the phenolic resin curing thing of the lowering viscousity during tackiness agent.In addition, as the organic filler of in sealing material for semiconductor or adhesive for semiconductor, using, the preferred ion foreign matter content, especially content of halide ions is little, but resol normally used ionic catalyzer originally and was able to polymeric in aqueous medium, so be difficult to obtain ionic impurity content is reduced to the phenolic resin curing thing that goes for semiconductor applications.
Open flat 10-60068 communique (patent documentation 13) the spy, the spy opens in the flat 2-245011 communique (patent documentation 14) and has put down in writing the resol that utilizes specific carrying out washing treatment to reduce ionic impurity, narrated this resol and can be used for purposes such as semi-conductive sealing material.But the resol of putting down in writing in these documents is uncured resol, is not the resol as organic filler.In addition, the washing methods of putting down in writing can not be used for removing the ionic impurity of phenolic resin curing thing in these documents.
Patent documentation 1: the spy opens clear 57-177011 communique
Patent documentation 2: the spy opens the 2000-239335 communique
Patent documentation 3: the spy opens clear 50-98537 communique
Patent documentation 4: the spy opens the 2001-114852 communique
Patent documentation 5: the spy opens clear 59-6208 communique
Patent documentation 6: the spy opens the 2002-226534 communique
Patent documentation 7: the spy opens flat 10-338728 communique
Patent documentation 8: the spy opens flat 7-18043 communique
Patent documentation 9: the spy opens flat 11-172077 communique
Patent documentation 10: the spy opens the 2000-269247 communique
Patent documentation 11: the spy opens the 2002-226824 communique
Patent documentation 12: the spy opens the 2004-168848 communique
Patent documentation 13: the spy opens flat 10-60068 communique
Patent documentation 14: the spy opens flat 2-245011 communique
Summary of the invention
The present invention proposes in view of such situation just, and its purpose is to provide granular phenol resin and the manufacture method thereof that a kind of median size is small, do not contain being shaped as spherical shape, having narrow size-grade distribution of 2 agglutinators, particle, non-thermofusible that free phenol content is few, safe.
In addition, another object of the present invention is to provide a kind of small, the granular phenol resin and manufacture method thereof that can realize the non-thermofusible that lowering viscousity and ionic impurity content reduce when becoming sealing material or tackiness agent of median size when having high heat resistance.
Another object of the present invention is to provide a kind of resin combination of the granular phenol resin with non-thermofusible that high heat resistance and low-viscosity while ionic impurity content reduces and sealing material for semiconductor and the adhesive for semiconductor that uses this resin combination.
The inventor etc. concentrate on studies; found that by in the presence of colloid protective agent; in aqueous medium; use an acidic catalyst of high density; make the reaction of aldehydes and phenols; reacting by heating liquid then can obtain having the granular phenol resin of the non-thermofusible of aforesaid good characteristic.
In addition, the inventor etc. also find, in containing the phenol resin composition of granular phenol resin, in order to realize lowering viscousity, must make the containing ratio of 2 agglutinators that the aggegation between the enough little and particle of the median size of this granular phenol resin causes little, and, for the ionic impurity that reduces the granular phenol resin cured article, content of halide ions especially, as long as wash granular phenolic resin curing thing with alcohols and/or alkaline aqueous solution.That is, the present invention is as described below.
Non-thermofusible granular phenol resin of the present invention is characterised in that median size is below the 20 μ m, and the simple grain rate is more than 0.7.Median size is preferably below the 10 μ m.Wherein, aftermentioned reaches the definition of " simple grain rate " to term " non-thermofusible ", " median size ".
In non-thermofusible granular phenol resin of the present invention, preferably the coefficient of variation by the size distribution of following formula [1] expression is below 0.65.
The coefficient of variation of size distribution=(d 84%-d 16%)/(2 * median size) [1]
At this, d 84%, d 16%It is respectively the particle diameter of expression cumulative frequency 84%, 16% in the frequency distribution that utilizes the laser diffraction and scattering method to obtain.
In addition, in non-thermofusible granular phenol resin of the present invention, the degree of sphericity of preferred particle is more than 0.5.
And then in non-thermofusible granular phenol resin of the present invention, preferred free phenol content is below the 500ppm.Wherein, aftermentioned reaches the definition of " free phenol content " to described term " degree of sphericity ".Non-thermofusible granular phenol resin of the present invention more preferably median size is below the 10 μ m, is below 0.65 by the coefficient of variation of the size distribution of above-mentioned formula [1] expression, and degree of sphericity is more than 0.5, and free phenol content is below the 500ppm.
In addition, in non-thermofusible granular phenol resin of the present invention, preferred cl content is below the 500ppm, more preferably below the 100ppm.
In addition, the present invention also provides a kind of manufacture method of non-thermofusible granular phenol resin, wherein, comprise: (1) by the volumetric molar concentration in reaction solution be an acidic catalyst more than the 2.0mol/L and colloid protective agent in the presence of, in aqueous medium, make the reaction of aldehydes and phenols, the granular phenol resin that forms granular phenol resin forms operation; (2) heating contains the reaction solution of granular phenol resin, thereby forms the non-hot melt operation of the granular phenol resin of non-thermofusible; (3) from reaction solution, separate the granular phenol resin of described non-thermofusible and the separating, washing operation of washing.Present method can be suitable for well as the method for making described non-thermofusible granular phenol resin of the present invention.
At this, preferred described an acidic catalyst is a hydrochloric acid, and described aldehydes is formaldehyde, paraformaldehyde or their mixture.
In addition, the adding mol ratio of the described relatively aldehydes of preferred described phenols is below 0.9.Preferred described colloid protective agent is the water-soluble polysaccharide analog derivative.
In addition, the separating, washing operation also can comprise: use the operation that the fluidity medium washs the granular phenol resin of described non-thermofusible more than a kind that is selected from alcohols and the alkaline aqueous solution.Like this, can obtain cl content is the following non-thermofusible granular phenol resin of 500ppm.
Preferably under the temperature more than the second-order transition temperature of the granular phenol resin of described non-thermofusible, used the washing of alcohols.
And then the present invention also provides a kind of compositions of thermosetting resin, and wherein, containing cl content is following non-thermofusible granular phenol resin of the present invention, Resins, epoxy and solidifying agent of 500ppm.Compositions of thermosetting resin of the present invention also can further contain mineral filler.
And then the present invention also provides a kind of sealing material for semiconductor and adhesive for semiconductor that is formed by described compositions of thermosetting resin.
If utilize the present invention, it is promptly to have very small particle diameter below the 20 μ m and contain 2 agglutinators that the aggegation of this small progenitor causes, the i.e. granular phenol resin of the non-thermofusible that the simple grain rate is high hardly that median size then can be provided.Non-thermofusible granular phenol resin of the present invention like this can be used as the additive of the material in the various industrial circles such as formed material, coating, refractory materials, papermaking, high-abrasive material, whetstone, tackiness agent well, especially can be used as the precursor of functional carbon materials such as organic filler or carbon electrode material, activated carbon, molecular-sieve carbon etc.
In addition, if utilize the present invention, it is the granular phenol resin of the non-thermofusible that reduces significantly of 2 agglutinators promptly having very small particle diameter below the 20 μ m and contain hardly that the aggegation of this small progenitor causes and content of halide ions that median size then can be provided.Non-thermofusible granular phenol resin of the present invention so also can be used as the additive of the material in the various industrial circles well.Especially the granular phenol resin of this non-thermofusible is extremely useful as sealing material for semiconductor and adhesive for semiconductor as the compositions of thermosetting resin of organic filler.
And then the present invention also provides and makes the preferred manufacture method of non-thermofusible granular phenol resin institute possess aforesaid outstanding characteristic.If utilize the manufacture method of non-thermofusible granular phenol resin of the present invention, the non-thermofusible granular phenol resin that then can utilize easier method manufacturing to have outstanding characteristic, method of the present invention is to be fit to mass-produced method.
Description of drawings
Fig. 1 is the SEM photo of a preference of non-thermofusible granular phenol resin of the present invention.
Fig. 2 is the optical microscope photograph of the non-thermofusible granular phenol resin that obtains in embodiment 2.
Fig. 3 is the optical microscope photograph of the non-thermofusible granular phenol resin that obtains in embodiment 3.
Fig. 4 is the optical microscope photograph of the granular phenol resin that obtains in comparative example 1.
Fig. 5 is the graphic representation of the relation between the median size of expression concentration (weight (ppm) of the colloid protective agent of relative response liquid gross weight) of colloid protective agent and granular phenol resin.
Fig. 6 is the scanning electron microscope photo (SEM photo) (500 times) of the granular phenol resin 12A-c that obtains in embodiment 12.
Fig. 7 is the SEM photo (3500 times) of the further amplification of granular phenol resin 12A-c.
Fig. 8 is the SEM photo of a preference of granular carbon electrode material of the present invention.
Fig. 9 is the optical microscope photograph of the granular carbon electrode material that obtains in reference example 9.
Figure 10 is the optical microscope photograph of the granular carbon electrode material that obtains in reference example 11.
Figure 11 is the optical microscope photograph of the granular carbon electrode material that obtains in reference comparative example 1.
Figure 12 is the graphic representation of the relation between the median size of expression concentration (weight (ppm) of the colloid protective agent of relative response liquid gross weight) of colloid protective agent and granular carbon electrode material.
Figure 13 is the summary sectional view that is illustrated in the electric double layer capacitor of trial-production in the reference example 15.
Figure 14 is the summary mode chart of a preference of expression PSA formula nitrogen generator unit of the present invention.
Figure 15 is the SEM photo on the molecular-sieve carbon surface that obtains in reference example 18.
Figure 16 is the summary mode chart of the device of the expression characterization of adsorption that is used to measure molecular-sieve carbon.
Figure 17 is the figure that the relation of the purity of the goods nitrogen in the PSA formula nitrogen generator unit of the different molecular-sieve carbon of yield and goods nitrogen flow has been used in expression.
Among the figure, 101a, the 101b-adsorption tower, the 102-compressor, the 103-instrument air dryer, 104-goods groove, 105,106a, 106b, 109a, 113a, 113b, 115a, 115b, 116, the 305-magnetic valve, 107a, 107b, 108a, 108b, 110,112,114,117, the 317-pipe arrangement, 111-pressure-regulator, 301-vacuum pump, 302,303,308, the 316-valve, 304, the 307-pressure warning unit, 306-constant pressure valve, 309-gas regulator, the 310-bomb, the 311-measuring cell, 312-sample chamber, 313, the 314-pressure transmitter, the 315-register, the carbon electrode material of 601-pulpous state, 602-current collector, 603-dividing plate, the 604-distance piece, the 605-terminal strip.
Embodiment
＜non-thermofusible granular phenol resin 〉
Non-thermofusible granular phenol resin of the present invention is the resol of the non-thermofusible that forms of the reaction product by phenols and aldehydes, it is characterized in that (term as relative 2 agglutinators is also referred to as progenitor to particle.) median size be below the 20 μ m, the simple grain rate that becomes at the index of the content of 2 agglutinators is more than 0.7.Like this, be below the 20 μ m, be preferably below the 10 μ m by the median size that makes the resol particle, the simple grain rate is more than 0.7, for example this granular phenol resin is being used as under the situation of organic filler, become possibility with higher filling ratio filling, and be filled with this granular phenol resin resin combination etc. be filled that thing is compared with the past to be low viscosity, handle easily so become.The lowering viscousity of such resin combination meets in recent years the characteristic that requires at the sealing material of semiconductor applications needs or tackiness agent.
In addition, granular phenol resin of the present invention can also be well as for example precursor of functional carbon materials such as activated carbon, carbon electrode material, molecular-sieve carbon.Be below the 20 μ m, be preferably below the 10 μ m by the median size that makes the resol particle, the simple grain rate is more than 0.7, can improve the space fillibility of utilizing the carbon dust that is fired into significantly.Thereby the granular phenol resin of the application of the invention can improve the performance of per unit volume of this functional carbon material or the surface-area of per unit weight significantly.And then, have and in the high density field, also be low viscous feature even will be scattered in the dispersion liquid that forms the fluidity medium such as water for example from the functional carbon material that granular phenol resin of the present invention obtains.Have the dispersion liquid of such feature can be well use such as when for example making the coating carbon electrode.This non-thermofusible granular phenol resin of the present invention not only can be used for above-mentioned purposes, but also can be suitable in the industrial circle of wide regions such as formed material, coating, refractory materials, papermaking, high-abrasive material, whetstone, tackiness agent.
In addition,, can enumerate and pulverize the method for solidified resol, but in the method, be shaped as unsettingly, can not obtain the good saccharoid of fillibility as the method in the past of the micropowder that obtains non-thermofusible resol.
Fig. 1 represents that the scanning electron microscope photo of a preference of non-thermofusible granular phenol resin of the present invention is (hereinafter referred to as the SEM photo.)。As shown in Figure 1, non-thermofusible granular phenol resin of the present invention is the small granular phenol resin of particle diameter, and 2 agglutinators that the aggegation of this particle (progenitor) causes are few.Wherein, the granular phenol resin of Fig. 1 be 5 μ m with undefined median size, the simple grain rate is 1.0.
Non-thermofusible granular phenol resin of the present invention is elaborated.Non-thermofusible granular phenol resin of the present invention is the resol of the non-thermofusible that forms of the reaction product by phenols and aldehydes.At this, the reaction product of phenols and aldehydes is the resultant that utilizes their generation addition reactions and condensation reaction to obtain basically, but comprises that also only the resultant of addition reaction takes place for some.As phenols, be not particularly limited, can exemplify out phenol, naphthols, quinhydrones, Resorcinol, xylenol, pyrogallol etc.Phenols can be a kind, also can be used in combination more than 2 kinds.Wherein, if the performance of the resol that consideration obtains and the balance of cost, then preferred phenols is a phenol.
As aldehydes, be not particularly limited, can exemplify out formaldehyde, paraformaldehyde, oxalic dialdehyde, phenyl aldehyde etc.Aldehydes can be a kind, also can be used in combination more than 2 kinds.Wherein, aldehydes is preferably formaldehyde, paraformaldehyde or their mixture.
At this, in this manual, " non-thermofusible " is meant under specific high-temperature pressurizing condition, granular phenol resin does not fuse, particularly, about 5g granular phenol resin sample is inserted between 2 thick stainless steel plates of 0.2mm, utilize heat in advance to 100 ℃ pressing machine with the total load punching press of 50kg in the time of 2 minutes, do not take place to form the character that is bonded to each other between flat board or distortion of resol particle or resol particle because of fusion and/or fusion granular phenol resin.Such character can after utilizing the reaction novolak resin of phenols and aldehydes, give this resol crosslinking curing by in the manufacturing of granular phenol resin.Crosslinking curing for example can be undertaken by heating the reaction solution that has carried out the reaction of phenols and aldehydes.
Non-thermofusible granular phenol resin of the present invention boil the dissolve with methanol degree preferably less than 30%, more preferably less than 20%.In this manual, " boiling the dissolve with methanol degree " is meant the content that boils the solvable composition of methyl alcohol in the granular phenol resin, particularly, is defined as the value of utilizing test as described below to calculate.That is, the about 10g of precision weighing resol sample, among the about 500mL of anhydrous actually methyl alcohol, heating under refluxing in 30 minutes, the glass filter with No.3 filters then, and then with the resistates on the anhydrous methanol cleaning glass strainer of about 100mL.Then, with the resistates on the glass filter after the washing in 5 hours of 40 ℃ of dryings, this resistates of precision weighing then.To utilize the value of calculating with following formula [2] as " boiling the dissolve with methanol degree ".
Boil dissolve with methanol degree (weight %)=(resol example weight and dried residue weight poor)/(resol example weight) * 100 [2]
" boiling the dissolve with methanol degree " is not to judge directly whether this resol has the standard of " non-thermofusible ", and can become an index of the degree of the thermally melting of understanding resol.That is, exist " boiling the dissolve with methanol degree " low more, then the also low more trend of thermally melting.If boil the dissolve with methanol degree is more than 30%, then under in use the heating or the effect of pressurization sometimes, thermally melting is shown, and particle may be out of shape or fuse.
As mentioned above, the median size that constitutes the particle (progenitor) of non-thermofusible granular phenol resin of the present invention is below the 20 μ m, is preferably below the 10 μ m.By making median size is below the 10 μ m, can further improve fillibility when granular phenol resin of the present invention is applicable to organic filler or functional carbon material or low viscosity, the low viscosity when being applicable to dispersion liquid.At this, in this manual, " median size " is meant that the measuring method that utilize to use laser diffraction formula particle size measurement machine is cumulative frequency 50% value of the frequency distribution that obtains of laser diffraction and scattering method (Microtrac method).As laser diffraction formula particle size measurement machine, can use day machine dress (strain) system MicrotracX100 well.
At this, surpass under the situation of 20 μ m in the median size of non-thermofusible resol particle, utilize the manufacture method cl content of non-thermofusible granular phenol resin of the present invention described later not reduce fully sometimes.On the basis of this sense, the median size of non-thermofusible resol particle is preferably below the 20 μ m, more preferably below the 10 μ m.
In addition, the simple grain rate of non-thermofusible granular phenol resin of the present invention is more than 0.7, to be preferably more than 0.8.The simple grain rate less than 0.7 situation under, fillibility when having the organic filler be applicable to sealing material for semiconductor or adhesive for semiconductor etc. or functional carbon material or low viscosity, the low viscosity when the being applicable to dispersion liquid inadequate trend that becomes.At this, in this manual, " simple grain " is meant the progenitor that does not form 2 agglutinators because of aggegation, " simple grain rate " is meant and disperses granular phenol resin in water droplet, carry out observation by light microscope, in the visual field of selecting at random that contains 300 progenitors of having an appointment, this when the total number of counting progenitor and the number of simple grain is than the total number of simple grain number/progenitor.
In addition, non-thermofusible granular phenol resin of the present invention preferably has narrow size distribution.Particularly, the coefficient of variation of size distribution that constitutes the particle (progenitor) of non-thermofusible granular phenol resin of the present invention is preferably below 0.65.The coefficient of variation of size distribution and then be preferably below 0.6.In this manual, " coefficient of variation of size distribution " is the value of utilizing following formula [1] to calculate.
The coefficient of variation of size distribution=(d 84%-d 16%)/(2 * median size) [1]
At this, in described formula [1], d 84%, d 16%Be respectively the particle diameter of representing cumulative frequency 84%, 16% in the frequency distribution that utilizes the laser diffraction and scattering method to obtain, median size is the median size in above-mentioned definition.Become below 0.65 by the coefficient of variation that makes median size, the further raising of fillibility and low viscosity the when organic filler that for example can realize as sealing material for semiconductor or adhesive for semiconductor etc. can be provided or the space fillibility when being applicable to functional carbon material, the granular phenol resin that can in the industrial circle of wide regions such as formed material, coating, refractory materials, papermaking, high-abrasive material, whetstone, tackiness agent, be suitable for simultaneously.As laser diffraction formula particle size measurement machine, can use day machine dress (strain) system Microtrac X100 well.
In order to improve the performance of sealing material for semiconductor etc., the preferred filling ratio that improves the filler of in adhesive resin, filling.As the method for the filling ratio that improves Ball-type packing, can enumerate the method that cooperates the different filler of granularity.That is the method that enters littler filler just in the closeest filling gap of the filler that matching design Cheng Zaigeng is big.For example, used fused silica usually in the past, but, mix fused silica and use with different median sizes in order to improve filling ratio as the sealing material use filler.When being suitable for such gimmick, must have the median size that needs, filler with narrow size distribution.If utilize the present invention, the organic filler that then can provide the sealing material for semiconductor that goes for such matching design to use.And then, for example in the specific fields such as tackiness agent that are used for the IC die bonding is used in substrate, even exist median size little, if but have the filler (being that size distribution is wide) of the big trace of particle diameter, bring detrimentally affect then can for the thickness of adhesive layer, thereby use the field that becomes difficulty.If utilize the present invention, even the non-thermofusible granular phenol resin that also can be suitable for well in this field then can be provided.
The particle shape of non-thermofusible granular phenol resin of the present invention is good more near spherical shape more.Particularly, degree of sphericity is preferably more than 0.5, more preferably more than 0.7, is preferably more than 0.9 especially.Particle shape is more near spherical shape, promptly, degree of sphericity is more near 1.0, the further raising of fillibility and low viscosity the when organic filler that for example can realize as sealing material for semiconductor or adhesive for semiconductor etc. then can be provided or the space fillibility when being applicable to functional carbon material, the granular phenol resin that can in the industrial circle of wide regions such as formed material, coating, refractory materials, papermaking, high-abrasive material, whetstone, tackiness agent, be suitable for simultaneously.At this, in this manual, " degree of sphericity " is meant in observation by light microscope, select to contain the visual field of 300 progenitors of having an appointment randomly, select the minimum progenitor of 10 aspect ratios (being the ratio of minor axis/major diameter), to these 10 progenitors, the mean value of these 10 aspect ratios when measuring the aspect ratio in its shadow area respectively.
The free phenol content of non-thermofusible granular phenol resin of the present invention is preferably below the 500ppm.This free phenol content is more preferably below the 300ppm, and then is preferably below the 200ppm.By making free phenol content is below the 500ppm, the security of the goods in the time of can improving the security when handling resol and be applicable to this resol in the various goods.At this, in this manual, " free phenol content " is defined as the value of utilizing test as described below to calculate.That is, the about 10g of precision weighing resol sample in the methyl alcohol of 190mL, extracted 30 minutes under refluxing, and filtered with glass filter.Utilize the phenols concentration in the quantitative filtrate of liquid chromatography, calculate the phenols weight in this filtrate.With the ratio of this phenols weight and example weight is that phenols weight/resol example weight is as " free phenol content ".
And then the cl content of non-thermofusible granular phenol resin of the present invention is preferably below the 500ppm.In semiconductor applications, to the viewpoint of environment or healthy security or the raising of characteristic electron, the viewpoint of the corrosive improvement of fine rule, need the halogenization of electronic material, preferred cl content is lower.If cl content surpasses 500ppm, then can influence the specific inductivity of the resin combination that contains non-thermofusible granular phenol resin, becoming causes the corrosion of lead-in wire etc. easily, becomes to satisfy the characteristic that requires as sealing material for semiconductor, adhesive for semiconductor.Cl content is preferably below the 100ppm, if be this content, then can be used for sealing material for semiconductor and adhesive for semiconductor better.At this, in this manual, " cl content " is the cl content of calculating from following measuring method.
Determinator: the system fluorescent x-ray analyzer ZSX100E of Co., Ltd. Neo-Confucianism
Measuring method: working sample (non-thermofusible resol particle) and mensuration are pressurizeed with binder powders, become to measure and use particle, use described determinator then, utilize the EZ scan pattern to carry out x-ray fluorescence analysis.That utilizes the phenolic resin curing thing infers molecular formula (C 7H 6O 1) the Alpha-ray diffracted intensity measured value of stdn chlorine K, as cl content (wt/wt).Wherein, the determination object that fluorescent X-ray is measured not only comprises chlorion, the chlorine atom that also comprises organochlorine compound etc., and using method of the present invention described later to make under the situation of non-thermofusible resol, owing to do not add organochlorine compound on the original idea, so we can say, utilize fluorescent X-ray to measure the cl content that obtains and equate in fact with chloride ion content.
The method that is used to make the non-thermofusible granular phenol resin that possesses aforesaid outstanding characteristic is not particularly limited, but can uses method shown below well.The manufacture method of non-meltbility granular phenol resin shown below also is included among the present invention.
The manufacture method of＜non-thermofusible granular phenol resin 〉
Operation (1)～(3) shown in below the manufacture method of non-thermofusible granular phenol resin of the present invention preferably contains.Below each operation is elaborated.
(1) by the volumetric molar concentration in reaction solution be an acidic catalyst more than the 2.0mol/L and colloid protective agent in the presence of, in aqueous medium, make the reaction of aldehydes and phenols, the granular phenol resin that forms granular phenol resin forms operation;
(2) heating contains the reaction solution of described granular phenol resin, thereby forms the non-hot melt operation of the granular phenol resin of non-thermofusible;
(3) from reaction solution, separate the granular phenol resin of described non-thermofusible and the separating, washing operation of washing.
(1) granular phenol resin forms operation
In this operation, by in the presence of an acidic catalyst and colloid protective agent, in aqueous medium, make the reaction of aldehydes and phenols, form granulous resol.As aldehydes, be not particularly limited, can exemplify out formaldehyde, paraformaldehyde, oxalic dialdehyde, phenyl aldehyde etc.Aldehydes can be a kind, also can be used in combination more than 2 kinds.Wherein, aldehydes is preferably formaldehyde, paraformaldehyde or their mixture.In addition, as described later, one of feature of method of the present invention is, use an acidic catalyst of high density, and under paraformaldehyde the situation as aldehydes of use as the polymkeric substance of formaldehyde, under such condition, paraformaldehyde is by depolymerization, so think that what in fact help to react is formaldehyde.Preferably the kind of the aldehydes that uses and usage quantity thereof are chosen to when reaction, in aqueous medium, dissolve.
As phenols, be not particularly limited, can exemplify out phenol, naphthols, quinhydrones, Resorcinol, xylenol, pyrogallol etc.Phenols can be a kind, also can be used in combination more than 2 kinds.Wherein, if consider the solvability in water and the performance and the balance of cost of the resol that obtains, then preferably phenols is a phenol.Preferably the kind of the phenols that uses and usage quantity thereof are chosen to when reaction, in aqueous medium, dissolve.
Particularly, for example using under the situation as phenols such as phenol, the concentration (weight ratio) that preferably usage quantity (add-on) of phenols is chosen to the phenols of relative response liquid gross weight is below the 10 weight %.Under the situation of using the lower phenols of solubleness in water (for example naphthols etc.), for guarantee when reaction in the dissolving in the aqueous medium, realize characteristic (small median size and high simple grain rate etc.) outstanding for granular phenol resin, preferably adopt lower concentration.At this, " reaction solution gross weight " is the gross weight of phenols, aldehydes, an acidic catalyst, colloid protective agent and aqueous medium.The concentration of the phenols by making relative response liquid gross weight is below the 10 weight %, can easily carry out forming from the reaction initial stage to granular phenol resin the temperature treatment in stage.For example under near the situation that begins the normal temperature to react, if making the concentration of phenols is below the 10 weight %, then because the over-drastic heating of not following uncontrolled reaction etc. to cause in initial reaction stage, so almost do not carry out temperature treatment, just can form median size little, suppress 2 agglutinative granular phenol resins.In addition, also can make the concentration (weight ratio) of the phenols of relative response liquid gross weight be higher than 10 weight %.In this case, the temperature treatment in the time of must suitably reacting mostly.
In addition, the adding mol ratio that preferably usage quantity (add-on) of described aldehydes is chosen to the phenols of relative aldehydes is below 0.9.Relatively the adding of the phenols of aldehydes is than more preferably below 0.75, and then is preferably below 0.5.The adding mol ratio of the phenols by making relative aldehydes is below 0.9, can form median size little, suppress 2 aggegations and then more near spherical shape, narrow diameter distribution, the poor granular phenol resin of free phenol.In addition, the adding mol ratio of the phenols by making relative aldehydes is below 0.75, can further suppress 2 aggegations.Better for the characteristic that makes these granular phenol resins, the adding mol ratio that especially preferably makes the phenols of relative aldehydes is below 0.5.Lower value to the adding mol ratio of the phenols of relative aldehydes, be not particularly limited, for example can be by in being dissolved in the scope of aqueous medium, increasing the adding mol ratio that aldehydes reduces the phenols of relative aldehydes, if but the service efficiency of consideration raw material, the then preferred adding mol ratio of the phenols of aldehydes relatively is more than 0.1.
In this operation, aforesaid aldehydes and phenols are reacted in aqueous medium, but one of feature of manufacture method of the present invention is to use an acidic catalyst of high density to carry out this reaction.This an acidic catalyst is preferably highly acid catalyzer.As such catalyzer, can exemplify out hydrochloric acid, phosphoric acid, sulfuric acid etc.Wherein, if consider the easy degree remove or the side reaction when residual, more preferably hydrochloric acid then.In addition, the purposes that the strong acid of non-volatility such as phosphoric acid or sulfuric acid also can corresponding granular phenol resin is used fully.In addition, " high density " specifically is meant under near the situation that begins the normal temperature to react, and the volumetric molar concentration of an acidic catalyst in the reaction solution is more than the 2.0mol/L, more preferably more than the 3mol/L.Using under the situation of hydrochloric acid as an acidic catalyst, " volumetric molar concentration of the hydrochloric acid in the reaction solution " is meant the concentration of the hydrogenchloride in the reaction solution.Median size is little in order to obtain, 2 agglutinative granular phenol resins of inhibition, and then for obtain in addition, more near spherical shape, narrow diameter distribution, the poor granular phenol resin of free phenol, under near the situation that begins the normal temperature to react, the volumetric molar concentration that must make an acidic catalyst in the reaction solution is more than the 2.0mol/L.In addition, from being suitable for the acid proof viewpoint of industrial speed of response and attendant equipment, the volumetric molar concentration of an acidic catalyst is preferably below the 6mol/L.In addition, be higher than normal temperature, and some to be lower than reaction beginning temperature be near the normal temperature situation for the volumetric molar concentration that realizes the necessary an acidic catalyst of equivalent responses speed becomes by the beginning temperature that makes reaction.
Another of manufacture method of the present invention is characterised in that, carries out the reaction of aldehydes and phenols in the presence of colloid protective agent.At this, colloid protective agent is the material that helps to form granulous resol.For form median size little, suppressed the agglutinative granular phenol resin 2 times, and then for form in addition, more near spherical shape, narrow diameter distribution, the poor granular phenol resin of free phenol, essentially use such colloid protective agent.In the present invention, preferably use water miscible colloid protective agent as colloid protective agent.As water-soluble colloid protective material, for example can use water miscible polysaccharide derivatives well.If enumerate the concrete example of the water miscible polysaccharide derivatives that can use well, then comprise the alkali metal salts or ammonium salt of carboxymethyl cellulose; It with gum arabic (gum arabic), gum arabic (acacia), guar gum (guar gum), carob bean gum water-soluble polysaccharide analog derivatives such as (locust bean gum) natural paste of main component etc.Under the situation of the alkali metal salts or ammonium salt that uses carboxymethyl cellulose, cellulosic carboxymethylation degree is not particularly limited, the fiber of carboxymethylation degree about 75% have sale, can use well.In addition, obtaining as dried powder under the situation of colloid protective agent, it directly can added in reaction solution, dissolves, perhaps, also can prepare the aqueous solution of colloid protective agent in advance, it is being added in reaction solution.
Usage quantity to described colloid protective agent is not particularly limited, and with the solids component Mass Calculation, is preferably 0.01～3 weight % of the usage quantity of described phenols.Under the situation of usage quantity less than 0.01 weight % of colloid protective agent, deficiency is so that the median size of resol particle is below the 20 μ m, for example also must utilize other parameters such as phenols usage quantity or stirring velocity to come control size.For the median size that makes the resol particle is below the 10 μ m, the usage quantity of colloid protective agent is preferably more than the 0.04 weight % of usage quantity of phenols.In addition, under the situation of usage quantity more than 3 weight % of the usage quantity of phenols of colloid protective agent, because the viscosity of reaction solution rises, in separating, washing operation described later, the trend that exists velocity of separation to reduce should be noted that.At this; the point that is worth specifying is; in colloid protective agent is described scope, be under the situation of 0.02～1 weight % of usage quantity of phenols especially in the usage quantity of colloid protective agent, can control the median size of resol particle by the usage quantity of adjusting colloid protective agent.
As described aqueous medium, can enumerate the mixed solvent of water or water and water-miscible organic solvent, and in the present invention, preferably use water solvent.The concentration that preferably usage quantity of aqueous medium is chosen to an acidic catalyst becomes in the described scope, and then the concentration that preferably usage quantity of aqueous medium is chosen to phenols becomes in the described preferable range.
Then, the concrete grammar that is used to use described aldehydes, phenols, an acidic catalyst and colloid protective agent to react is narrated.As the concrete grammar of reaction, can enumerate 2 following methods.(i) in aqueous medium, mix an acidic catalyst, colloid protective agent and aldehydes and prepare mixed solution, the method that stirs this mixed solution then and add phenols simultaneously; (ii) colloid mixture protective material, aldehydes and phenols and prepare mixed solution in aqueous medium, the method that stirs this mixed solution then and add an acidic catalyst simultaneously.
At this, in described (i) and (ii) any means, all preferred described mixed solution is the solution of homogeneous roughly.That is, preferably in aqueous medium the blended solute fully dissolve or at least almost entirely the dissolving.In the preparation of mixed solution, the blended order is not particularly limited.In addition, the temperature the when reaction of this mixed solution is begun is not particularly limited, and is preferably about 10～50 ℃, and then is preferably about 20～40 ℃.
In described (i) method, stir described mixed solution limit by the limit and add phenols, carry out the reaction of aldehydes and phenols.The interpolation of phenols can be undertaken by directly add phenols in mixed solution, perhaps also can in advance phenols be dissolved in the water, and adds this aqueous solution again in mixed solution.The temperature of reaction of this reaction preferably is controlled to about 10～60 ℃, more preferably about 20～50 ℃.Temperature of reaction less than about 10 ℃ situation under, thickization of particle diameter or the increase of 2 agglutinators if temperature of reaction surpasses 60 ℃, then may take place in the trend that exists speed of response to diminish.In addition, temperature when beginning by the reaction that makes described mixed solution is near the normal temperature about 20～30 ℃, the concentration of the phenols of relative response liquid gross weight is below the 10 weight %, owing to do not follow the over-drastic heating, so carry out temperature treatment hardly, can react in described preferred temperature range.
In described (ii) method, stir described mixed solution limit by the limit and add an acidic catalyst, carry out the reaction of aldehydes and phenols.The interpolation of an acidic catalyst can once be carried out, and perhaps also can instil with the regular hour and carry out.In addition, the interpolation of an acidic catalyst can be undertaken (for example using under the situation of hydrochloric acid as an acidic catalyst, also can directly adding concentrated hydrochloric acid by directly add an acidic catalyst in mixed solution.), perhaps also can dilute with water an acidic catalyst (for example concentrated hydrochloric acid), in mixed solution, add this diluent and carry out.Temperature of reaction is identical with the situation of described (i), preferably is controlled to about 10～60 ℃, more preferably about 20～50 ℃.
In described (i) and any means (ii), along with the reaction progress, reaction solution is gonorrhoeaization (suspensionization) little by little, thereby forms granular phenol resin, but such gonorrhoeaization is typically in tens of second after the interpolation of phenols or an acidic catalyst～take place after several minutes.Gonorrhoeaization is to have the (ii) method trend shorter than (i) method the needed time of separating out of resol particle.In addition, after the gonorrhoeaization, reaction solution typically presents lightpink～deep pink, in the present invention, preferred continues reaction until visible so painted.Present time till the gonorrhoea after stain probably for about tens of minutes～a few hours.In addition; in the method for in described patent documentation 1, putting down in writing; become pie for fear of particle assembly; must after separating out, the resol particle stop to stir; if but utilize to use the manufacture method of the present invention of colloid protective agent, even then after the separating out of resol particle, also could continue to stir.Thereby, if utilize manufacture method of the present invention, then can control the temperature of reaction solution more closely, and then can be under the state of homogeneous also in the polymerization degree and the degree of crosslinking of resol, be provided to next non-thermofusible operation.This can help the uniformity of the granular phenol resin that finally obtains.
(2) non-hot melt operation
In this operation, contain the reaction solution of described granular phenol resin by heating, make this granular phenol resin become non-thermofusible.The resin that such non-thermofusible also can cause by heating crosslinked, solidify and obtain.The Heating temperature of the reaction solution in this operation is preferably more than 60 ℃, more preferably more than 70 ℃.In addition, the Heating temperature of reaction solution is preferably below 100 ℃, more preferably below 90 ℃.Heating temperature less than 60 ℃ situation under, may not obtain enough non-thermofusibles.Wherein, enough non-thermofusibles described herein are meant " non-thermofusible " with above-mentioned definition.In addition, under Heating temperature surpassed 100 ℃ situation, the acid resistance that must have the reactor of condenser (condenser) or attendant equipment etc. sometimes became problem.In addition, even lower in Heating temperature, to about 60 ℃ situation, also can give enough non-thermofusibles by enough hold-times are set.By with Heating temperature and be adjusted to described preferable range heat-up time, can corresponding purposes be adjusted to the ideal polymerization degree and degree of crosslinking.
As long as can give enough non-thermofusibles heat-up time to granular phenol resin, be not particularly limited, though different and different according to Heating temperature, typically be several minutes～about a few hours.In addition, finish the back in this heat treated, when next operation advances, reaction solution can be cooled to suitable temperature, perhaps also can not cool off reaction solution and directly enter next operation.
(3) separating, washing operation
In this operation, from the non-thermofusible granular phenol resin that reaction solution separates and washing obtains.As separation method, for example can use filtration or squeezing etc. well.As the device that is used to carry out such lock out operation, for example can use filtration unit, centrifuge, belt press (belt press), pressure filter (filter press) etc.Decompression is heated up in a steamer, the separation method of spray-dryer utilizations such as (spray dryer) evaporation contains an acidic catalyst of high density and may damage machine owing to reaction solution.When utilizing filtering lock out operation, also can use various flocculating aidss or agglutinants such as diatomite.Wherein, the proportion of granular phenol resin of the present invention is about 1.2～1.3, carries out sedimentation owing to utilize to leave standstill, so also can carry out decant preparatory functions such as (decantation) before this lock out operation.
Then, wash isolating granular phenol resin.Utilize this washing operation, reaction almost completely finishes.Concrete grammar as washing, for example can enumerate (i) adds washings in utilizing the isolating resol filter cake of described lock out operation method (for example inject washings in the resol filter cake on isolating filter, utilize pressurization or decompression to remove washings etc.); Isolating resol filter cake is disperseed in washings, and then carry out the method for lock out operation.As washings, can make water well.By washing with water, can remove the acidic component in the resol filter cake.
In addition,, perhaps replace the described washing operation that utilizes water, it is contacted with the aqueous solution that is alkalescence carry out neutralization reaction as the part of washing operation.By carrying out neutralization reaction, can remove an acidic catalyst composition that contains in the resol filter cake effectively.As the aqueous solution that is alkalescence that in neutralization reaction, uses, preferably use the weak alkaline aqueous solution of organic or inorganic.If use alkaline concentrated aqueous solutions, then the resol particle may variable color or dissolving.As weak alkaline aqueous solution, for example can use the dilute aqueous soln of ammonia well.This is because under the situation of the dilute aqueous soln that uses ammonia, because the salt that generates is water-soluble, so may utilize washing to remove this salt, ammonia self can utilize heating sublimation to remove.
At this, the chlorion that permeates in the granular phenol resin in order to utilize reaction, extraction to be separated in preferably uses the isolating granular phenol resin of alcohols and/or alkaline aqueous solution washing.In order to carry out the extracting and separating of chlorion effectively, also can and be used to wash out the washing that utilizes water of the reaction solution on aforesaid resol surface, or with in the alkaline aqueous solution with the operation of the chlorion on resol surface.
As the cleaning solvent (washings medium) that uses for the extracting and separating chlorion, can be any one of alcohols, basic solution, also can use both sides.Utilize the washing of alcohols and/or alkaline aqueous solution, can reduce the chloride ion content in the non-thermofusible granular phenol resin effectively.Particularly, can make the cl content in the non-thermofusible granular phenol resin is below the 500ppm, and then it is following or lower also can to make it become 100ppm.
At this, the point that be worth to specify is, the chloride ion content that can utilize the washing of this alcohols and/or alkaline aqueous solution to reduce in the non-thermofusible granular phenol resin is because the median size of non-thermofusible granular phenol resin is enough small, simple grain rate height.That is, under the situation that median size is big or the simple grain rate is low of non-thermofusible granular phenol resin,, also be difficult to realize the minimizing of cl content even utilize the washing of alcohols and/or alkaline aqueous solution.Thereby even from this point, in the present invention, the median size that also needs non-thermofusible granular phenol resin is below the 20 μ m, and the simple grain rate is more than 0.7.
As the preference of the concrete grammar of the washing that utilizes alcohols and/or alkaline aqueous solution, can enumerate and make that isolating non-thermofusible granular phenol resin is scattered in this cleaning solvent (washings solvent) from reaction solution, stir the method for certain hour.As mentioned above, utilizing before alcohols and/or alkaline aqueous solution wash, also can make preparation washing isolating non-thermofusible granular phenol resins from reaction solution such as water in advance.As the method for preparation washing, can enumerate isolating non-thermofusible granular phenol resin for example is scattered in the fluidity medium such as water, stirring method under normal temperature～less than 100 ℃ temperature.The preparation washing is more preferably used and is added hot water.But, although can utilize this preparation washing to realize the minimizing to a certain degree of cl content, but can not only utilize this preparation washing to become below the 500ppm, perhaps need extremely long-time in order to become below the 500ppm, so, preferably utilize the washing of alcohols and/or alkaline aqueous solution in order to reduce cl content fully.
As alcohols, be not particularly limited, for example can enumerate methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, ethylene glycol, diethylene glycol, triglycol, propylene glycol etc.As described later, the second-order transition temperature of the non-thermofusible granular phenol resin among the present invention is about about 80～200 ℃, if utilize the extracting operation of alcohols in the zone that surpasses this temperature, then rate of extraction improves significantly.Using lower boiling alcohols under the situation of the extraction of carrying out chlorine component under this preferred temperature province, the essential pressure kettle etc. that uses.In addition, under the situation of using high boiling alcohols, can under normal pressure, carry out described extracting operation under preferred temperature province, but the drying operation after the washing (extraction) may become hard to tackle.If consider this point, then in illustrative alcohols, the balance of the boiling point of the second-order transition temperature of the relative non-thermofusible resol of ethylene glycol is good, and washing (extraction) operation and drying operation are easy, so can preferably use.In addition, alcohols can only use a kind, and also two or more kinds may be used.
Usage quantity to alcohols is not particularly limited, and for example can be preferably more than 200 weight parts relatively from solids component 100 weight parts of the isolating non-thermofusible granular phenol resin of reaction solution.
Wash temperature in the carrying out washing treatment of use alcohols is preferably more than the second-order transition temperature of non-thermofusible granular phenol resin, more preferably surpasses the temperature of second-order transition temperature.By washing with the temperature more than the second-order transition temperature, non-thermofusible granular phenol resin becomes rubbery state, so the chlorine component (especially chlorion) that can contain in this granular phenol resin of extraction in alcohols effectively.The upper limit to wash temperature is not particularly limited, and for fear of the thermolysis of non-thermofusible granular phenol resin and alcohols, is preferably below 250 ℃.In addition, the second-order transition temperature of the non-thermofusible granular phenol resin among the present invention is generally about 80～200 ℃.
Pressure condition when utilizing alcohols to wash is not particularly limited, and can or add to depress under normal pressure and wash.For example,, become more than the second-order transition temperature of non-thermofusible granular phenol resin, can wash adding to depress in order to make wash temperature using under the situation of more lower boiling alcohols.In addition, be that the churning time of non-thermofusible granular phenol resin dispersion liquid is not particularly limited to washing time, for example can be several minutes～tens of hours.
The washing of described use alcohols can only be carried out 1 time, perhaps in order to become the cl content that needs, also can carry out repeatedly repeatedly.
Alkaline aqueous solution as in the washing of using alkaline aqueous solution is not particularly limited, and is preferably weak alkaline aqueous solution.If use alkaline concentrated aqueous solutions, then the resol particle might variable color or dissolving.In addition, the hydroxide aqueous solution of basic metal or alkaline-earth metal is except above-mentioned, and ion component is non-volatile, even utilize the drying operation after the washing, and also might be residual.As weak alkaline aqueous solution, for example can use ammonia soln, pyridine solution, dimethylamine agueous solution etc. well.Especially ammonia soln is because chlorion is removed the ability height, so more preferably.Ammonia concentration to ammonia soln is not particularly limited, and is preferably the concentration～30 weight % that surpass 0.5 weight %, more preferably 1～25 weight %.Under ammonia concentration is situation below the 0.5 weight %, the chlorion in the extraction granular phenol resin in ammonia soln effectively.In addition, if ammonia concentration surpasses 30 weight %, then the resol particle might variable color or dissolving.In addition, if ammonia concentration surpasses 30 weight %, then because the vapour pressure height, though and different and different according to wash temperature (extraction temperature), the maybe essential pressure kettle that uses of essential condenser.
Usage quantity to alkaline aqueous solution is not particularly limited, and depends on the concentration of the alkaline matter that contains, and for example solids component 100 weight parts of isolating non-thermofusible granular phenol resin from reaction solution relatively become more than 200 weight parts.
Wash temperature in the carrying out washing treatment of using alkaline aqueous solution is not particularly limited,, also can from non-thermofusible granular phenol resin, removes chlorion effectively even be temperature less than the second-order transition temperature of non-thermofusible granular phenol resin.Certainly, also can under the temperature more than the second-order transition temperature of non-thermofusible granular phenol resin, wash.By under the temperature more than the second-order transition temperature, washing, can extract chlorine component more effectively, in short time mostly.At high temperature use under the situation of washing of ammonia soln, preferably use pressure kettle etc.The upper limit to wash temperature is not particularly limited, but for fear of the thermolysis of non-thermofusible granular phenol resin, is preferably below 250 ℃.More preferably below 100 ℃.
Pressure condition when utilizing alkaline aqueous solution to wash is not particularly limited, and can or add to depress under normal pressure and wash.In addition, be that the churning time of non-thermofusible granular phenol resin dispersion liquid is not particularly limited to washing time, for example can be several minutes～tens of hours.
The washing of described use alkaline aqueous solution can only be carried out 1 time, perhaps in order to become the cl content that needs, also can repeat repeatedly.
In the present invention, in order to reduce cl content fully, preferably use the both sides of alcohols and alkaline aqueous solution to wash non-thermofusible granular phenol resin.At this, " using the both sides of alcohols and alkaline aqueous solution " comprises i) use the mixed solution of alcohols and alkaline aqueous solution as cleaning solvent; Ii) after using the alcohols washing, use alkaline aqueous solution to wash; And, use alcohols to wash iii) using after alkaline aqueous solution washs.Wherein, preferably ii) reach iii) method, owing to can reduce cl content fully, can also remove the employed alkaline matter that derives from alkaline aqueous solution simultaneously, so more preferably iii) method.
In the present invention, preferably after the described washing that utilizes alcohols and/or alkaline aqueous solution, the operation (after scouring operation) that use and alcohols, the different fluidity medium of alkaline aqueous solution wash is set.This fluidity medium does not preferably contain ionic impurity in fact, as such fluidity medium, for example can enumerate pure water, ion exchanged water etc.Utilize this after scouring, the salt that can remove the alcohols that is attached on the non-thermofusible granular phenol resin, alkaline aqueous solution, generates because of the neutralization reaction of alkaline aqueous solution and an acidic catalyst etc.Wherein, after the washing of having used alcohols and/or alkaline aqueous solution or the solid-liquid separation of granular phenol resin after the after scouring operation and washings can similarly carry out with described separation circuit.
Can not make the granular phenol resin that washed dry and use under the state that contains the fluidity medium, such non-thermofusible granular phenol resin that contains the fluidity medium also belongs to scope of the present invention.The granular phenol resin that for example contains water can be in the inferior use of situation of preparation aqueous dispersions.Perhaps, also drying process can be set after washing procedure.As under the situation of organic filler, preferably carry out drying.As the exsiccant method, be not particularly limited, for example can enumerate the method for the standing and drying machine that uses the canopy type, pneumatic drier, fluid bed dryer etc.By carrying out drying, can obtain fluidity medium containing ratio and be about the non-thermofusible granular phenol resin powder that good flowability is shown below 5%.If utilize method of the present invention, then can obtain the granular phenol resin of high simple grain rate by carrying out slight fragmentation as required, but also can be when described drying process or use crusher etc. further to improve the simple grain rate afterwards.
If utilize the manufacture method of aforesaid non-thermofusible granular phenol resin of the present invention, then can utilize easier method and utilization be suitable for mass-produced method make median size be 20 μ m following, be preferably that 10 μ m are following especially, the simple grain rate is 0.7 or more, preferably cl content is the non-thermofusible granular phenol resin below the 500ppm.In addition, if utilize manufacture method of the present invention, then can make possess these characteristics simultaneously narrow diameter distribution, particle be spherical shape, the considerably less non-thermofusible granular phenol resin of free phenol content, and then can also to make chloride ion content be below the 100ppm.Non-thermofusible granular phenol resin of the present invention so for example can use in semiconductor applications well.
＜compositions of thermosetting resin 〉
Compositions of thermosetting resin of the present invention contains described non-thermofusible granular phenol resin of the present invention, Resins, epoxy and solidifying agent.The preferred cl content of non-thermofusible granular phenol resin is below the 500ppm.Because this compositions of thermosetting resin contains the especially non-thermofusible granular phenol resin of the present invention that reduced of amount of chloride ions of chlorine component, so can give high heat resistance that resol has, mechanical property etc., can be used as sealing material for semiconductor and adhesive for semiconductor well.At this, the high heat resistance of compositions of thermosetting resin not only results from the high heat resistance that non-thermofusible granular phenol resin himself is had, and forms complex body but also result from non-thermofusible granular phenol resin and Resins, epoxy.That is, utilize the reaction of the glycidyl of the hydroxyl of the phenol skeleton that non-thermofusible granular phenol resin has and Resins, epoxy, non-thermofusible granular phenol resin and Resins, epoxy form tough complex body.Utilize the formation of this complex body, the intensity at the interface of non-thermofusible granular phenol resin and Resins, epoxy increases, so compositions of thermosetting resin of the present invention has excellent heat resistance.In addition, the difference of the linear expansivity of non-thermofusible granular phenol resin and Resins, epoxy is little also is a reason of high heat resistance.
In compositions of thermosetting resin of the present invention, use level as the non-thermofusible granular phenol resin of organic filler is not particularly limited, for example use under the situation of Resins, epoxy as adhesive resin, total amount 100 weight parts of this Resins, epoxy and its solidifying agent can be 20～900 weight parts relatively.Under the situation as sealing material for semiconductor or adhesive for semiconductor, total amount 100 weight parts of this Resins, epoxy and its solidifying agent are preferably 60～500 weight parts, more preferably 300～400 weight parts relatively.At total amount 100 weight parts of relative this Resins, epoxy of use level and its solidifying agent, under situation, exist to be difficult to obtain stable on heating trend of giving effect less than 20 weight parts.In addition, if use level surpasses 900 weight parts,,, be defined to the not purposes of essential compactness mostly so be difficult to obtain fine and close tissue then because the resol powder is a non-thermofusible.In addition, if total amount 100 weight parts of this Resins, epoxy and its solidifying agent add the non-thermofusible granular phenol resin of the amount that surpasses 500 weight parts relatively, then can not obtain good flowability as sealing material for semiconductor or adhesive for semiconductor sometimes.
As Resins, epoxy, can use known in the past Resins, epoxy, for example can use the Resins, epoxy of the glycidyl ether type of phenol well.If enumerate concrete example, bisphenol A-type (or AD type for example then, the S type, the F type) glycidyl ether, the glycidyl ether of hydrogenation bisphenol A-type, oxyethane adds the glycidyl ether of adult bisphenol A-type, propylene oxide adds the glycidyl ether of adult bisphenol A-type, the glycidyl ether of phenol novolac resin, the glycidyl ether of cresols novolac resin, the glycidyl ether of bisphenol-A phenolic varnish resin, the glycidyl ether of naphthalene resin, the glycidyl ether of 3 functional-type (or 4 functional-type), the glycidyl ether of Dicyclopentadiene (DCPD) resol, the glycidic ester of dimeracid, the glycidyl amine of 3 functional-type (or 4 functional-type), the glycidyl amine of naphthalene resin etc.They may be used alone, can also be used in combination two or more.
Solidifying agent is the material that adds in order to make described epoxy resin cure.As hardener for epoxy resin, be not particularly limited, can use known in the past hardener for epoxy resin.If enumerate concrete example, then for example phenol system compound, fatty amine, cycloaliphatic amines, aromatic series polyamine, polymeric amide, aliphatic anhydride, alicyclic acid anhydrides, aromatic anhydride, Dyhard RU 100, organic acid dihydrazide, boron trifluoride amine complex, imidazoles, tertiary amine etc.
Use level to solidifying agent is not particularly limited, and can be normally used scope in this field, and for example relative Resins, epoxy 100 weight parts can be 5～200 weight parts.Wherein, solidifying agent adds the weight of the epoxy equivalent (weight) that is equivalent to Resins, epoxy usually, but in the present invention, preferably adds some weight that are equivalent to epoxy equivalent (weight) that are less than.This be because, as mentioned above because non-thermofusible granular phenol resin of the present invention is at its surface or the Racemic glycidol radical reaction of its near surface and epoxy group(ing), so if add the solidifying agent that epoxy equivalent (weight) divides, the solidifying agent surplus that becomes then.Reduction or leakage detrimentally affects such as (bleed) that superfluous solidifying agent can bring hot rerum natura.Because the amount that should reduce depends on the kind of Resins, epoxy, the use level of non-thermofusible granular phenol resin, the kind of solidifying agent etc., thus cannot treat different things as the same, but can become the epoxy equivalent (weight) that is equivalent to Resins, epoxy weight about about 5～10%.
Compositions of thermosetting resin of the present invention also can further contain curing catalyst.As curing catalyst, can use known in the past curing catalyst, for example can enumerate imidazoles, cyanoguanidine derivative, dicarboxyl acid dihydrazide, triphenylphosphine, tetraphenylphosphoniphenolate tetraphenyl boric acid ester, 2-ethyl-4-methylimidazole-tetraphenyl boric acid ester, 1,8-diazabicyclo [5.4.0] undecylene-7-tetraphenyl boric acid ester etc.Use level to curing catalyst is not particularly limited, and for example relative Resins, epoxy 100 weight parts can be 0～30 weight part.
Compositions of thermosetting resin of the present invention also can contain above-mentioned other additives in addition.As other additives, for example can enumerate defoamer, flow agent, tinting material, thinner (organic solvent etc.), viscosity modifier, tensio-active agent, photostabilizer, antioxidant, flame retardant, thermoplastic resin, Resins, epoxy thermosetting resin in addition etc.In addition, compositions of thermosetting resin of the present invention also can further contain non-thermofusible granular phenol resin of the present invention other organic fillers or mineral filler in addition.As other organic fillers, for example can enumerate carbon, rubber is filler (acrylonitrile butadiene rubber filler, silicone rubber filler etc.) etc.In addition, as mineral filler, can enumerate metallic stuffings such as silver powder, bronze, copper powder, nickel powder; Silicon-dioxide (fused silica, broken silicon-dioxide, aerosil (fumed silica) etc.), aluminum oxide, boron nitride, titanium oxide, glass, ferric oxide, pottery, Calucium Silicate powder, mica etc.
Compositions of thermosetting resin of the present invention can be by using three-roller open mill (triple rollmill), ball mill (ball mill) etc., and mixing, mixing non-thermofusible granular phenol resin, Resins, epoxy, solidifying agent and other additives that add as required obtain.
In addition, with compositions of thermosetting resin of the present invention as under the situation of adhesive for semiconductor, the operability raisings when realizing that semi-conductor is made etc. also preferably are shaped as film like with compositions of thermosetting resin.As the method for making adhesive film, for example can enumerate the layer of coating compositions of thermosetting resin formation resin combination on base material, make its drying, remove the method for base material then.Drying temperature is not particularly limited, for example can be about 50～200 ℃.
＜granular carbon electrode material 〉
Utilize the present invention, can provide that a kind of to have very small particle diameter, narrow diameter distribution and contain 2 agglutinators that the aggegation of this small progenitor produces hardly be the high granular carbon electrode material of simple grain rate.Granular carbon electrode material of the present invention like this can be realized the raising of the electrostatic capacitance and the power density of per unit area, can be used as electric double layer capacitor, lithium ion battery and lithium-ion capacitor electrode materials well.
Lithium ion battery is used as negative pole with carbonaceous material usually, and lithium-containing compound as anodal, is moved between positive pole and negative pole by making lithium ion, discharges and recharges.In addition, electric double layer capacitor uses the bigger carbonaceous material of specific area as positive pole and negative pole, utilizes the absorption of electrolyte ion, desorption to discharge and recharge.Recently the lithium-ion capacitor that proposes use with the bigger carbonaceous material of the same specific area of common electrical condenser as positive pole, negative pole uses and the same carbonaceous material of lithium ion battery.Lithium-ion capacitor utilizes the absorption of lithium ion and electrolyte ion, desorption to discharge and recharge, as the novel electrical condenser of the energy density of having improved electric double layer capacitor and receive publicity.
These lithium ion batteries are in order to make the further high performance of electric double layer capacitor and lithium-ion capacitor, are that the exploitation of the high carbon electrode material of the electrostatic capacitance of per unit area and power density is indispensable to the carbon electrode material of high performance.Past, in order to obtain the carbon electrode material of such high performance, carried out various discussions, for the fillibility that improves per unit area or in order to improve the contact interface area with electrolytic solution, the little granular carbon material of particle diameter has been proposed.But, all having enough space fillibilities hardly, thereby, in order to obtain the more lithium ion battery of high performance, must further improve carbon electrode material.
Granular carbon electrode material of the present invention is characterised in that median size is below the 10 μ m, and the simple grain rate is more than 0.7, and is below 0.65 by the coefficient of variation of the size distribution of described formula [1] expression.The degree of sphericity of carbon electrode material particle is preferably more than 0.5.In addition, utilize the present invention, a kind of granular carbon electrode material mixture that the different granular carbon electrode material of the present invention more than 2 kinds of median size forms that mixes can be provided.
Below granular carbon electrode material of the present invention is elaborated.(term as relative 2 agglutinators is also referred to as progenitor to the particle of granular carbon electrode material of the present invention.) median size be below the 10 μ m.By making median size is below the 10 μ m, and it is big that the outer surface area of carbon particles becomes.Like this, lithium ion or the electrolyte ion intrusion frequency in carbon particles increases, and the diffusion length of these ions in granular carbon electrode material inside also shortens, so this ionic turnover when discharging and recharging accelerates, the result can improve power density.In addition, as described later,, the tamped density of carbon electrode material can be improved, like this, the electrostatic capacitance of per unit area can be increased by with littler carbon electrode material of suitable ratio combination average particle diameter and bigger carbon electrode material.Lower value to median size is not particularly limited, if too small, then when the non-thermofusible resol particle that the raw material of making as granular carbon electrode material of the present invention preferably uses, the solid-liquid separation difficulty that becomes sometimes.In addition, if median size is too small, then using this granular carbon electrode material preparation slip, it is coated with on current collector, thereby when making the coating electrode, cause of the reduction of this slip sometimes, thereby the reduction of visible surface covered based on the flowability of swelling property (dilatancy).Thereby from such viewpoint, the median size of granular carbon electrode material is preferably 0.5 μ m, more preferably more than the 1 μ m.
At this, the meaning of " median size " of granular carbon electrode material is identical with " median size " at granular phenol resin of above-mentioned definition.
In addition, granular carbon electrode material of the present invention has narrow size distribution, and particularly, the coefficient of variation of size distribution that constitutes the particle (progenitor) of granular carbon electrode material of the present invention is below 0.65.The coefficient of variation of size distribution and then be preferably below 0.6.At this, the meaning of " coefficient of variation of size distribution " is identical with " coefficient of variation of size distribution " at granular phenol resin of above-mentioned definition,, is the value of utilizing described formula [1] to calculate that is.
As mentioned above, by with littler carbon electrode material of suitable ratio combination average particle diameter and bigger carbon electrode material, can improve the tamped density of carbon electrode material, if but the size distribution of these granular carbon electrode materials wide (coefficient of variation surpasses 0.65), then be difficult to obtain sufficiently high tamped density, thereby, be not enough to improve electrostatic capacitance.
In addition, the simple grain rate of granular carbon electrode material of the present invention is more than 0.7, to be preferably more than 0.8.If less than 0.7, there is agglutinator 2 times in the simple grain rate morely, then generate the gap of progenitor, tamped density reduces.Thereby especially under the situation of mixing the different carbon electrode material raising tamped density of median size, be difficult in the gap of progenitor, fill the littler carbon electrode material of median size owing to become, so not only can not improve tamped density, also have the trend of the flowability reduction of this slip when using electrolytic solution pulp carbon electrode material on the contrary.At this, the meaning of " the simple grain rate " of granular carbon electrode material is identical with " the simple grain rate " at granular phenol resin of above-mentioned definition.
Fig. 8 represents that the scanning electron microscope photo of a preference of granular carbon electrode material of the present invention is (hereinafter referred to as the SEM photo.)。As shown in Figure 8, granular carbon electrode material of the present invention is the small granular phenol resin of particle diameter, and 2 agglutinators that the aggegation of this particle (progenitor) produces are few, and narrow size distribution is shown.Wherein, the median size of the granular carbon electrode material of Fig. 8 is 4 μ m, and the simple grain rate is 0.98, and the coefficient of variation of size distribution is 0.51.
And then the particle shape of granular carbon electrode material of the present invention is good more near spherical shape more.Particularly, degree of sphericity is preferably more than 0.5, more preferably more than 0.7, is preferably more than 0.9 especially.Particle shape is more near spherical shape, and promptly degree of sphericity then can further improve the tamped density of granular carbon electrode material more near 1.0, can also further improve the flowability of this slip when using electrolytic solution pulp carbon electrode material simultaneously.At this, the meaning of " spherical shape " is identical with " spherical shape " at granular phenol resin of above-mentioned definition.
The specific area that the BET method of utilizing nitrogen absorption of granular carbon electrode material of the present invention is measured is not particularly limited, and under the situation of the negative material that is used as lithium ion battery or lithium-ion capacitor, is preferably 1～500m 2/ g, more preferably 1～200m 2/ g, and then be preferably 1～50m 2/ g.If specific area surpasses 500m 2/ g, the trend that then exists the ratio of the relative charging capacity of loading capacity to reduce.In addition, using under the situation of electrode materials as electric double layer capacitor, specific area is preferably 600～2300m 2/ g, more preferably 800～2000m 2/ g.At specific area less than 600m 2Under the situation of/g, the trend that exists electrolyte ion successfully not invade in pore is if surpass 2300m 2/ g then becomes the big pore beyond the pore that utilizes in the absorption that is created on electrolyte ion, the desorption, thereby exists the density of electrode materials to reduce the trend that can not guarantee enough electrostatic capacitances.
As the raw material of granular carbon electrode material of the present invention, get final product so long as can access carbon electrode material with described specific characteristic, be not particularly limited, can use known in the past raw material.As this raw material, can exemplify out thermosetting resins such as resol, melamine resin, urea resin, Resins, epoxy.Granular carbon electrode material of the present invention preferably obtains by the saccharoid that burns till (carbonization) and/or activate these resins.In above-mentioned resin, from the point of carbon residue rate, preferred resol, the above-mentioned non-thermofusible granular phenol resin of the present invention of preferred especially use.
Under with the situation of non-thermofusible granular phenol resin of the present invention as the raw material of granular carbon electrode material, it boils the dissolve with methanol degree preferably less than 30%, more preferably less than 20%.Basically the degree of sphericity and the simple grain rate of granular carbon electrode material controlled in the raw material composition in the time of can utilizing the granular phenol resin that becomes raw material to make or the adjustment of reaction conditions, but also can boil the dissolve with methanol degree less than 30% granular phenol resin, improve the degree of sphericity and the simple grain rate of the granular carbon electrode material that obtains by use.
And then the free phenol content that becomes the non-thermofusible granular phenol resin of raw material is preferably below the 500ppm.This free phenol content is more preferably below the 300ppm, and then is preferably below the 200ppm.By making free phenol content is below the 500ppm, can suppress or avoid following the generation of the fine crack that burns till or the reduction of carbon residue rate, in addition, the distribute granular carbon electrode material of sharp-pointed (sharp) of the pore diameter after can also obtaining activating.In addition, because free phenol is harmful to human body or environment,, can provide human body or the safe manufacture method of environment by using such granular phenol resin.
At this, granular carbon electrode material of the present invention is being used under the situation of electrode materials as electric double layer capacitor, lithium ion battery and lithium-ion capacitor, also can mix and use the different granular carbon electrode material more than 2 kinds of median size.If utilize manufacture method of the present invention described later, then the median size of granular carbon electrode material can be controlled to the value that needs, have median size that needs and the granular carbon electrode material that its size distribution is sharp-pointed, the simple grain rate is high so can provide.Wherein, the difference of the expression of " kind " in " more than 2 kinds " median size.Use the different granular carbon electrode material more than 2 kinds of median size by mixing, can between the bigger carbon electrode material of median size, enter the littler carbon electrode material of median size, so can improve the tamped density of carbon electrode material.Under the situation of mixing the different granular carbon electrode material more than 2 kinds of median size, its the suitableeest mixture ratio depends on the median size of these carbon electrode materials etc., so cannot treat different things as the same, the median sizes of preferred corresponding blended carbon electrode material etc., the electrostatic capacitance of suitably setting per unit area for becomes the highest.
Obtain under the situation of carbon electrode material mixture at the different granular carbon electrode material more than 2 kinds of mixing median size, at least a carbon electrode material composition must be carbon electrode material of the present invention.In order to obtain the effect that tamped density and power density improve effectively, preferred all carbon electrode material compositions are carbon electrode material of the present invention.That is, be below the 10 μ m by the median size that makes the whole carbon electrode material compositions of blended, can improve power density effectively as carbon electrode material mixture integral body.In addition, if the size distribution of each carbon electrode material composition is sharp-pointed, the space that the particle that then median size is bigger constitutes becomes roughly certain size is shown, become and to mix the Mixed Design of more small particle, so can improve fillibility easily as carbon electrode material mixture integral body with the suitable size that can bury this space.On the other hand, under the situation of the electrode materials composition that mixes the particle diameter wider distribution, the space that the particle that median size is bigger constitutes becomes and distributes with all size, but is difficult to make the more fine particle of the size-grade distribution with the space of burying such all size just.On the contrary, even can obtain having the electrode materials composition of the size distribution of such complexity, in order in meeting the space of each particle diameter, to accommodate all particles, essential special married operation, bad situation such as needs are long-time in the time of can mixing.In addition, from the viewpoint that fillibility improves, preferred all carbon electrode material compositions are near spherical shape (degree of sphericity is more than 0.5).
Then, the manufacture method to granular carbon electrode material describes.The manufacture method of granular carbon electrode material of the present invention shown below can be well with acting on the method for making described granular carbon electrode material of the present invention.If utilize method of the present invention, then can utilize the adjustment of the concentration of colloid protective agent to control the median size of the granular carbon electrode material that obtains.In addition,, then can implement Mechanical Crushing to the resol that becomes intermediate raw material and carbon electrode material if utilize the present invention, and obtain that median size is small, narrow diameter distribution and the high carbon electrode material of simple grain rate.
Operation (a)～(d) shown in below the manufacture method of granular carbon electrode material of the present invention comprises.
(a) by the volumetric molar concentration in reaction solution be an acidic catalyst more than the 2.0mol/L and colloid protective agent in the presence of, in aqueous medium, aldehydes and phenols are reacted, the granular phenol resin that forms granular phenol resin form operation,
(b) heating contains the reaction solution of described granular phenol resin, thereby the non-hot melt operation of the granular phenol resin of formation non-thermofusible,
(c) from reaction solution, separate the granular phenol resin of this non-thermofusible separation circuit,
(d) burn till the firing process of the granular phenol resin of this non-thermofusible.
Below each operation is elaborated, but for operation (a)～(c), because identical,, describe so omit a part with the manufacture method of described thermally melting granular phenol resin.
An acidic catalyst as in the granular phenol resin formation operation can preferably use highly acid catalyzer such as hydrochloric acid, phosphoric acid, sulfuric acid, more preferably hydrochloric acid.This is because because hydrochloric acid is volatile acid, can utilize drying operation easily to remove, so the oxidizing reaction of residual acid composition brings dysgenic situation seldom for the surface chemistry or the intensity of granular phenol resin.
Granular phenol resin forms the usage quantity of the colloid protective agent in the operation with the solids component Mass Calculation, be preferably about the 0.04 weight % of usage quantity of phenols more than.Under the situation of usage quantity less than 0.04 weight % of colloid protective agent, deficiency is so that the median size of granular carbon electrode material is 10 μ m, for example must utilize other parameters such as phenols usage quantity or stirring velocity to come control size.In addition, the upper limit of the usage quantity of colloid protective agent is not particularly limited, is preferably below the 3 weight % of usage quantity of phenols.Under situation, can not obtain median size and be the following granular carbon electrode materials of 10 μ m, and because the rising of the viscosity of reaction solution, the trend that in separation circuit described later etc., exists velocity of separation to reduce more than 3 weight %.
Also can after separation circuit, the operation of the isolating granular phenol resin of washing be set.Concrete grammar as washing, for example can enumerate (i) adds washings in utilizing the isolating resol filter cake of described lock out operation method (for example inject washings in the resol filter cake on isolating filter, utilize pressurization or decompression to remove washings etc.); (ii) in washings, disperse isolating resol filter cake, and then carry out the method for lock out operation.As washings, can make water well.Wash with water by making, can remove the acidic component in the resol filter cake.
In addition,, perhaps replace the described washing operation that utilizes water, it is contacted with the aqueous solution that is alkalescence carry out neutralization reaction as the part of washing operation.By carrying out neutralization reaction, can remove an acidic catalyst that is attached to the granular phenol resin surface effectively and become to grade.As the aqueous solution that is alkalescence that in neutralization reaction, uses, preferably use the weak alkaline aqueous solution of organic or inorganic.If use alkaline concentrated aqueous solutions, then the resol particle may variable color or dissolving.As weak alkaline aqueous solution, for example can use ammonia soln well.Under the situation of using ammonia soln, because the salt that generates is water-soluble, so can utilize washing to remove this salt.In addition, Wei Liang salt residue also can utilize heating sublimation to remove.
Typically, the coefficient of variation of the size distribution of the non-thermofusible granular phenol resin that obtains as described above is below 0.65, and the simple grain rate is more than 0.7.In addition,, can utilize the adjustment of the usage quantity of colloid protective agent, for example become the value that needs in the scope below the 20 μ m about median size.In addition, also utilize the firing process and/or the activation procedure of next operation, the median size what (typically being about 3 one-tenth) have been dwindled particle is so consider this point, the median size of essential control non-thermofusible granular phenol resin.The characteristic of granular carbon electrode material (median size, size distribution, simple grain rate etc.) is by the characteristic decision as the non-thermofusible granular phenol resin of intermediate raw material.If utilize method of the present invention, then the Characteristics Control of non-thermofusible granular phenol resin can be become suitable scope, so can obtain well having as electric double layer capacitor, lithium ion battery and lithium-ion capacitor granular carbon electrode material with the characteristic of electrode material ideal.In addition, if utilize described method, then can make the non-thermofusible granular phenol resin of free phenol content considerably less (500ppm is following).The granular carbon electrode material that uses such non-thermofusible granular phenol resin to obtain has sharp-pointed pore diameter and distributes.
Then, firing process is described.Non-thermofusible granular phenol resin burn till (carbonization) under the non-oxidizing atmosphere of rare gas elementes such as nitrogen, argon, helium, 500～2500 ℃, preferred 500～1200 ℃, more preferably carry out in 550～1000 ℃ the temperature range.After firing process, carry out under the situation of activation treatment, firing temperature is become about 900 ℃ can advance activation effectively when following, so preferred.As the device that burns till, for example can use known in the past devices such as electric furnace, external-heat gas furnace.
After firing process, then carry out activation treatment as required.The temperature of activation treatment is 500～1100 ℃, preferred 800～1000 ℃ and then preferred 850～950 ℃.Be higher than in the temperature of activation treatment under 1100 ℃ the situation, reduction of the carbon residue rate that the oxidation of oxidation, the carbon skeleton on carbon electrode material surface causes etc. takes place sometimes.In addition, be lower than under 500 ℃ the situation, do not utilizing the pore of activation treatment to form fully.
Activation treatment can be used oxygen, carbonic acid gas, water vapour or the mixed gas more than 2 kinds wherein, or contains the atmosphere gas such as nitrogen, argon, helium of these gases, combustion gases such as methane, propane, butane etc.Activation treatment preferably becomes activation makes the weight decrement of carbon material become 5～90%.In addition, be called as in formation under the situation of bigger pore of mesopore (mesopore), also can suitably add metals such as nickel, cobalt, iron or metallic compound and carry out activation treatment.And then, also can add the medicine activation of medicines such as potassium hydroxide, zinc chloride.
directly use non-thermofusible granular phenol resin through described operation (a)～(c) obtain to burn till and/or the situation of activation treatment under, the resol particle waits in firing furnace to be waved in the wind, it is discharged in company with waste gas, and therefore the reduction of yield, the reduction of operability take place sometimes.Under these circumstances, also can be before firing process progenitor be a granulated into have appropriateness intensity and the particle of size.In granulation,, can use coal tar, pitch, creosote, liquid phenolic resin, liquid melamine resin, polyvinyl alcohol, starch, crystallinity cellulose powder, methylcellulose gum etc. as tackiness agent.They may be used singly or in combination of two or more.
Granulation can be by making at mixing machines such as using kneader after non-thermofusible granular phenol resin and tackiness agent mix equably; use wet type extruding granulator, vertical tablets press, half dry type tablets press (semidry disc pellete), tablets press etc., form saccharoid and carry out.Be shaped and at room temperature carry out usually, but under pitch becomes to grade more situation, also can under heating, implement.Shape, size to the granulation thing are not particularly limited, and for example can become cylindric about diameter 0.5～5mm, long 1～10mm, spherical etc. about diameter 0.1～10mm.In addition, the raising of the operability during with mixing, shaping etc. is a purpose, for example also can add tensio-active agents such as ethylene glycol, polyethylene oxide, alkyl oxide, polyoxyethylene fatty acid ester, poly-ammonium carbonate salts, solidifying agent such as liquid thermosetting resin, the softening agent that pastes such as polyvinyl alcohol, extruding pelletization are used etc.The intensity of granulation thing for burn till and/or activation treatment during can keep shape to a certain extent and can broken intensity after these processing finish.Fragmentation for example can be used ball mill, vibration mill, go round and round a millstone (rotor mill), hammer crusher, jet mill pulverizer, crushers such as (jet mill).
＜molecular-sieve carbon 〉
If utilize the present invention, then can be provided in nitrogen generator unit, especially transformation absorption (PressureSwing Adsorption is designated hereinafter simply as PSA.) molecular-sieve carbon that uses well in the formula nitrogen generator unit.
In recent years,, developed transformation absorption (PSA method), be practical as the technology of nitrogen in the separation of air and oxygen.The PSA method is by sorbing materials such as filling molecular-sieve carbons in the adsorption tower more than 1 tower, be repeated periodically in the regeneration that adds the selective adsorption of depressing and the sorbing materials such as molecular-sieve carbon under decompression or normal pressure, the method for coming the special component in the separate raw materials gas.Think the gas delivery of molecular-sieve carbon can result from adsorbed material with the molecular diameter that approaches the pore diameter that molecular-sieve carbon has with have poor than the rate of adsorption of each adsorbed material in the specific combination of the adsorbed material of its little molecular diameter.
The PSA nitrogen generator unit that molecular-sieve carbon is used as the air separation of sorbent material is the normal temperature separate mode, because the usage quantity of nitrogen or the purity of its use, compare with the nitrogen generator unit of low temperature separation process mode, favourable aspect cost, be widely used industrial, and in order can more to use in the multi-usage, in addition, also in order to obtain more cheap nitrogen, need PSA nitrogen generator unit, the high performance of molecular-sieve carbon especially, various molecular-sieve carbons have been proposed in recent years.
But,, still reckon without the width of median size or its size distribution of carbon initial size at present although there is the look-ahead technique of the certain limit of having mentioned the carbon initial size that constitutes particulate molecular sieve carbon.
This be because, though think different and different, summarize to get up according to its size distribution, the density of aggregate of carbon progenitor with size distribution of wide region uprises easily, the performance of such character pair molecular-sieve carbon is favourable.In addition, the reason that can also enumerate is, the molecular-sieve carbon that is difficult to have a particle size range that is controlled at several μ m unit in industrial manufacturing is with resin raw material, globular resin raw material especially; And the spherical resin raw material that will have a particle size range that is controlled at several μ m unit is processed into particulate molecular sieve carbon about preferred particle diameter 0.5～5mm as sorbent material; Deng.In addition, the reason that can also enumerate is, as raw material, wait under the situation that reduces particle diameter at the big raw material of powder particle diameter, owing to particle diameter can not be controlled at several μ units, perhaps, promptly allow to utilize classification to wait and control size distribution, but it is the raw material of number μ units can not be classified into narrow size distribution, so narrow in the size distribution of the industrial particle diameter raw material that is difficult to make several μ units.
Utilize the present invention, the kryptol particle that can provide that particle diameter is small and have narrow particle size range is compared with molecular-sieve carbon in the past, significantly the molecular-sieve carbon of high efficiency as progenitor.
Promptly, molecular-sieve carbon of the present invention is to have a plurality of carbon progenitors three-dimensionally stack and the structure of zoariumization brokenly, the median size of this carbon progenitor is below the 10 μ m, and be below 0.65 by the coefficient of variation of the size distribution of the carbon progenitor of following formula [3] expression, particle volume density is the molecular-sieve carbon of 0.7～1.2g/cc.
The coefficient of variation of the size distribution of carbon progenitor=(standard deviation of carbon initial size)/(median size of carbon progenitor) [3]
Molecular-sieve carbon of the present invention is preferred: use oxygen, 25 ℃, 0.3MPa what add the per unit weight molecular-sieve carbon depressed when carrying out the absorption of single composition is 24～28mg/g from measuring the adsorptive capacity of beginning after 60 seconds, and, use nitrogen, 25 ℃, 0.3MPa what add the per unit weight molecular-sieve carbon depressed when carrying out single composition absorption is 0.5～5mg/g from measuring the adsorptive capacity of beginning after 10 seconds.In addition, the carbon progenitor is preferably spherical.
By will this molecular-sieve carbon of the present invention as sorbent material that for example nitrogen generator unit of the PSA mode of separating nitrogen is used from the gaseous mixture of oxygen such as air and nitrogen, can utilize the raising of the nitrogen recovery that the raising of nitrogen gas purity causes, realize the raising of the nitrogen generating capacity of per unit weight molecular-sieve carbon.
Below molecular-sieve carbon of the present invention is elaborated.Molecular-sieve carbon of the present invention typically uses binder constituents etc. raw material powder is formed, carrying out the molecular-sieve carbon that carbonization is fired into then, is to have a plurality of carbon progenitors granular carbonization shaping thing of stack and the internal structure that forms of zoariumization brokenly three-dimensionally.This coating of particles is not particularly limited, for example can be column, spherical even-granular such as cylindric.Under the situation that is cylindrical particle, its diameter and length (highly) are preferably respectively about 0.5～3mm, and under the situation that is granular particle, its diameter is preferably about 0.5～3mm.Wherein, the carbon progenitor is meant the small carbon particles of the formation particulate molecular sieve carbon that carbonization obtains as granular phenol resin powder of raw material powder etc.
The sorbent material that molecular-sieve carbon of the present invention can be used as the nitrogen generator unit of the PSA mode of separating nitrogen from the gaseous mixture of oxygen such as air and nitrogen, in addition, can also be in the middle use that separates of the various mixed gass such as purifying of the separating of the separation of perfluorocarbon (perf1uorocarbon), methane and carbonic acid gas, hydrogen.
The median size of carbon progenitor is below the 10 μ m, and is below 0.65 by the coefficient of variation of the size distribution of the carbon progenitor of above-mentioned formula [3] expression.The coefficient of variation of the size distribution of carbon progenitor is preferably below 0.6.
By the median size that makes the carbon progenitor is below the 10 μ m, can become the separation energy of the oxygen/nitrogen that keeps high and have the high oxygen adsorptive capacity and the molecular-sieve carbon of rate of adsorption simultaneously.Think this be because, form in the operation at pores such as carbonizations, the generating capacity of the thermolysis gas of each progenitor tails off, so the fine pore number that forms on carbon progenitor surface increases and particle diameter is little, so the velocity of diffusion of adsorbed gas to carbon progenitor inside accelerates.Therefore, for example under the situation of the sorbent material that is used as PSA formula nitrogen generator unit, can improve the nitrogen generating capacity of nitrogen recovery or per unit weight molecular-sieve carbon.Lower limit to median size is not particularly limited, if consider productivity, security on the industrial production, then is preferably more than the 0.5 μ m.In addition, the shape of carbon progenitor is as long as for granular, be not particularly limited, and when 500～1100 ℃ of following heating raws, in order to form the more pore of homogeneous, be preferably spherical.In the present invention, " spherical " may not be spherical shape, and for example cross-sectional shape also can be ellipticity etc.But, from form for the pore of homogeneous or industrial production on the production stability of shaping and raw material near the ball point that to be favourable point or the pore carbonization and other processes the thermolysis gas when forming further improve to the uniformity of the diffusion of outside, the shape of carbon progenitor is also good more near spherical shape more.
At this, in the present invention, " median size of carbon progenitor " is in the observation of scanning electron microscope (hereinafter referred to as SEM) photo, to molecular-sieve carbon surface and surface of fracture, select the visual field respectively randomly, when each visual field is at random selected to confirm as 100 carbon progenitors of globular, utilize the mean value of the particle diameter of these 200 carbon progenitors that the SEM photo measures.In addition, " standard deviation of carbon initial size " is the above-mentioned standard deviation that can confirm as the particle diameter of 200 carbon progenitors of globular.
Molecular-sieve carbon of the present invention is owing to the coefficient of variation of the size distribution of being represented by above-mentioned formula [3] is below 0.65 and the narrow carbon progenitor formation of size distribution, so compare with molecular-sieve carbon in the past, the separating power of the mixed gas of oxygen and nitrogen is outstanding.Think this be because, particle diameter narrow by the size distribution that makes the carbon progenitor, that reduce between each carbon progenitor is poor, forms in the operation at the isochronous pore of carbonized stock, the generating capacity of decomposition gas etc. becomes necessarily.Therefore, homogenized between each carbon progenitor at the inner pore that forms of carbon progenitor.Think also that in addition the degree of depth of the pore that the carbon progenitor is had by homogenization, roughly necessarily also is one of reason so the velocity of diffusion of adsorbed gas becomes between each carbon progenitor between each carbon progenitor.
In addition, the particle volume density of molecular-sieve carbon of the present invention is 0.7～1.2g/cc, is preferably 0.8～1.15g/cc.Particle volume density can be calculated from the volume and weight of particulate molecular sieve carbon.The carbon containing ratio of molecular-sieve carbon is preferably more than the 80 weight %, more preferably more than the 85 weight %.
It is the function of adsorb oxygen optionally the unstripped gas that constitutes of oxygen and nitrogen that molecular-sieve carbon of the present invention has from principal constituent.As its characterization of adsorption, use oxygen, 25 ℃, 0.3MPa (gauge pressure) add the per unit weight molecular-sieve carbon depressed when carrying out single composition absorption be preferably 24～28mg/g from measuring the adsorptive capacity of beginning after 60 seconds.That is, in an optimal way of the present invention, molecular-sieve carbon of the present invention illustrates hyperoxia adsorptive capacity (rate of adsorption).In addition, use nitrogen, 25 ℃, 0.3MPa (gauge pressure) add the per unit weight molecular-sieve carbon depressed when carrying out single composition absorption be preferably 0.5～5mg/g from measuring the adsorptive capacity of beginning after 10 seconds, 1.5～5mg/g more preferably.That is, in an optimal way of the present invention, molecular-sieve carbon of the present invention illustrates low nitrogen rate of adsorption.If the nitrogen adsorptive capacity in stage (for example between the several seconds) is many in the early stage, the trend that then exists the isolating separation accuracy of oxygen/nitrogen to reduce, and by reducing from measuring the adsorptive capacity of beginning after 10 seconds can suppress the reduction of such separation accuracy.Molecular-sieve carbon of the present invention and then preferred oxygen adsorptive capacity after described 60 seconds are that 24～28mg/g and the nitrogen adsorptive capacity after described 10 seconds are 0.5～5mg/g.
Molecular-sieve carbon of the present invention can carry out carbonization after the shaping raw material powder such as binder constituents and burns till and obtain by using.As raw material powder, as long as the median size of the carbon progenitor of formation molecular-sieve carbon and the coefficient of variation of size distribution can satisfy described scope, be not particularly limited, but preferably use the described non-thermofusible granular phenol resin of the present invention of having controlled the coefficient of variation of particle diameter and size distribution.
As raw material powder, under the situation of the granular phenol resin of use non-thermofusible, it boils the dissolve with methanol degree preferably less than 30%, more preferably less than 20%, and then preferably less than 10%.Boiling the dissolve with methanol degree also can be for more than 30%, but " non-thermofusible " in this case, is not shown sometimes.
In addition, as raw material powder, the also preferred granular phenol resin that uses thermally melting.In this case, it boils the dissolve with methanol degree preferably less than 50%." boiling the dissolve with methanol degree " can become 1 index of the degree of the thermally melting of understanding granular phenol resin.That is, exist " boiling the dissolve with methanol degree " low more, then the also low more trend of thermally melting.If boiling the dissolve with methanol degree becomes more than 30%, then under the effect of heating in use or pressurization, thermally melting is shown, particle may be out of shape or fuse, if become more than 50% but boil the dissolve with methanol degree, significant thermally melting then is shown, particles Deformation, fusion during owing to carbonization, and may be less than the pore obturation that form pore or formation in inside fully." boiling the dissolve with methanol degree " described herein is meant and boils the dissolve with methanol degree by above-mentioned formula [2] expression.
At this, the definition of " non-thermofusible " as mentioned above.In addition, " thermally melting " is defined by about 5g granular phenol resin sample is inserted between 2 thick stainless steel plates of 0.2mm, utilize heat in advance to 100 ℃ pressing machine with the total load punching press of 50kg in the time of 2 minutes, the granular phenol resin fusion, particularly, under above-mentioned high-temperature pressurizing condition, because fusion and/or fusion and granular phenol resin forms dull and stereotyped character.The granular phenol resin that " thermally melting " that defined in this wise be shown illustrates thermoset under for example about temperature more than 120 ℃ being higher than under 100 ℃ the temperature." thermoset " is meant gelation in gel time (gel time) test at 180 ℃.
(term as relative 2 agglutinators is also referred to as progenitor to the particle of formation non-thermofusible or thermally melting granular phenol resin.) median size be preferably below the 12 μ m.As raw material, be granular phenol resin below the 12 μ m by using median size, can form median size is the following carbon progenitors of 10 μ m.At this, for the definition of " median size " of non-thermofusible and thermally melting granular phenol resin, identical with the definition of " median size " of described non-thermofusible granular phenol resin.
Non-thermofusible of Shi Yonging or thermally melting granular phenol resin have narrow size distribution in the present invention, and particularly, formation is preferably below 0.65 by the coefficient of variation of the size distribution of the particle (progenitor) of the granular phenol resin of above-mentioned formula [1] definition.The coefficient of variation of size distribution is more preferably below 0.6.
By making the coefficient of variation by the size distribution of above-mentioned formula [1] expression is below 0.65, and the coefficient of variation of the size distribution of carbon progenitor is become below 0.65, and the result can obtain the outstanding molecular-sieve carbon of separation energy of mixed gas.Wherein, the coefficient of variation of carbon progenitor is different with the condition determination of the coefficient of variation of granular phenol resin, if but the coefficient of variation that uses above-mentioned formula [1] is the granular phenol resin below 0.65, can confirm that then the carbon progenitor that constitutes the molecular-sieve carbon that obtains satisfies the coefficient of variation of above-mentioned formula [3] below 0.65.
The simple grain rate of non-thermofusible or thermally melting granular phenol resin is preferably more than 0.7, more preferably more than 0.8.The simple grain rate less than 0.7 situation under, the heterogeneity that becomes of the pyrolysated gas when utilizing carbonizing treatment is utilized the heterogeneities that also become such as the shape of the pore that thermolysis forms and distribution, result, the trend that exists the separating power of mixed gas to reduce.The definition that " simple grain " reaches " simple grain rate " as mentioned above.
The particle shape of non-thermofusible or thermally melting granular phenol resin is good more near spherical shape more.Particularly, degree of sphericity is preferably more than 0.5, more preferably more than 0.7, is preferably more than 0.9 especially.Particle shape more near spherical shape be degree of sphericity more near 1.0, then can improve more to the density of the particulate molecular sieve carbon that the homogeneous mixture forms, carbonization obtains of binder constituents etc.In addition, can also make the generation of thermolysis gas when utilizing carbonizing treatment and the shape and the more homogeneous that distributes of the pore that forms, so can further improve the separation energy of mixed gas.The definition of " degree of sphericity " as mentioned above.
And then the free phenol content of non-thermofusible or thermally melting granular phenol resin is preferably below the 1000ppm.This free phenol content is more preferably below the 500ppm, and then is preferably below the 400ppm.By making the content as the free phenol of objectionable constituent is below the 1000ppm, the security in the time of can improving granular phenol resin and handle.The definition of " free phenol content " as mentioned above.
Then, the manufacture method to the granular phenol resin of the described raw material that is preferably used as molecular-sieve carbon of the present invention describes.For non-thermofusible granular phenol resin, can use described method of the present invention to make well.At this moment, the usage quantity of colloid protective agent is with the solids component Mass Calculation, is preferably more than about 0.05 weight % of usage quantity of described phenols.Under the situation of usage quantity less than about 0.05 weight % of colloid protective agent, deficiency for example must utilize other parameters such as phenols usage quantity or stirring velocity to come control size so that the median size of granular phenol resin is below the 12 μ m.The upper limit to the usage quantity of colloid protective agent is not particularly limited, and for example is below the 3 weight % of usage quantity of phenols.Under situation, there is because the viscosity of reaction solution rises the trend of velocity of separation reduction in separation circuit described later etc. more than 3 weight %.
The thermally melting granular phenol resin can obtain by omit non-hot melt operation in the manufacture method of described non-thermofusible granular phenol resin of the present invention.For the separating, washing operation, identical with non-thermofusible granular phenol resin.
Non-thermofusible that has been washed or thermally melting granular phenol resin also can not make its dry and under aqueous state directly as the raw material of molecular-sieve carbon, but preferably make its drying.
Then, the manufacture method to molecular-sieve carbon of the present invention describes.Method of the present invention can be applicable to well makes described molecular-sieve carbon of the present invention.The manufacture method of molecular-sieve carbon of the present invention comprises following operation.
(i) to contain median size be below the 12 μ m and the coefficient of variation of size distribution is the operation that the homogeneous mixture of granular phenol resin below 0.65 and binder constituents forms the thing that obtains being shaped; And
(ii) under non-oxidizing atmosphere, under the temperature of 500～1100 ℃ scopes this shaping thing of heating, obtain the operation of the shaping thing of carbonization thus.
(i) forming process
In this operation, be below the 12 μ m to median size and the coefficient of variation of size distribution is after the granular phenol resin, binder constituents below 0.65 and other uniform component ground of adding as required mix, form, thereby obtain particulate state shaping thing.For granular phenol resin, as mentioned above, more preferably possess simple grain rate more than 0.7, degree of sphericity more than 0.5 and the following granular phenol resin of free phenol content 1000ppm.
As binder constituents, can enumerate polyvinyl alcohol, water-soluble or water-swellable derivatived cellulose, coal tar oils etc.If enumerate concrete example water-soluble or the water-swellable derivatived cellulose, then comprise methylcellulose gum, carboxymethyl cellulose, hydroxypropylcellulose etc.In addition, as coal tar oils, can enumerate coal tar, coal-tar pitch, creosote and the mixture more than 2 kinds wherein.In addition, as other binder constituents, also can add thermosetting resins such as resol or melamine resin.
Relative granular phenol resin 100 weight parts of the addition of binder constituents are preferably about 1～50 weight part, more preferably 1～30 weight part.
In addition, binder constituents also can use for example starch, its derivative or its modification body.These compositions of starch etc. can be well form material as pore, and to form pore relevant in thermolysis when carrying out carbonization under non-oxidizing atmosphere.If enumerate the concrete example of starch etc., for example starch such as yam starch, W-Gum; Starch derivative such as esterification starch, etherification starch, cross-linking starch; Treated starches such as enzyme-modified dextrin etc.Relative granular phenol resin 100 weight parts of the addition of starch, its derivative or its modification body are preferably about 1～50 weight part, more preferably 1～30 weight part.
In addition, sieve in the scope of the characteristic of carbon,, for example can add tensio-active agents such as ethylene glycol, polyethylene oxide alkyl ethers, polyoxyethylene fatty acid ester, poly-ammonium carbonate salts on a small quantity in order to improve operability saboteur not; Solidifying agent such as liquid thermosetting resin; Linking agents such as polyvinyl alcohol; The softening agent that extruding pelletization is used; The Exocarpium cocois (Cocos nucifera L) micropowder; The coal micropowder; Other synthetic resins etc.
When preparation homogeneous mixture, for example can use ribbon blender, V-Mixer, cone-type mixer (cone mixer), kneader etc.In addition, as the homogeneous mixture is configured as granular method, can use prilling process such as extruding pelletization, rotation granulation, compression granulation.Shape to particulate state shaping thing is not particularly limited, and for example can be column, spherical even-granular such as cylindric.Under the situation that is cylindrical particle, its diameter and length (highly) are preferably respectively about 0.5～3mm, and under the situation that is granular particle, its diameter is preferably about 0.5～3mm.
(ii) carbonation process
In this operation,, obtain the shaping thing of carbonization by the described particulate state shaping thing of heating under non-oxidizing atmosphere, under the temperature of 500～1100 ℃ scope.Temperature during carbonization is preferably 650～850 ℃.Carbonization temperature less than 500 ℃ situation under, do not have sufficient loading capacity, existence can only obtain lacking the trend of the carbide of selecting adsorptivity, is being higher than under 1100 ℃ the situation, the pore of the carbide that obtains shrinks, and has the trend that is difficult to obtain enough loading capacities.For example can be 1～24 hour heat-up time, is preferably 1～12 hour.As the gas that is used under non-oxidizing atmosphere, using, can enumerate nitrogen, argon etc.
As the process furnace that is used for carbonizing treatment, can use the formula of leaving standstill, flowing-type, process furnace such as rotary, but preferably use revolving rotary kiln (rotary kiln).
After described carbonizing treatment,, also can under temperature below 500 ℃ or the temperature below 1100 ℃, implement thermal treatment once more in order to adjust the characteristic of molecular-sieve carbon.In addition, the also particulate state shaping thing that can utilize described carbonizing treatment to obtain by pulverizing mixes with binder constituents etc., granulation once more, and then implements thermal treatment, adjusts the characteristic of molecular-sieve carbon.
Molecular-sieve carbon of the present invention can be used as the sorbent material of nitrogen generator unit well.As nitrogen generator unit, can enumerate in being filled with the adsorption tower of molecular-sieve carbon of the present invention, for example supply with the unstripped gas that principal constituent is oxygen and nitrogen, in adsorption tower, repeat the nitrogen generator unit of the PSA mode separation of nitrogen of high pressure absorption process and low pressure regeneration operation.The molecular-sieve carbon of the application of the invention is compared with nitrogen generator unit in the past, can utilize the raising of the nitrogen recovery that the raising of nitrogen gas purity causes, improves the nitrogen generating capacity of per unit weight molecular-sieve carbon.Below be that example illustrates nitrogen generator unit of the present invention with PSA formula nitrogen generator unit.
Figure 14 is the summary mode chart of a preference of expression PSA formula nitrogen generator unit of the present invention.PSA formula nitrogen generator unit shown in Figure 14 comprises following structure, is filled with the 2 adsorption tower 101a and the 101b of molecular-sieve carbon of the present invention that is:; The unstripped gas supply unit that constitutes by compressor 102 and instrument air dryer 103 etc.; Lay in the goods groove 104 of isolating nitrogen; Be used to link the pipe arrangement of these integrants; Mobile magnetic valve and its Controlling System of being used for pilot-gas; Flow-rate adjustment is taken into account the analysis meter of gas concentration etc.
Operation method to PSA formula nitrogen generator unit shown in Figure 14 describes.Wherein, following operation method is only represented an example, does not limit the present invention fully.At first, in the high pressure absorption process of adsorption tower 101a, the unstripped gas of utilizing compressor 102 compressions via magnetic valve 105 and magnetic valve 106a, pipe arrangement 107a, is supplied with to adsorption tower 101a then by instrument air dryer 103 dryings.At this, the principal constituent of the unstripped gas of supply is oxygen and nitrogen (for example air), utilizes compressor 102 to be forced into preferred 3～10kgf/cm 2About G.
The molecular-sieve carbon that oxygen is adsorbed in the tower 101a optionally absorbs, and after the nitrogen that has been concentrated temporarily is stored in the goods groove 104 by pipe arrangement 108a, magnetic valve 109a and pipe arrangement 110, is used as goods by pressure-regulator 111, pipe arrangement 112 again and takes out.Then, after adsorption time, close magnetic valve 106a and magnetic valve 109a through regulation.
In the low pressure regeneration operation of adsorption tower 101a, open magnetic valve 113a, the unstripped gas that is full of in the adsorption tower 101a under being in pressurized state is discharged into the atmosphere by pipe arrangement 114, and the interior pressure of adsorption tower 101a is reduced near the normal atmosphere apace, makes molecular-sieve carbon regeneration.And then, open magnetic valve 115a and magnetic valve 116, the nitrogen in the goods groove 104 is circulated by pipe arrangement 117 to adsorption tower flow direction (with nitrogen removing direction reverse direction), carry out the regeneration of adsorption tower 101a thus.If this step for regeneration finishes, then close magnetic valve 113a, magnetic valve 115a and magnetic valve 116, carry out pressure process as required, and then carry out the high pressure absorption process.As described later,, the regeneration of the molecular-sieve carbon in the adsorption tower can be successfully carried out, highly purified nitrogen can be taken out simultaneously by repeating absorption process and step for regeneration.Wherein, described operation method is that the situation of using 1 adsorption tower is illustrated, and under the situation of using 2 adsorption towers, uses 2 adsorption towers alternately to carry out the circulation of absorption process-step for regeneration.
In described operation method, also can add pressure process and reflow process, for example operate with the circulation of absorption process-pressure process-step for regeneration-pressure process-reflow process-absorption process and so on.Pressure process is meant and using under the situation of 2 above adsorption towers, and the adsorption tower of the adsorption tower of the high pressure absorption process that is through with and the low pressure regeneration operation that is through with carries out the operation of the pressure equalization of pressure in the adsorption tower.For example under for the situation of nitrogen generator unit of utilizing 2 adsorption towers, the situation that only links the top of 2 adsorption towers is called all pressures, the situation that only links the bottom is called down all pressures, is called up and down all pressures linking the situation that reaches the both sides between the bottom between the top.
Reflow process is meant that the part of nitrogen gets back in the adsorption tower from the goods groove, and this nitrogen is not discharged outside system and stayed in the adsorption tower, thereby makes the nitrogen that takes out high density in the absorption process easy operation that becomes.
Below enumerate embodiment and illustrate in greater detail the present invention, but the present invention is not limited to these.
[preparation of non-thermofusible granular phenol resin]
＜embodiment 1 〉
Use 35 weight % hydrochloric acid and 36 weight % formalins, the preparation concentration of formaldehyde is that 10 weight % and concentration of hydrochloric acid are the mixing solutions 2000g of 16 weight %, in this mixing solutions, add 2 weight % aqueous solution 8g of sodium carboxymethyl-cellulose then, stir into uniform solution.Then, the temperature of this uniform solution is adjusted to 20 ℃, adds 30 ℃ 95 weight % phenol 70g then while stirring.Wherein, the concentration of the phenols of relative response liquid gross weight is 3.2 weight %, and the adding mol ratio of the phenol of phase PARA FORMALDEHYDE PRILLS(91,95) is 0.11, and the volumetric molar concentration of the hydrochloric acid in the reaction solution is 4.7mol/L.When adding phenol and begin about 120 seconds, the reaction solution gonorrhoeaization.Reduce stirring velocity and proceed reaction after gonorrhoeaization, the result is after about 30 minutes after phenol adds, and reaction solution is coloured to lightpink.At this moment, the temperature of reaction solution reaches 30 ℃.After reaction solution is painted, utilize indirect heating, reaction solution is heated to 80 ℃, under this temperature, kept 30 minutes.Then, filter this reaction solution, the filter cake with the water washing of 500g obtains makes in its 0.5 weight % ammonia soln that is suspended in 500g then, carries out 1 hour neutralization reaction under 40 ℃.After the neutralization reaction, use vent fan to attract to filter this suspension,, utilize 50 ℃ drying machine to make its dry 10 hours, obtain the lurid granular phenol resin 1A of 80g thus with the water washing of 500g.
＜embodiment 2 〉
Making the concentration of formaldehyde in the mixed solution is that 18 weight %, concentration of hydrochloric acid are 18 weight %, in addition, reacts similarly to Example 1, obtains granular phenol resin 2A.Wherein, the concentration of the phenols of relative response liquid gross weight is 3.2 weight %, and the adding mol ratio of the phenol of phase PARA FORMALDEHYDE PRILLS(91,95) is 0.06, and the volumetric molar concentration of the hydrochloric acid in the reaction solution is 5.3mol/L.The gonorrhoeaization of reaction solution is taking place after adding phenol to begin to count about 150 seconds, does not also have operational problems such as resin adhering on wall.Fig. 2 represents the optical microscope photograph of the granular phenol resin that obtains in the present embodiment.
＜embodiment 3 〉
Making the concentration of formaldehyde in the mixed solution is that 7 weight %, concentration of hydrochloric acid are 20 weight %, in addition, reacts similarly to Example 1, obtains granular phenol resin 3A.Wherein, the concentration of the phenols of relative response liquid gross weight is 3.2 weight %, and the adding mol ratio of the phenol of phase PARA FORMALDEHYDE PRILLS(91,95) is 0.15, and the volumetric molar concentration of the hydrochloric acid in the reaction solution is 5.9mol/L.The gonorrhoeaization of reaction solution is taking place after adding phenol to begin about 30 seconds, does not also have operational problems such as resin adhering on wall.Fig. 3 represents the optical microscope photograph of the granular phenol resin that obtains in the present embodiment.
＜embodiment 4 〉
Add 95 weight % phenol 52g, in addition, react similarly to Example 1, obtain 62g granular phenol resin 4A.Wherein, the concentration of the phenols of relative response liquid gross weight is 2.4 weight %, and the adding mol ratio of the phenol of phase PARA FORMALDEHYDE PRILLS(91,95) is 0.08, and the volumetric molar concentration of the hydrochloric acid in the reaction solution is 6.0mol/L.
＜embodiment 5 〉
Add 95 weight % phenol 105g, in addition, react similarly to Example 1, obtain 115g granular phenol resin 5A.Wherein, the concentration of the phenols of relative response liquid gross weight is 4.7 weight %, and the adding mol ratio of the phenol of phase PARA FORMALDEHYDE PRILLS(91,95) is 0.16, and the volumetric molar concentration of the hydrochloric acid in the reaction solution is 5.8mol/L.
＜embodiment 6 〉
Mix 36 weight % formalin 556g and 95 weight % phenol 70g and water 530g, preparation mixing solutions 1156g, 2 weight % aqueous solution 8g of interpolation sodium carboxymethyl-cellulose in this mixing solutions stir into uniform solution then.Then, the temperature of this uniform solution is adjusted to 20 ℃, adds 30 ℃ 35 weight % hydrochloric acid 914g then while stirring.Wherein, the concentration of the phenols of relative response liquid gross weight is 3.2 weight %, and the adding mol ratio of the phenol of phase PARA FORMALDEHYDE PRILLS(91,95) is 0.11, and the volumetric molar concentration of the hydrochloric acid in the reaction solution is 4.7mol/L, and is identical with embodiment 1.When adding hydrochloric acid and begin about 20 seconds, the reaction solution gonorrhoeaization.Still continue reaction after gonorrhoeaization, the result is after interpolation hydrochloric acid begins about 30 minutes, and reaction solution is coloured to pink colour.Then, carry out similarly to Example 1, heat, separate, wash and drying, obtain 78g granular phenol resin 6A thus.
＜embodiment 7 〉
Add 95 weight % phenol 204g, in addition, react similarly to Example 6, obtain 240g granular phenol resin 7A.Wherein, the concentration of the phenols of relative response liquid gross weight is 8.8 weight %, and the adding mol ratio of the phenol of phase PARA FORMALDEHYDE PRILLS(91,95) is 0.31, and the volumetric molar concentration of the hydrochloric acid in the reaction solution is 4.4mol/L.
＜embodiment 8 〉
In the preparation of mixed solution, use 36 weight % formalin 278g, 95 weight % phenol 204g and water 803g, in addition, react similarly to Example 6, obtain 200g granular phenol resin 8A.Wherein, the concentration of the phenols of relative response liquid gross weight is 8.8 weight %, and the adding mol ratio of the phenol of phase PARA FORMALDEHYDE PRILLS(91,95) is 0.62, and the volumetric molar concentration of the hydrochloric acid in the reaction solution is 4.4mol/L.
＜embodiment 9 〉
Replace 36 weight % formalins, use the paraformaldehyde aqueous solution of identical weight concentration, in addition, react similarly to Example 1.Process and the embodiment 1 of reaction obtain the granular phenol resin 9A of 77g much at one.
＜embodiment 10 〉
Making the concentration of hydrochloric acid in the mixing solutions is 8 weight %, and after adding 95 weight % phenol, utilizes indirect heating, reaction solution is warming up to 50 ℃, after reaction solution is painted, is heated to 80 ℃, in addition, react similarly to Example 1, obtain granular phenol resin 10A.The concentration of the phenols of relative response liquid gross weight is 3.2 weight %, and the adding mol ratio of the phenol of phase PARA FORMALDEHYDE PRILLS(91,95) is 0.11, and the volumetric molar concentration of the hydrochloric acid in the reaction solution is 2.3mol/L.
＜comparative example 1 〉
The 2 weight % aqueous solution 8g that replace sodium carboxymethyl-cellulose use 8g water, in addition, react similarly to Example 1, obtain 80g granular phenol resin 1C.The process of reaction except add phenol begin about 95 seconds after the reaction solution generation gonorrhoea, identical with embodiment 1.Fig. 4 is illustrated in the optical microscope photograph of the granular phenol resin that obtains in this comparative example.For granular phenol resin 1C, as shown in Figure 4, the aggegation of more progenitor has taken place as can be known.The simple grain rate of granular phenol resin 1C is 0.60.
＜comparative example 2 〉
Making the concentration of hydrochloric acid among the mixing solutions 2000g is 5 weight %, in addition, reacts similarly to Example 1.Do not see the gonorrhoea of reaction solution, can not obtain granular phenol resin.Wherein, the volumetric molar concentration of the hydrochloric acid in the reaction solution is 1.5mol/L.
＜comparative example 3 〉
In the preparation of mixed solution, use 36 weight % formalin 140g, 95 weight % phenol 204g and water 940g, in addition, react similarly to Example 6.The concentration of the phenols of relative response liquid gross weight is 8.8 weight %, and the adding mol ratio of the phenol of phase PARA FORMALDEHYDE PRILLS(91,95) is 1.23, and the volumetric molar concentration of the hydrochloric acid in the reaction solution is 4.5mol/L.If resin is then adhered in the heating of beginning reaction solution on reactor wall.Leach the powder that is in suspended state when heating finishes, washing, neutralization, drying obtain the granular phenol resin 3C of about 50g.Utilize the microscopic examination particle, there are a lot of atypic particles in the result, can not try to achieve degree of sphericity, simple grain rate.
To granular phenol resin 1A～10A, 1C and 3C, measure the various characteristics shown in the table 1.Measurement result is shown in table 1 with reaction conditions.
Figure A20078003485200501
＜embodiment 11 〉
To carry out various changes as the sodium carboxymethyl-cellulose phase Pyrogentisinic Acid's of colloid protective agent amount, in addition, react similarly to Example 1, obtain granular phenol resin, measure the median size of each granular phenol resin then.Fig. 5 is the graphic representation of concentration (weight (ppm) of the colloid protective agent of relative response liquid gross weight) with the relation of the median size of granular phenol resin of expression colloid protective agent.Wherein, if the measurement range 13 of colloid protective agent concentration～about 103ppm is converted into colloid protective agent usage quantity/phenol usage quantity than (weight %), then be equivalent to the scope of 0.04～0.32 weight %.As shown in Figure 5, can control the median size of the granular phenol resin that obtains by adjusting the usage quantity of colloid protective agent as can be known.That is, can reduce median size by the usage quantity that increases colloid protective agent as can be known.
＜embodiment 12 〉
Use 35 weight % hydrochloric acid and 36 weight % formalins, the preparation concentration of formaldehyde is that 8 weight % and concentration of hydrochloric acid are the mixing solutions 10kg of 17 weight %, in this mixing solutions, add 2 weight % aqueous solution 20g of sodium carboxymethyl-cellulose then, stir into uniform solution.Then, the temperature of this uniform solution is adjusted to 20 ℃, adds 40 ℃ 95 weight % phenol 400g then while stirring.Wherein, the concentration of the phenols of relative response liquid gross weight is 3.65 weight %, and the adding mol ratio of the phenol of phase PARA FORMALDEHYDE PRILLS(91,95) is 0.15, and the volumetric molar concentration of the hydrochloric acid in the reaction solution is 5.0mol/L.When adding phenol and begin about 70 seconds, the reaction solution gonorrhoeaization.Reduce stirring velocity and still continue reaction after gonorrhoeaization, the result is after the phenol interpolation begins about 30 minutes, and reaction solution is coloured to lightpink.At this moment, the temperature of reaction solution reaches 30 ℃.After reaction solution painted, utilize indirect heating, reaction solution is heated to 80 ℃, under this temperature, kept 30 minutes.Then, filter this reaction solution, the granular phenol resin filter cake with the water washing of 1kg obtains obtains the about 700g granular phenol resin 12A-a that wets thus.Utilize 50 ℃ drying machine to make its part dry with 10 hours, carry out fluorescent X-ray then and measure, the cl content of granular phenol resin is about 6500ppm as a result.In addition, the median size of granular phenol resin 12A-a is 3.5 μ m.
Then, described wet granular phenol resin 12A-a 500g is scattered among the ion exchanged water 5L, is heated to 95 ℃ while stirring, under this temperature, kept 24 hours.Then, filter this dispersion liquid, the granular phenol resin with on the ion-exchange water washing filter paper of 500g obtains granular phenol resin 12A-b (being equivalent to dry weight 320g).Made the part of the granular phenol resin that obtains dry with 10 hours down at 105 ℃, carry out fluorescent X-ray then and measure, cl content is about 1100ppm as a result.
Then, wet granular phenol resin 12A-b (being equivalent to dry weight 300g) is scattered in the ethylene glycol of 900g, is heated to 180 ℃ while stirring, under this temperature, kept 3 hours.Then, be cooled to normal temperature after, filter this dispersion liquid, with the granular phenol resin on the ion-exchange water washing filter paper of 500g.In nitrogen gas stream, the granular phenol resin that obtains 180 ℃ of following dryings 5 hours obtains 280g granular phenol resin 12A-c.The cl content of granular phenol resin 12A-c is 70ppm.
＜embodiment 13 〉
Carry out the washing that 2 times (2 times is the same terms with embodiment 12 all) makes spent glycol altogether, in addition, carry out similarly to Example 12, obtain the granular phenol resin 13A of 280g.The cl content of granular phenol resin 13A is 10ppm.Wherein, between the washing of the 1st time washing and the 2nd time, drying process is not set.
＜embodiment 14 〉
Use 35 weight % hydrochloric acid and 36 weight % formalins, the preparation concentration of formaldehyde is that 8 weight % and concentration of hydrochloric acid are the mixing solutions 10kg of 18 weight %, in this mixing solutions, add 2 weight % aqueous solution 30g of sodium carboxymethyl-cellulose then, stir into uniform solution.Then, the temperature of this uniform solution is adjusted to 20 ℃, adds 40 ℃ 95 weight % phenol 400g then while stirring.Wherein, the concentration of the phenols of relative response liquid gross weight is 3.64 weight %, and the adding mol ratio of the phenol of phase PARA FORMALDEHYDE PRILLS(91,95) is 0.15, and the volumetric molar concentration of the hydrochloric acid in the reaction solution is 5.3mol/L.When the interpolation from phenol begins about 60 seconds, the reaction solution gonorrhoeaization.Reduce stirring velocity and still continue reaction after gonorrhoeaization, the result is after the phenol interpolation begins about 30 minutes, and reaction solution is coloured to lightpink.At this moment, the temperature of reaction solution reaches 30 ℃.After reaction solution is painted, utilize indirect heating, reaction solution is heated to 80 ℃, under this temperature, kept 30 minutes.Then, filter this reaction solution, the granular phenol resin filter cake with the water washing of 1kg obtains obtains the about 700g granular phenol resin 14A-a that wets thus.Utilize 50 ℃ drying machine to make its part dry with 10 hours, carry out fluorescent X-ray then and measure, the cl content of granular phenol resin is about 6500ppm as a result.In addition, the median size of granular phenol resin 14A-a is 5.8 μ m.
Then, described wet granular phenol resin 14A-a 500g is scattered among the ion exchanged water 5L, is heated to 95 ℃ while stirring, under this temperature, kept 24 hours.Then, filter this dispersion liquid, the granular phenol resin with on the ion-exchange water washing filter paper of 500g obtains granular phenol resin 14A-b (being equivalent to dry weight 320g).Made the part of the granular phenol resin that obtains dry with 10 hours down at 105 ℃, carry out fluorescent X-ray then and measure, cl content is 1700ppm as a result.
Then, wet granular phenol resin 14A-b (being equivalent to dry weight 300g) is scattered in the ethylene glycol of 900g, is heated to 180 ℃ while stirring, under this temperature, kept 3 hours.Then, be cooled to normal temperature after, filter this dispersion liquid, with the granular phenol resin on the ion-exchange water washing filter paper of 500g.In nitrogen gas stream, the granular phenol resin that obtains 180 ℃ of following dryings 5 hours obtains 280g granular phenol resin 14A-c.The cl content of granular phenol resin 14A-c is 90ppm.
＜embodiment 15 〉
Carry out the washing that 2 times (2 times is the same terms with embodiment 14 all) makes spent glycol altogether, in addition, carry out similarly to Example 14, obtain the granular phenol resin 15A of 280g.The cl content of granular phenol resin 15A is 30ppm.Wherein, between the washing of the 1st time washing and the 2nd time, drying process is not set.
＜embodiment 16 〉
The granular phenol resin 12A-a 500g that will obtain in embodiment 12 is scattered among the 25 weight % ammonia soln 1.5L (1350g), is heated to 37 ℃ while stirring, keeps 24 hours under this temperature.Then, filter this dispersion liquid, with the granular phenol resin on the ion-exchange water washing filter paper of 500g.The granular phenol resin that obtains 105 ℃ of following dryings 10 hours obtains 320g granular phenol resin 16A.The cl content of granular phenol resin 16A is 300ppm.
＜embodiment 17 〉
Carry out the washing that 2 times (2 times is the same terms with embodiment 16 all) uses 25 weight % ammonia solns altogether, in addition, carry out similarly to Example 16, obtain the granular phenol resin 17A of 320g.The cl content of granular phenol resin 17A is 50ppm.Wherein, between the washing of the 1st time washing and the 2nd time, drying process is not set.
＜embodiment 18 〉
The wet granular phenol resin 12A-b (being equivalent to dry weight 300g) that will obtain in embodiment 12 is scattered among the 25 weight % ammonia soln 900g, uses pressure kettle, stirs 2 hours down at 80 ℃.Then, filter this dispersion liquid, with the granular phenol resin on the ion-exchange water washing filter paper of 500g.The granular phenol resin that obtains 105 ℃ of following dryings 10 hours obtains 280g granular phenol resin 18A.The cl content of granular phenol resin 18A is below the limit of detection (10ppm).
＜embodiment 19 〉
The wet granular phenol resin 12A-a (being equivalent to dry weight 300g) that will obtain in embodiment 12 is scattered in the ethylene glycol of 900g, is heated to 180 ℃ while stirring, keeps 3 hours under this temperature.Then, after being cooled to room temperature, filter this dispersion liquid, with the granular phenol resin on the ion-exchange water washing filter paper of 500g.In nitrogen gas stream, the granular phenol resin that obtains 180 ℃ of following dryings 5 hours obtains 280g granular phenol resin 19A.The cl content of granular phenol resin 19A is 300ppm.
＜embodiment 20 〉
Carry out the washing that 2 times (2 times is the same terms with embodiment 19 all) makes spent glycol altogether, in addition, carry out similarly to Example 19, obtain the granular phenol resin 20A of 280g.The cl content of granular phenol resin 20A is 60ppm.In addition, between the washing of the 1st time washing and the 2nd time, drying process is not set.
＜comparative example 4 〉
Phenol 100 weight parts, 92 weight % paraformaldehyde, 39 weight parts, vulkacit H 9 weight parts and gum arabic 1 weight part are dissolved in the water of 100 weight parts.Add Bellpearl R800 (liking water (strain) system) 7 weight parts and stir also lentamente and be warming up to 85 ℃ with 60 minutes simultaneously, and then keep 85 ℃ temperature and make its reaction 60 minutes simultaneously as nuclear substance.The reaction solution that cooling obtains carries out solid-liquid separation, obtains the spherical resole that median size is about 500 μ m.These spherical resole 100 weight parts are scattered in the solution that contains 17 weight % hydrochloric acid and 9 weight % formaldehyde of 1000 weight parts, are warming up to 80 ℃, kept 1 hour.Utilize to filter reaction solution is carried out solid-liquid separation, after the washing, drying is 5 hours under 85 ℃.The resin maintenance globular form and the granularity that obtain are constant, and non-thermofusible is shown in fact.Degree of sphericity is 1.0, and the simple grain rate is 1.0, and median size is about 500 μ m, and boiling the dissolve with methanol degree is 6%, and cl content is 4500ppm.Median size directly reads from the size-grade distribution of optical microphotograph mirror image.
Method according to record among the embodiment 13 makes spent glycol, and the non-thermofusible resol particle that this median size is about 500 μ m carries out carrying out washing treatment 2 times, obtains granular phenol resin 4C.The cl content of granular phenol resin 4C is 1200ppm.In addition, between the washing of the 1st time washing and the 2nd time, drying process is not set.
＜reference example 1 〉
The granular phenol resin 14A-b 500g (chloride ion content 1700ppm) that will obtain in described embodiment 14 is scattered among the ion exchanged water 5L, is heated to 95 ℃ while stirring, keeps 24 hours under this temperature.Then, filter this dispersion liquid, with the granular phenol resin on the ion-exchange water washing filter paper of 500g.The granular phenol resin that obtains 105 ℃ of following dryings 10 hours obtains granular phenol resin 1S.The cl content of granular phenol resin 1S is 700ppm.
＜reference example 2 〉
Granular phenol resin 1S is carried out and reference example 1 identical operations, obtain granular phenol resin 2S.The cl content of granular phenol resin 2S is 600ppm.
＜reference example 3 〉
Granular phenol resin 2S is carried out and reference example 1 identical operations, obtain granular phenol resin 3S.The cl content of granular phenol resin 3S is 550ppm.
To granular phenol resin 12A～20A, 4C and 1S～3S, measure the various characteristics shown in the table 2.Measurement result is shown in table 2 with reaction conditions.Granular phenol resin 1C and 3C also are shown together.
Figure A20078003485200561
From described embodiment 12～20 as can be known, utilize the washing of ethylene glycol and/or the washing of ammonia soln, can obtain the following granular phenol resin of cl content 100ppm effectively.Think that alcohols such as ethylene glycol has easily the chemical property to the internal divergence of resol particle, can improve the velocity of diffusion of chlorion in resol, so can wash effectively.In addition, think that also the high-temperature area that the mobility of preferably utilizing the resol molecule improves washs.Think use ammonia soln situation too because ammonia soln can improve the velocity of diffusion of chlorion in resol, so can wash effectively like this to the internal divergence of resol particle.
On the other hand, if observe reference example 1～3, cl content 1700ppm) and the 2nd (granular phenol resin 1S: when washing cl content 700ppm) then as seen utilizing hot water to carry out (granular phenol resin 14A-b: the 1st time, cl content reduces owing to remove the chlorion of resol particle surface, but there is the chlorion that closes resol inside on the contrary more, it is controlled to the diffusion translational speed of particle surface to be present in this inner chlorion, the result is utilizing hot water to carry out the 3rd time and the 4th when washing, and washing effect reduces significantly.Use under the situation of hot water, even carry out 4 washings, cl content can not become below the 500ppm yet, and is very inefficent.And then shown in comparative example 4, even the resol that median size is bigger as can be known utilizes the washing of alcohol, cl content is not reduced fully yet.
Fig. 6 is the scanning electron microscope photo (SEM photo, 500 times) of the granular phenol resin 12A-c that obtains in embodiment 12.In addition, Fig. 7 is the SEM photo (3500 times) of the further amplification of granular phenol resin 12A-c.Can confirm from Fig. 6, Fig. 7 and table 2, even utilize ethylene glycol washing and/or ammonia soln washing, the condition of surface of median size, simple grain rate, degree of sphericity and resol particle etc. almost do not change, and make the washing of spent glycol or ammonia soln bring detrimentally affect can for the resol particle.
[preparation of compositions of thermosetting resin]
＜embodiment 21 〉
Heat to 70 ℃ of limits at mixing granular phenol resin 13A 6 weight parts that in described embodiment 13, obtain and Resins, epoxy (Dongdu system of changing into " Epotohto YD-128 ") 4 weight parts on the hot-rolling on the limit, further add 2-ethyl-4-methylimidazole 0.2 weight part then as solidifying agent, mixing, peel off mixing thing from hot-rolling, pulverize the cooling back, obtains the powder as compositions of thermosetting resin.This compositions of thermosetting resin illustrates good melt fluidity, and 150 ℃ of following gel times are 33 seconds, and 200 ℃ of following gel times are 18 seconds.
Then, this compositions of thermosetting resin is installed in the mould that is heated to 180 ℃, with 20kgf/cm 2Pressure kept 3 minutes, obtain cured article.The proportion of the cured article that obtains is 1.24, for light-duty.
＜embodiment 22 〉
Heat to 70 ℃ of limits at mixing granular phenol resin 13A 6 weight parts that in described embodiment 13, obtain and Resins, epoxy (Dongdu system of changing into " Epotohto YD-8125 ") 4 weight parts on the hot-rolling on the limit, further add 2-ethyl-4-methylimidazole 0.2 weight part then as solidifying agent, mixing, peel off mixing thing from hot-rolling, pulverize the cooling back, obtains the powder as compositions of thermosetting resin.This compositions of thermosetting resin illustrates good melt fluidity, and 150 ℃ of following gel times are 25 seconds, and 200 ℃ of following gel times are 14 seconds.
Then, this compositions of thermosetting resin is installed in the mould that is heated to 180 ℃, with 20kgf/cm 2Pressure kept 3 minutes, obtain cured article.The proportion of the cured article that obtains is 1.24, for light-duty.In addition, the cl content of the cured article that obtains is 70ppm, can be used as sealing material for semiconductor or adhesive for semiconductor well.
＜embodiment 23 〉
Mixing granular phenol resin 13A 15 weight parts that obtain in described embodiment 13, Resins, epoxy (Dongdu system of changing into " Epotohto YD-8125 ") 60 weight parts and as phenol novolac resin (big Japanese ink chemical industry system TD-2093) 6 weight parts and Dyhard RU 100 4 weight parts of solidifying agent obtain the compositions of thermosetting resin of semi liquid state.
＜embodiment 24 〉
Mixing granular phenol resin 15A 60 weight parts that obtain in described embodiment 15, Resins, epoxy (Dongdu system of changing into " Epotohto YD-8125 ") 40 weight parts and as 2-ethyl-4-methylimidazole 2 weight parts of solidifying agent obtain compositions of thermosetting resin I.On the other hand, replace granular phenol resin 15A, mixing fused silica (electrochemical industry system FB-301) 106 weight parts, as 2-ethyl-4-methylimidazole 2 weight parts of solidifying agent obtain compositions of thermosetting resin II.The volumetric ratio of the fused silica among the volumetric ratio of the granular phenol resin 15A among the compositions of thermosetting resin I and the compositions of thermosetting resin II is identical.Then, under 150 ℃ temperature condition, compositions of thermosetting resin I and compositions of thermosetting resin II are heating and curing, obtain cured article (being called cured article Ia, IIa).To cured article Ia and IIa, use ORIENTEC system curast meterVPS, measure 150 ℃ of torques (torque) of cured article.As a result, 150 of cured article Ia ℃ of torque values are 1.34 times of cured article IIa.Can confirm that from this some the obdurability during cured article hot of compositions of thermosetting resin of using non-thermofusible granular phenol resin of the present invention is improved.
[preparation of granular carbon electrode material]
＜reference example 4 〉
At first, utilize the method for record among the embodiment 1, obtain 804g granular phenol resin 1A.Then, 680g in this granular phenol resin is divided into these 4 parts of granular phenol resin 1A-a (200g), granular phenol resin 1A-b (200g), granular phenol resin 1A-c (200g) and granular phenol resin 1A-d (80g), condition shown in below utilizing, burn till activation treatment respectively, obtain carbon electrode material 1～4 respectively.
(1) carbon electrode material 1 (yield 94g): 1A-a puts into crucible with granular phenol resin, and this crucible is put into electric furnace.Use fully in the nitrogen replacement electric furnace, then flow into nitrogen then and heat up with 100 ℃/hour speed from room temperature simultaneously, in the moment thermal treatment 3 hours that reaches 600 ℃.Then, heat up with 100 ℃/hour speed once more, with 850 ℃ following 5 hours, in the saturated nitrogen gas stream that water vapour arranged, activate.The weight decrement of expression activation degree is 33%.
(2) carbon electrode material 2 (yield 60g): the temperature when making activation treatment is 900 ℃, in addition, similarly carries out with granular phenol resin 1A-a, burns till, activation treatment granular phenol resin 1A-b.The weight decrement is 56%.
(3) carbon electrode material 3 (yield 35g): the temperature when making activation treatment is 950 ℃, in addition, similarly carries out with granular phenol resin 1A-a, burns till, activation treatment granular phenol resin 1A-c.The weight decrement is 75%.
(4) carbon electrode material 4 (yield 44g): 1A-d puts into crucible with granular phenol resin, and this crucible is put into electric furnace.Use fully in the nitrogen replacement electric furnace, then flow into nitrogen then and heat up with 100 ℃/hour speed from room temperature simultaneously, in the moment thermal treatment 3 hours that reaches 950 ℃.
＜reference example 5 〉
The granular phenol resin 2A 200g that the method for utilizing among the embodiment 2 record is obtained, utilize the condition identical with the granular phenol resin 1A-a of reference example 4, burn till, activation treatment, the weight decrement when obtaining the 90g activation treatment is 36% carbon electrode material 5.
＜reference example 6 〉
The granular phenol resin 3A 200g that the method for utilizing among the embodiment 3 record is obtained, utilize the condition identical with the granular phenol resin 1A-a of reference example 4, burn till, activation treatment, the weight decrement when obtaining the 91g activation treatment is 35% carbon electrode material 6.
＜reference example 7 〉
The granular phenol resin 4A 200g that the method for utilizing among the embodiment 4 record is obtained, utilize the condition identical with the granular phenol resin 1A-a of reference example 4, burn till, activation treatment, the weight decrement when obtaining the 91g activation treatment is 35% carbon electrode material 7.
＜reference example 8 〉
The granular phenol resin 5A 200g that the method for utilizing among the embodiment 5 record is obtained, utilize the condition identical with the granular phenol resin 1A-a of reference example 4, burn till, activation treatment, the weight decrement when obtaining the 92g activation treatment is 34% carbon electrode material 8.
＜reference example 9 〉
The granular phenol resin 6A 200g that the method for utilizing among the embodiment 6 record is obtained, utilize the condition identical with the granular phenol resin 1A-a of reference example 4, burn till, activation treatment, the weight decrement when obtaining the 90g activation treatment is 36% carbon electrode material 9.Fig. 9 represents the optical microscope photograph of the granular carbon electrode material of this reference example.
＜reference example 10 〉
The granular phenol resin 7A 200g that the method for utilizing among the embodiment 7 record is obtained, utilize the condition identical with the granular phenol resin 1A-a of reference example 4, burn till, activation treatment, the weight decrement when obtaining the 92g activation treatment is 34% carbon electrode material 10.
＜reference example 11 〉
The granular phenol resin 8A 200g that the method for utilizing among the embodiment 8 record is obtained, utilize the condition identical with the granular phenol resin 1A-a of reference example 4, burn till, activation treatment, the weight decrement when obtaining the 95g activation treatment is 32% carbon electrode material 11.Figure 10 represents the optical microscope photograph of the granular carbon electrode material of this reference example.
＜reference example 12 〉
The granular phenol resin 9A 200g that the method for utilizing among the embodiment 9 record is obtained, utilize the condition identical with the granular phenol resin 1A-a of reference example 4, burn till, activation treatment, the weight decrement when obtaining the 90g activation treatment is 36% carbon electrode material 12.
＜reference example 13 〉
The granular phenol resin 10A 200g that the method for utilizing among the embodiment 10 record is obtained, utilize the condition identical with the granular phenol resin 1A-a of reference example 4, burn till, activation treatment, the weight decrement when obtaining the 91g activation treatment is 35% carbon electrode material 13.
＜with reference to comparative example 1 〉
The granular phenol resin 1C 70g that the method for utilizing in the comparative example 1 record is obtained, utilize the condition identical with the granular phenol resin 1A-a of reference example 4, burn till, activation treatment, the weight decrement when obtaining the 35g activation treatment is 30% carbon electrode material 14.Figure 11 is illustrated in this optical microscope photograph with reference to the granular phenol resin that obtains in the comparative example.
＜with reference to comparative example 2 〉
The granular phenol resin 3C 200g that the method for utilizing in the comparative example 3 record is obtained, utilize the condition identical with the granular phenol resin 1A-a of reference example 4, burn till, activation treatment, the weight decrement when obtaining the 88g activation treatment is 30% carbon electrode material 15.
＜with reference to comparative example 3 〉
The exsiccant Exocarpium cocois (Cocos nucifera L) is put into crucible, this crucible is put into electric furnace.Use fully in the nitrogen replacement electric furnace, then flow into nitrogen then and also heat up from the speed of room temperature simultaneously, burnt till in 3 hours in the moment thermal treatment that reaches 600 ℃ with 100 ℃/hour.Then, then heat up with 100 ℃/hour speed, with 850 ℃ following 5 hours, in the saturated nitrogen gas stream that water vapour arranged, activate.Utilize power mill (dynamic mill) [MYD] (Mitsui Mining Co Ltd. BJ Offc's system), it is crushed to median size becomes 9 μ m, as granular carbon electrode material 16.
＜with reference to comparative example 4 〉
The granular phenol resin 1C 70g that utilizes the condition identical with the granular phenol resin 1A-d of reference example 4 to burn till to utilize the method for comparative example 1 record to obtain obtains 36g carbon electrode material 17.
To described granular carbon electrode material 1～17, measure the various characteristics shown in the table 3.Measurement result is shown in table 3.Wherein, in the granular carbon electrode material 15 of the reference comparative example 2 in table 3, simple grain rate and degree of sphericity become "-", show to have a lot of atypic particles, can not measure.
[table 3]
Figure A20078003485200621
＜reference example 14 〉
Amount as the phase Pyrogentisinic Acid of the sodium carboxymethyl-cellulose of colloid protective agent is carried out various variations; in addition; similarly carry out with reference example 4; carry out the preparation of granular phenol resin and burn till; under 850 ℃, carry out 5 hours activation treatment then; obtain granular carbon electrode material, measure the median size of granular carbon electrode material.Figure 12 is the graphic representation of concentration (weight (ppm) of the colloid protective agent of relative response liquid gross weight) with the relation of the median size of granular carbon electrode material of expression colloid protective agent.Wherein, if the measurement range 13 of colloid protective agent concentration～about 103ppm is converted into colloid protective agent usage quantity/phenol usage quantity than (weight %), then be equivalent to the scope of 0.04～0.32 weight %.As shown in figure 12, can control the median size of the granular carbon electrode material that obtains by adjusting the usage quantity of colloid protective agent as can be known.That is, can reduce median size by the usage quantity that increases colloid protective agent as can be known.
[being suitable in electric double layer capacitor, lithium ion battery and lithium-ion capacitor of granular carbon electrode material]
＜reference example 15 〉
According to order shown below, make the simple type electric double layer capacitor of structure shown in Figure 13.Figure 13 is the summary sectional view of the electric double layer capacitor of expression trial-production.At first, as current collector 602, use the discoid platinum plate of thick 1mm, external diameter 18mm, on this current collector 602, press sticking as thick 0.5mm, the internal diameter 3mm of distance piece 604, the discoid silicon rubber of external diameter 18mm, in the hole of dark 0.5mm, the internal diameter 3mm that in current collector 602 and distance piece 604, forms, fill the carbon electrode material 601 of the pulpous state of preparation in addition, with it as the polarity electrode.Make 2 such polarity electrodes.Then, the discoid polypropylene system dividing plate 603 of the thick 25 μ m of clamping, external diameter 18mm makes this 2 polarity electrode contrapositions between these 2 polarity electrodes.Then, press the sticking terminal strip 605 that is used to take out the stainless steel of terminal from two side direction current collectoies 602.And then, apply the load of 10kg by upside from the terminal strip 605 of the stainless steel that is used for fixing, make electric double layer capacitor.
Carry out as described below, prepare the carbon electrode material 601 of described pulpous state.With the weight ratio shown in the table 4, in container, add the granular carbon electrode material (carbon electrode material 13, median size 9 μ m) of reference example 13 and the granular carbon electrode material (carbon electrode material 9, median size 1 μ m) of reference example 9, then, add a certain amount of 30 weight % aqueous sulfuric acids, outgas as electrolytic solution.Then, add 30 weight % aqueous sulfuric acids while stirring lentamente in this mixed solution, the mixture in container stops to add when argillaceous is varied to pulpous state, obtains the pulpous state carbon electrode material.With the totally 7 kinds of pulpous state carbon electrode materials (slip 1～7) shown in such order preparation table 4.The employed electrolyte content of every 1g carbon electrode material (g) is called " electrolytic solution/electrode materials ratio ", is shown in table 4.
Then, to diverse 7 kinds of electric double layer capacitors of the carbon electrode material 601 of pulpous state, measure the electrostatic capacitance (F/g) of per unit weight carbon electrode material respectively.Apply the voltage of 0.9V to two interpolars of electric double layer capacitor, carry out 6 hours constant voltage charges, make its constant-current discharge with 100 μ A then, utilize voltage to reduce to the needed time of 0.45V from 0.54V, try to achieve the electrostatic capacitance (F) of electric double layer capacitor, calculate the electrostatic capacitance (F/g) of per unit weight carbon electrode material from this value and one group of (2) weight of polarity electrode.Show the result in table 4.
In addition,, utilize following formula, try to achieve the coefficient of electrostatic capacity of per unit volume from the weight of the electrolytic solution of the weight of the electrostatic capacitance (F/g) of per unit weight carbon electrode material, the carbon electrode material that uses and interpolation.Show the result in table 4.
The coefficient of electrostatic capacity of per unit volume=
(electrostatic capacitance of per unit weight carbon electrode material (F/g)) * (carbon electrode material weight)/(carbon electrode material weight+electrolyte weight)
Figure A20078003485200651
Controlled the carbon electrode material of the present invention 9 and 13 that median size, size-grade distribution and simple grain rate are made closely by mixing to use as can be known, compare with the situation of independent use, can carry out slip with electrolytic solution still less regulates, so can in electric double layer capacitor, fill more carbon electrode material, thereby, can further increase the coefficient of electrostatic capacity of per unit volume.Especially under the situation of mixing carbon electrode material 9 and 13 with 15 pairs 85 (weight ratio) (slip 4), the coefficient of electrostatic capacity of per unit volume becomes the highest as can be known.
In addition, mensuration is with reference to the granular carbon electrode material (carbon electrode material 16 of comparative example 3, median size 9 μ m) " electrolytic solution/electrode materials ratio ", the result is 1.49, granular carbon electrode material (carbon electrode material 13 with reference example 13, median size 9 μ m) 1.37 (with reference to the slips 7 of table 4) are compared, and higher value is shown.This can infer it is that degree of sphericity is low simultaneously because wide with reference to the size distribution of the granular carbon electrode material of comparative example 3, so that the gap of the carbon electrode material in the slip becomes is big, for slipization, needs the more electrolytic solution of volume.
＜reference example 16 〉
Use the granular carbon electrode material (carbon electrode material 1 of reference example 4, median size 4 μ m), with reference to the granular carbon electrode material (carbon electrode material 14 of comparative example 1, median size 15 μ m), they are utilized the order identical with reference example 15 respectively, make electric double layer capacitor, measure electrostatic capacitance.At this moment, the discharging current amount is become 1.0mA from 0.1mA, measure the electrostatic capacitance under each discharging current.Show the result in table 5.
[table 5]
Figure A20078003485200661
* 1: the electrostatic capacitance of per unit weight carbon electrode material.
Electrostatic capacitance greatly reduces when using discharging current with reference to the electric double layer capacitor of the granular carbon electrode material of comparative example 1 to increase as can be known, and uses the reduction of electrostatic capacitance of electric double layer capacitor of granular carbon electrode material of reference example 4 few.Think this be because, under the situation that is carbon electrode material 1, compare with carbon electrode material 14, the median size of electrode materials is little, so 1) because the increase of the ratio that contacts on carbon electrode material and the electrolytical interface, so utilize the absorption of the relative carbon electrode material of electrolyte ion that discharges and recharges, desorption is successfully carried out, and 2) the ionic diffusion length owing to carbon electrode material inside shortens, so utilize the absorption of the relative carbon electrode material of electrolyte ion that discharges and recharges, desorption is successfully carried out, promptly, under the little situation of the median size of carbon electrode material, even the increase discharging current, the desorption of electrolyte ion also can promptly be replied, and under the big situation of median size, the desorption of electrolyte ion can not promptly be replied, and electrostatic capacitance reduces along with the increase of discharging current.
＜reference example 17 〉
Carry out the evaluation of the negative material of using as lithium ion battery or lithium-ion capacitor of granular carbon electrode material of the present invention as described below.Be dissolved in the solution that N-Methyl pyrrolidone 80 weight parts form by the granular carbon electrode material of hybrid reference embodiment 4 (carbon electrode material 4, median size 3 μ m) 100 weight parts fully with polyvinylidene difluoride (PVDF) powder 10 weight parts, it is become slip, this slip is coated Copper Foil (20 μ m are thick), dry, punching press obtains negative pole.This negative pole is cut into 1.5cm * 2.0cm size, as the evaluation negative pole.The in-service evaluation negative pole, as the 1.5cm * 2.0cm size of counter electrode, the metallic lithium of thick 200 μ m, the polyethylene system non-woven fabrics as the thick 50 μ m of dividing plate is assembled into evaluation electricity pool (cell).As reference electrode, use metallic lithium.As electrolytic solution, use with 1mol/L concentration LiPF 6Be dissolved in the solution that forms in the Texacar PC.For relatively, use granular carbon electrode material (carbon electrode material 17, median size 15 μ m) with reference to comparative example 4, make identical evaluation electricity pool.
Described each evaluation electricity pool is discharged and recharged test.Discharge and recharge for the first time on the basis of restriction current potential, charging, discharge are all with 0.2mA/cm 2Carry out.Potential range under the lithium benchmark is from 0V to 2V.Then, with 0.2mA/cm 2, the potential range from 0V to 0.5V is carried out the 2nd time～the 7th time discharge and recharge, and then, with 1.0mA/cm 2, the potential range from 0V to 0.5V is carried out the 8th time～the 15th time discharge and recharge.
With current density 0.2mA/cm 2The 7th time the loading capacity of estimating with 1.0mA/cm 2(capability retention %), for the granular carbon electrode material 4 of reference example 4, is 92% to the ratio of the 15th time the loading capacity of estimating, and for the granular carbon electrode material 17 of reference comparative example 4, is 69%.From this result as can be known, the granular carbon electrode material of the application of the invention even improve current density, also can suppress the reduction of loading capacity.
[preparation of molecular-sieve carbon]
＜reference example 18 〉
Use 35 weight % hydrochloric acid and 36 weight % formalins, preparation is as the mixing solutions 2000g of concentration of formaldehyde 10 weight % and concentration of hydrochloric acid 18 weight %, add 2 weight % aqueous solution 8g of sodium carboxymethyl-cellulose then in this mixing solutions, stirring becomes uniform solution.Then, the temperature with this uniform solution is adjusted to 20 ℃, limit stirring then, the 95 weight % phenol 70g that the limit adding is 30 ℃.Wherein, the concentration of phenols relative response liquid gross weight is that the adding mol ratio of 3.2 weight %, phenol phase PARA FORMALDEHYDE PRILLS(91,95) is 0.11, and the volumetric molar concentration of the hydrochloric acid in the reaction solution is 5.0mol/L.Began reaction solution generation gonorrhoeaization about 120 seconds from adding phenol.Reduce stirring velocity and still continue reaction after gonorrhoeaization, the result is after interpolation phenol begins about 30 minutes, and reaction solution is coloured to lightpink.At this moment, the temperature of reaction solution arrives 30 ℃.After reaction solution is painted, utilize indirect heating, reaction solution is heated to 80 ℃, under this temperature, kept 30 minutes.Then, filter this reaction solution, the filter cake with the water washing of 500g obtains makes it be suspended in the 0.5 weight % ammonia soln of 500g then, carries out 1 hour neutralization reaction under 40 ℃.After the neutralization reaction, use vent fan to attract to filter this suspension,, utilize 50 ℃ drying machine to make its dry 10 hours, obtain the lurid granular phenol resin 21A of 80g thus with the water washing of 500g.
Then, metering granular phenol resin 21A 100 weight parts, coal tar 23 weight parts, the melamine resin aqueous solution 5 weight parts (solids component conversion) of solid component concentration 80 weight %, polyvinyl alcohol water solution (use warm water, the polyvinyl alcohol of the polymerization degree 1700, saponification deg 99% is dissolved into the aqueous solution of 20 weight %) 20 weight parts, W-Gum 24 weight parts, tensio-active agent (Kao Corp's system, PELLEX NB-L) 9.3 weight parts and water 4 weight parts.
Wherein, mix 10 minutes compositions beyond the granular phenol resin 21A, add granular phenol resin 21A then, further mixed 20 minutes.Use two-way extruding granulator (only Paudal Co., Ltd. system, Pelletta-Double EXDF-100 type) to extrude this blend compositions, obtain the cylindrical pellet of diameter 1.3mm * length (height) 1～3mm.Under nitrogen gas stream, with 350 ℃, the particle that thermal treatment obtained in 4 hours, then to the rotary kiln of effective dimensions 100mm φ * 1000mm, supply with 100g/h, under the nitrogen gas stream of 2L/min, carry out carbonizing treatment with under 750 ℃ of 6 hours residence times, treatment temp, under nitrogen gas stream, cool off then, obtain molecular-sieve carbon MSC-1.Figure 15 is the SEM photo on the molecular-sieve carbon MSC-1 surface that obtains in the present embodiment.
＜reference example 19 〉
The granular phenol resin 10A that use obtains in described embodiment 10 in addition, similarly carries out with reference example 18, obtains molecular-sieve carbon MSC-2.
＜reference example 20 〉
Be blended in the melamine resin aqueous solution 4 weight parts (solids component conversion) and water 40 weight parts of granular phenol resin 6A 100 weight parts that obtain among the described embodiment 6, coal tar 10 weight parts, solid component concentration 80 weight %; use two-way extruding granulator (Fuji Paudal Co., Ltd. system then; Fine Ryuzer EXR-60 type) extrudes the blend compositions that obtains, be a granulated into cylindric.Then, use marmelizer (only Paudal Co., Ltd. system, QJ-230 type), granulation obtains the cylindrical pellet of diameter 1mm * length 2～3mm.Under nitrogen gas stream, with 350 ℃, the particle that thermal treatment obtained in 4 hours, the rotary kiln that adds effective dimensions 100mm φ * 1000mm then under nitrogen gas stream, is warming up to 780 ℃, under this temperature, kept 3 hours, under nitrogen gas stream, cool off then, obtain molecular-sieve carbon MSC-3.
＜reference example 21 〉
Mix 36 weight % formalin 556g, 95 weight % phenol 70g and water 530g, prepare mixing solutions 1156g, add 2 weight % aqueous solution 8g of sodium carboxymethyl-cellulose then in this mixing solutions, stirring becomes uniform solution.Then, the temperature with this uniform solution is adjusted to 20 ℃, limit stirring then, the 35 weight % hydrochloric acid 914g that the limit adding is 30 ℃.Wherein, the concentration of phenols relative response liquid gross weight is that the adding mol ratio of 3.2 weight %, phenol phase PARA FORMALDEHYDE PRILLS(91,95) is 0.11, and the volumetric molar concentration of the hydrochloric acid in the reaction solution is 4.7mol/L.Began reaction solution generation gonorrhoeaization about 20 seconds from adding hydrochloric acid.Still continue reaction after gonorrhoeaization, the result is after interpolation hydrochloric acid begins about 30 minutes, and reaction solution is coloured to pink colour.At this moment, the temperature of reaction solution arrives 30 ℃.Then, filter this reaction solution, the filter cake with the water washing of 500g obtains makes it be suspended in the 0.5 weight % ammonia soln of 500g then, carries out 1 hour neutralization reaction under 40 ℃.After the neutralization reaction, use vent fan to attract to filter this suspension,, utilize 50 ℃ drying machine to make its dry 10 hours, obtain the lurid granular phenol resin 5C of 75g thus with the water washing of 500g.
Then, use granular phenol resin 5C, in addition, similarly carry out, obtain molecular-sieve carbon MSC-4 with reference example 20.
＜with reference to comparative example 5 〉
The melamine resin aqueous solution 8 weight parts of granular phenol resin 1C 100 weight parts that metering obtains in described comparative example 1, solid component concentration 80 weight % (solids component conversion), polyvinyl alcohol water solution (use warm water, the polyvinyl alcohol of the polymerization degree 1700, saponification deg 99% is dissolved into the aqueous solution of 20 weight %) 20 weight parts, yam starch 2 weight parts and tensio-active agent (Kao Corp's system, PELLEX NB-L) 0.7 weight part.
Wherein, mix 5 minutes compositions beyond the granular phenol resin 1C, add granular phenol resin 1C then, further mixed 10 minutes.Use two-way extruding granulator (only Paudal Co., Ltd. system, Pelletta-Double EXDF-100 type) to extrude the blend compositions that obtains, obtain the cylindrical pellet of diameter 1.3mm * length (height) 1～3mm.Utilize the method identical, the particle that obtains is handled, obtain molecular-sieve carbon MSC-5 with reference example 18.
＜with reference to comparative example 6 〉
Use 35 weight % hydrochloric acid and 36 weight % formalins, the preparation concentration of formaldehyde is that 10 weight % and concentration of hydrochloric acid are the mixing solutions 2000g of 16 weight %, in this mixing solutions, add 2 weight % aqueous solution 8g of sodium carboxymethyl-cellulose then, stir into uniform solution.Then, the temperature of this uniform solution is adjusted to 20 ℃, adds 30 ℃ 95 weight % phenol 70g then while stirring.Wherein, the concentration of the phenols of relative response liquid gross weight is 3.2 weight %, and the adding mol ratio of the phenol of phase PARA FORMALDEHYDE PRILLS(91,95) is 0.11, and the volumetric molar concentration of the hydrochloric acid in the reaction solution is 4.7mol/L.After the interpolation of phenol about 120 seconds the time, the reaction solution gonorrhoeaization.Reduce stirring velocity and still continue reaction after gonorrhoeaization, the result is after the phenol interpolation begins about 30 minutes, and reaction solution is coloured to lightpink.At this moment, the temperature of reaction solution reaches 30 ℃.Then, filter this reaction solution, the filter cake with the water washing of 500g obtains makes in its 0.5 weight % ammonia soln that is suspended in 500g then, carries out 1 hour neutralization reaction under 40 ℃.After the neutralization reaction, use vent fan to attract to filter this suspension,, utilize 50 ℃ drying machine to make its dry 10 hours, obtain the lurid granular phenol resin 6C of 78g thus with the water washing of 500g.
Then, use granular phenol resin 6C, in addition, similarly carry out, obtain molecular-sieve carbon MSC-6 with reference example 18.
To be summarized in table 6 as the granular phenol resin of raw material.
Figure A20078003485200711
To described molecular-sieve carbon MSC-1～MSC-6, use characterization of adsorption determinator shown in Figure 16, utilize following method, carry out single composition adsorptive capacity of oxygen and nitrogen and measure.In Figure 16, in sample chamber 312 (250ml), add the sample (molecular-sieve carbon) of 30g, shut-off valve 303, magnetic valve 305 are opened valve 302, use vacuum pump 301, outgas 30 minutes, and shut-off valve 302 then.Then, under the state of closing magnetic valve 305, flow into mensuration gas (oxygen or nitrogen), control valve 308, valve 316, gas regulator 309 to measuring cell 311 from bomb 310, pressure in the measuring cell is adjusted to 1.5MPa (gauge pressure), shut-off valve 308 and valve 316.And then, close magnetic valve 305, the interior pressure of measuring in the measuring cell 311 in the specified time changes, and tries to achieve and measures the adsorptive capacity of gas under each time.The pressure of constant pressure valve 306 at this moment is adjusted to 0.3MPa (gauge pressure).Applying pressure transmitter 313,314 is measured the interior pressure of measuring cell 311 and sample chamber 312, and this measured value is used the identical displayed value of displayed value with the JISB7505 Bourdon tube pressure gauge of 1.6 grades of class of precision.
The equation of state PV=nRT of using gas calculates adsorptive capacity Q (mg/g).At this, P is for measuring pressure (mensuration intraventricular pressure), and V is the spatial volume in the mensuration system, and n is the mensuration number of moles of gas in the mensuration system, and R is a gas law constant, and T is for measuring temperature (25 ℃).Utilize the pressure P of the A-stage of measuring cell 0With the pressure P after the absorption tPressure difference, use following formula, calculate the mole number n at initial stage 0With the mole number n after the absorption tPoor Δ n.
N＝PV/RT
Δn＝(n 0-n t)＝(P 0-P t)V/RT
Δ n is the summation of mole number and the mole number of the gas that imports the sample chamber system of the mensuration gas of absorption, so use the mole number Δ n of mensuration gas of absorption that removes the mole number gained of the gas that imports the sample chamber system from Δ n 0, utilize following formula, try to achieve the adsorptive capacity Q of every 1g molecular-sieve carbon.Q (mg/g)=1000 * Δ n 0(mol) * molecular weight (the g/mol)/molecular-sieve carbon weight (g) of adsorbed molecules (mensuration gas)
The mensuration of utilizing described measuring method to obtain is begun oxygen adsorptive capacity Q after 60 seconds O, 60sAnd from measuring the nitrogen adsorptive capacity Q of beginning after 10 seconds N, 10sBe shown in table 7.
[table 7]
Reference example 18 Reference example 19 Reference example 20 Reference example 21 With reference to comparative example 5 With reference to comparative example 6
Molecular-sieve carbon MSC-1 MSC-2 MSC-3 MSC-4 MSC-5 MSC-6
Oxygen adsorptive capacity Q O，60s(mg/g) 25.8 24.7 27.8 24.3 22.8 20.5
Nitrogen adsorptive capacity Q N，10s(mg/g) 4.4 2.0 3.3 3.0 2.7 2.0
In addition, adsorption tower 101a and 101b with described molecular-sieve carbon MSC-1～MSC-6 is filled in PSA formula nitrogen generator unit shown in Figure 14 estimate the nitrogen generating ability.The weight of the molecular-sieve carbon of filling is all identical.
At first, with utilizing the air of compressor 102 compressions to deliver to adsorption tower 101a and 101b, make the pressure of adsorption tower become gauge pressure 9.5kgf/cm 2G utilizes 4 operations of all pressure-absorption up and down-all pressure-regeneration up and down (purging (purge)) to implement the PSA operation.Under the control of sequencer (sequencer), carry out the switching of each operation.It is 2.5Nl/min that the taking-up flow (goods nitrogen amount) of goods nitrogen is unified into corresponding employed every 1kg molecular-sieve carbon, utilizes oxymeter to measure the oxygen concn of the goods nitrogen that obtains, and estimates.In addition, the optimization adsorption time reaches and all presses the time.Table 8 illustrates the oxygen concn (ppm) in the goods nitrogen.In addition, the median size of each molecular-sieve carbon, the coefficient of variation and the particle volume density of size distribution also are shown in table 8 in the lump.Wherein, for molecular-sieve carbon MSC-6, fuse between the carbon progenitor, can not measure median size and coefficient of variation.
[table 8]
Reference example 18 Reference example 19 Reference example 20 Reference example 21 With reference to comparative example 5 With reference to comparative example 6
Molecular-sieve carbon MSC-1 MSC-2 MSC-3 MSC-4 MSC-5 MSC-6
Median size (μ m) 4.2 9.8 1.4 1.4 15
The coefficient of variation of size distribution 0.2 0.6 0.1 0.1 0.7
Particle volume density (g/cc) 1.1 1.0 0.92 0.82 1.0 1.1
Oxygen concn (ppm) 25 60 10 55 100 800
The molecular-sieve carbon of the application of the invention (MSC-1～MSC-4), can reduce the oxygen concn in the goods nitrogen significantly as can be known.At this, in PSA formula nitrogen generator unit, usually known under the situation of using same molecular sieve carbon, if increase the goods nitrogen amount, nitrogen purity drop then, if reduce the goods nitrogen amount, then nitrogen purity rise (for example reference 1: " pressure swing adsorption is integrated " just sharp long industrial technology meeting of Chkawai, issue clear and in January, 61).Figure 17 be expression used yield (that is, and the separation energy of oxygen/nitrogen poor, yield is in being filled with the nitrogen generator unit of molecular-sieve carbon, with yield=(nitrogen amount in goods nitrogen amount/base feed gas) expression.) figure of the purity of goods nitrogen in the PSA formula nitrogen generator unit of different molecular-sieve carbon and the relation of goods nitrogen flow.Like this, illustrate in use under the situation of molecular-sieve carbon of high yield, can improve goods nitrogen purity with same nitrogen flow.That is, such relation shows: used can situation with the molecular-sieve carbon of the goods nitrogen of same goods nitrogen amount generation higher degree under, under the condition of same goods nitrogen purity, can further increase the goods nitrogen amount.
Thereby, the molecular-sieve carbon of the application of the invention, compared with the past, can make the goods nitrogen amount bigger, so can utilize the improvement of nitrogen recovery, greatly improve the nitrogen generating capacity of per unit weight molecular-sieve carbon.
In addition, the measuring method of the various characteristics for granular phenol resin, granular carbon electrode material and molecular-sieve carbon and condition determination are as described below.
(1) non-thermofusible and thermally melting: about 5g granular phenol resin sample is inserted between 2 thick stainless steel plates of 0.2mm, utilize and heat in advance to 100 ℃ pressing machine, total load with 50kg, punching press 2 minutes, at this moment, because fusion and/or fusion granular phenol resin take place form in the absence about being bonded to each other between flat board or distortion of resol particle or the resol particle, judge " non-thermofusible ".In addition, under this high-temperature pressurizing condition, because fusion and/or fusion, granular phenol resin forms under the dull and stereotyped situation, judges " thermally melting ".
(2) boil the dissolve with methanol degree: the about 10g granular phenol resin of precision weighing sample, among the about 500mL of anhydrous actually methyl alcohol, heating under refluxing in 30 minutes, the glass filter with No.3 filters then, and then with the resistates on the anhydrous methanol cleaning glass strainer of about 100mL.Then, with the resistates on the glass filter after the washing in 5 hours of 40 ℃ of dryings, this resistates of precision weighing then.From dried residue weight and the granular phenol resin example weight that obtains,, calculate and boil the dissolve with methanol degree based on following formula.
Boil dissolve with methanol degree (weight %)=(granular phenol resin example weight and dried residue weight poor)/(granular phenol resin example weight) * 100
(3) median size: be to use carbon electrode material or granular phenol resin, the preparation aqueous dispersions, the cumulative frequency of utilizing the frequency distribution of laser diffraction formula particle size measurement machine (day machine dress (strain) system Microtrac X100) instrumentation is 50% value.
(4) simple grain rate: be meant and in water droplet, disperse carbon electrode material or granular phenol resin, utilize opticmicroscope to observe, in containing the visual field of selecting at random of 300 progenitors of having an appointment, this when the total number of counting progenitor and the number of simple grain is than the total number of simple grain number/progenitor.
(5) coefficient of variation of size distribution: use carbon electrode material or granular phenol resin, the preparation aqueous dispersions from utilizing the frequency distribution of laser diffraction formula particle size measurement machine (day machine dress (strain) system MicrotracX100) instrumentation, utilizes following formula [1] to calculate.
The coefficient of variation of size distribution=(d 84%-d 16%)/(2 * median size) [1]
At this, in above-mentioned formula [1], d 84%, d 16%It is respectively the particle diameter of expression cumulative frequency 84%, 16% in the frequency distribution that obtains.The earthquake coefficient is under the situation below 0.65, to judge to become to have narrow size-grade distribution.
(6) degree of sphericity: be meant in observation by light microscope, select to contain the visual field of 300 progenitors of having an appointment randomly, select the minimum progenitor of 10 aspect ratios (being the ratio of minor axis/major diameter), to these 10 progenitors, the mean value of these 10 aspect ratios when measuring the aspect ratio in its shadow area respectively.
(7) free phenol content: be defined as the value of utilizing test as described below to calculate.That is, the about 10g of precision weighing granular phenol resin sample, in the methyl alcohol of 190mL, extraction is 30 minutes under refluxing, and filters with glass filter.Utilize the phenols concentration in the quantitative filtrate of liquid chromatography, calculate the phenols weight in this filtrate.With the ratio of this phenols weight and example weight is that phenols weight/granular phenol resin example weight is as " free phenol content ".
(8) cl content: working sample (non-thermofusible resol particle) and mensuration are pressurizeed with binder powders, become to measure and use particle, use the system fluorescent x-ray analyzer ZSX100E of Co., Ltd. Neo-Confucianism then, utilize the EZ scan pattern to carry out x-ray fluorescence analysis.That utilizes the phenolic resin curing thing infers molecular formula (C 7H 6O 1) the Alpha-ray diffracted intensity measured value of stdn chlorine K, as cl content (wt/wt).
(9) specific area: the accurate about 0.1g carbon electrode material of weighing, in the dedicated slot (cell) of the full-automatic gas adsorption unit of the high precision of packing into then BELSORP-miniII (Japanese Bel Co., Ltd. system), utilize the B.E.T method that nitrogen adsorbs to try to achieve.
(10) median size of the carbon progenitor of formation molecular-sieve carbon: under the observation that utilizes the scanning electron microscope photo, to molecular-sieve carbon surface and surface of fracture, select the visual field respectively randomly, when each visual field is at random selected to confirm as 100 carbon progenitors of globular, utilize the mean value of the particle diameter of these 200 carbon progenitors that the SEM photo measures.In addition, " standard deviation of carbon initial size " is the above-mentioned standard deviation that can confirm as the particle diameter of 200 carbon progenitors of globular.
(11) coefficient of variation of the size distribution of the carbon progenitor of formation molecular-sieve carbon: utilize following formula to try to achieve.
The coefficient of variation of the size distribution of carbon progenitor=(standard deviation of carbon initial size)/(median size of carbon progenitor)
Please be careful: this time disclosed embodiment and embodiment are illustration from all senses, are not restrictive embodiment and embodiment.Scope of the present invention is not described explanation and representing with claim, is included in and the meaning of claim equalization and the whole change in the scope.

Claims (18)

1. non-thermofusible granular phenol resin, wherein,
Median size is below the 20 μ m, and the simple grain rate is more than 0.7.
2. non-thermofusible granular phenol resin according to claim 1, wherein,
Median size is below the 10 μ m.
3. non-thermofusible granular phenol resin according to claim 1, wherein,
The coefficient of variation of the size distribution shown in the following formula [1] is below 0.65,
The coefficient of variation of size distribution=(d 84%-d 16%)/(2 * median size) [1]
At this, d 84%, d 16%It is respectively the particle diameter of expression cumulative frequency 84%, 16% in the frequency distribution that utilizes the laser diffraction and scattering method to obtain.
4. non-thermofusible granular phenol resin according to claim 1, wherein,
Degree of sphericity is more than 0.5.
5. non-thermofusible granular phenol resin according to claim 1, wherein,
Free phenol content is below the 500ppm.
6. non-thermofusible granular phenol resin according to claim 2, wherein,
The coefficient of variation of the size distribution shown in the described formula [1] is below 0.65, and degree of sphericity is more than 0.5, and free phenol content is below the 500ppm.
7. according to any described non-thermofusible granular phenol resin in the claim 1～6, wherein,
Cl content is below the 500ppm.
8. non-thermofusible granular phenol resin according to claim 7, wherein,
Cl content is below the 100ppm.
9. the manufacture method of a non-thermofusible granular phenol resin, it is the method that is used to make the described non-thermofusible granular phenol resin of claim 1, wherein,
Comprise:
(1) granular phenol resin forms operation, its by the volumetric molar concentration in reaction solution be an acidic catalyst more than the 2.0mol/L and colloid protective agent in the presence of, in aqueous medium, make aldehydes and phenols reaction formation granular phenol resin;
(2) non-hot melt operation, its heating contain the reaction solution of described granular phenol resin and form the granular phenol resin of non-thermofusible;
(3) separation, washing procedure, it separates the granular phenol resin of described non-thermofusible and washs from reaction solution.
10. the manufacture method of non-thermofusible granular phenol resin according to claim 9, wherein,
Described an acidic catalyst is a hydrochloric acid, and described aldehydes is formaldehyde, paraformaldehyde or their mixture.
11. the manufacture method of non-thermofusible granular phenol resin according to claim 9, wherein,
The adding mol ratio of the described relatively aldehydes of described phenols is below 0.9.
12. the manufacture method of non-thermofusible granular phenol resin according to claim 9, wherein,
Described colloid protective agent is the water-soluble polysaccharide analog derivative.
13. the manufacture method of non-thermofusible granular phenol resin according to claim 9, wherein,
Comprise in described separation, the washing procedure: use the operation that the fluidity medium washs the granular phenol resin of described non-thermofusible more than a kind that is selected from alcohols and the alkaline aqueous solution.
14. the manufacture method of non-thermofusible granular phenol resin according to claim 13, wherein,
Under the temperature more than the second-order transition temperature of the granular phenol resin of described non-thermofusible, used the washing of described alcohols.
15. a compositions of thermosetting resin, wherein,
Contain the described non-thermofusible granular phenol resin of claim 7, Resins, epoxy and solidifying agent.
16. compositions of thermosetting resin according to claim 15, wherein,
Also contain mineral filler.
17. a sealing material for semiconductor, it is formed by the described compositions of thermosetting resin of claim 15.
18. an adhesive for semiconductor, it is formed by the described compositions of thermosetting resin of claim 15.
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