WO2006129360A1

WO2006129360A1 - Method for producing carbon black being surface-treated with organic compound

Info

Publication number: WO2006129360A1
Application number: PCT/JP2005/010164
Authority: WO
Inventors: Masafumi Uchida; Shingo Asai; Chihi Go
Original assignee: Konica Minolta Business Technologies, Inc.
Priority date: 2005-06-02
Filing date: 2005-06-02
Publication date: 2006-12-07
Also published as: JP5228483B2; JPWO2006129360A1

Abstract

A method for producing carbon black, which comprises a surface treatment step of treating the surface of a carbon black containing secondary particles comprising an aggregate structure of basic particles with an organic compound having or capable of forming an active free radical, and a grafting step of grafting the organic compound at least to a surface separated from secondary particles.

Description

Specification

Method for producing carbon black surface-treated with organic compound

Technical field

The present invention relates to a method for producing carbon black grafted with an organic compound. It is related to carbon black, which is widely used in many industries such as rubber industry, plastic industry, oil-based ink, paint, and dry battery, and it is a method for producing carbon black to make it exist stably in the state of primary particles. .

Background art

[0002] Since carbon black is excellent in colorability, conductivity, weather resistance, chemical resistance, etc., it is widely used for various purposes such as plastic and elastomer reinforcing agents and fillers.

[0003] Normally, carbon black exists as secondary particles, ie, aggregates (structures) in which a plurality of basic particles are chemically and Z or physically bonded (Fig. 4). This structure has a complex agglomerated structure that is branched into irregular chains, and its shape is uneven, so even if dispersed in a desired medium, uniform colorability, conductivity, etc. It was difficult to obtain.

[0004] Conventional strength Improvement of carbon black has been studied, but it has been limited to the improvement of the agglomeration dimension (low agglomerate, medium agglomerate, high agglomerate, etc.) and surface properties of the agglomerates. The That is, it improves the properties of the aggregate, and no report has been made on improving the non-uniformity of the shape of the aggregate. In addition, there is no report on the agglomeration force focusing on primary particle formation.

[0005] In addition, since carbon black is in the form of powder or granules, it is rarely used alone. Usually, carbon black is applied to a solid substrate such as rubber resin or a liquid such as water or a solvent. Disperses evenly and exhibits its properties. However, since carbon black has a weak affinity with other substances such as organic polymers, water, and organic solvents compared to the cohesion between particles, it can be mixed uniformly or mixed under normal mixing or dispersion conditions. It was very difficult to disperse. In order to solve this problem, the surface of the carbon Many studies have been made to improve the dispersibility of carbon black by coating it with an agent and increasing the affinity with a solid substrate or liquid.

[0006] For example, carbon black grafted with an organic compound obtained by polymerizing a polymerizable monomer in the presence of carbon black (structure) can be obtained by appropriately selecting the type of polymerizable monomer. Attention has been paid to the fact that hydrophilicity and Z or lipophilicity can be appropriately changed (for example, US Pat. No. 6,417,283). However, with the conventional method, even if the dispersibility with respect to the medium can be improved, the shape cannot be made uniform. Also, such grafted carbon black was in a form grafted on the surface of the structure.

Disclosure of the invention

Problems to be solved by the invention

[0007] Accordingly, the present invention has been made in view of the above-described problems, and an object thereof is to provide a novel method for producing carbon black grafted with an organic compound.

Another object of the present invention is to provide a method for producing primary particles of carbon black grafted with an organic compound.

Another object of the present invention is to provide a carbon black production method capable of improving dispersibility in a polymer matrix of carbon black or in an organic solvent.

Means for solving the problem

[0008] The above-mentioned objects are achieved by the following (1) to (5).

(1) a surface treatment step for treating the surface of carbon black containing secondary particles that also have a force having active free radicals or an organic compound that can be generated and at least a primary particle aggregate (structure) force; and at least a secondary particle A method for producing carbon black, which has a grafting step in which the organic compound is grafted onto the separated separation surface.

(2) The method for producing carbon black as described in (1) above, further comprising a step of applying a mechanical shearing force to at least the surface treatment step or the grafting step.

(3) The step of imparting the mechanical shear force is at least equal to or higher than the melting point of the organic compound. The method for producing carbon black as described in (2) above, wherein the temperature is a temperature.

(4) The method for producing carbon black as described in (1), (2) or (3) above, wherein the organic compound contains at least a phenol compound and / or an amine compound

(5) The method for producing carbon black according to (1) above or (4), wherein 5 to 300 parts by weight of the organic compound is added to 100 parts by weight of carbon black.

[0009] The present inventors have conducted research in view of at least the above problems. The inventors of the present invention have noticed that, even if carbon black aggregates are made finer, they are aggregated again due to the strength and cohesive strength between carbon blacks. In other words, it was studied to eliminate the reaggregation site so that the aggregate would not be reaggregated even if it was made fine. As a result, the aggregate surface is treated with an organic compound to reduce the number of re-aggregation sites, cracks are formed at the joints between the basic particles of the aggregate, and the organic compound is grafted to the cracks, eventually becoming stable. It was found that primary particles can be obtained.

The stable primary particles have a uniform shape as compared with the aggregates, and the design efficiency can be improved in controlling the powder characteristics resulting from the shape. In addition, it was an unexpected effect that the dispersibility of carbon black could be improved during this manufacturing process.

[0010] The primary particles referred to in the present application will be described. Ordinary carbon black exists in the form of aggregates, but these aggregates are in a form in which a plurality of basic particles are chemically aggregated physically. As used herein, primary particles refer to the basic particles. However, it does not refer to the basic particles in the state of constituting the aggregate, but refers to particles that are separated and separated stably from the aggregate force. As used herein, secondary particles refer to aggregates formed by aggregation of basic particles. Here, secondary aggregates in which aggregates are aggregated are also collectively referred to as secondary particles in the present application.

FIG. 2 is a diagram illustrating the relationship between secondary particles and basic particles. The state in which the basic particles are aggregated is defined as secondary particles. Fig. 3 shows the state in which the basic particles constituting the secondary particles are separated from the secondary particles and exist stably, and the particles existing as a single basic particle are defined as primary particles.

[0011] Hereinafter, this will be described in detail. Surface treatment process for treating the surface of carbon black containing secondary particles that have active free radicals or organic compounds that can be produced and also have at least primary particle agglomeration (structural) forces

In this step, the surface of the carbon black aggregate is surface-treated with the organic compound.

In this step, radicals are generated on the surface of the structure, which is the smallest agglomeration unit, by heat or mechanical force, and the surface is treated with an organic compound that can capture these radicals. This step effectively reduces the re-aggregation sites that have been agglomerated due to the strong agglomeration force between the carbon blacks, and prevents the primary particles of the structure and carbon black from aggregating and adhering.

Here, the surface treatment includes a treatment for adsorbing the surface with an organic compound and a treatment for grafting the organic compound. In order to stabilize the particles after the primary particles are formed, it is preferable that the organic compound is grafted on the entire surface of the secondary particles on a portion other than the surface separated from the secondary particle force! In order to make the primary particles stably exist after the grafting step described later, it is preferable to graft an organic compound on the carbon black surface in this step.

[0013] As the surface treatment method, for example, the carbon black aggregate and the force having an active free radical or an organic compound that can be generated are mixed to perform the surface treatment. In this surface treatment, it is preferable to include a mixing step for applying a mechanical shearing force. In other words, the surface of the carbon black secondary particles is activated in the process of applying mechanical shearing force, and the organic compound itself is also activated by shearing force, resulting in a so-called radical state. As a result, it is estimated that the drafting of organic compounds on the carbon black surface is likely to be promoted.

[0014] In the surface treatment step, an apparatus capable of applying a mechanical shearing force is preferable. In the present invention, the mixing apparatus used in the surface treatment process is preferably a polylab system mixer (manufactured by Thermo Electron), a refiner, a single screw extruder, a twin screw extruder, a planetary screw extruder. Machines, cone-screw extruders, continuous kneaders, sealed mixers, Z-type kneaders, etc. can be used.

[0015] When the above apparatus is used during the surface treatment process, mixing in the mixing zone in the mixer It is preferable to set the material fullness to be 80% or more. The degree of fullness is calculated by the following formula.

Z = Q / A

Z: Filling degree (%) Q: Filling volume (m ² ) A: Mixing space void volume (m ² )

[0016] That is, a mechanical shearing force can be uniformly applied to the entire particles by setting a high filling state during mixing. If the degree of fullness is low, the transmission of shearing force is insufficient, and grafting, which makes it difficult to increase the activity of carbon black and organic compounds, may not progress.

[0017] During mixing, the temperature of the mixing zone is preferably equal to or higher than the melting point of the organic compound, preferably within the melting point + 200 ° C, and more preferably within the melting point + 150 ° C. When plural kinds of organic compounds are mixed, it is preferable to set the temperature with respect to the melting point of the organic compound having the highest melting point.

[0018] At the time of mixing, surface treatment is performed by using electromagnetic waves such as ultrasonic waves, microwaves, ultraviolet rays and infrared rays, ozone action, oxidant action, chemical action and Z or mechanical shear force action in combination. It is possible to change the process time. The mixing time is about 15 seconds to 120 minutes depending on the desired degree of surface treatment. Preferably 1 to: LOO minutes.

The organic compound used for the surface treatment is preferably added in a range of 5 to 300 parts by weight with respect to 100 parts by weight of the carbon black to perform the surface treatment step. More preferably, it is 10 to 200 parts by weight. By adding the organic compound in such a range, the organic compound can be uniformly attached to the surface of the bonbon black, and further, sufficient to attach to the separation surface generated when the secondary particles are formed. The amount can be made small. For this reason, it is possible to effectively prevent the decomposed primary particles from aggregating again, and carbon black produced by an organic compound that is excessively present in the finished carbon black, which is generated when added in excess of the amount of added calories. The possibility of losing inherent properties is reduced.

[0020] The grafting step is a step of grafting the organic compound onto the separation surface of the primary particles separated by at least the secondary particle force. In this process, the organic compound can be grafted to the newly formed separation surface on the primary particles from the secondary particles. Primary particles can be stabilized and present, and furthermore, primary particles uniformly treated with an organic compound can be formed on the surface, so that good dispersibility can be ensured. .

[0021] This step is a step of converting the carbon black that has undergone the surface treatment step into stable primary particles. That is, for example, a mechanical shearing force is applied to the carbon black surface-treated in the above-described process, and secondary particles are cleaved to form primary particles, and at the same time, the organic material is applied to the cleavage plane, so-called separation plane. The compound is grafted to form primary particles and at the same time stabilized. For example, a mechanical shearing force is applied to the carbon black surface-treated with the organic compound to cause cracks in the agglomerated portion of the basic particles present in the secondary particles, or at the same time or thereafter, the organic compound is at least in that portion. Is intended to suppress reaggregation of the formed basic particles (primary particles). The force is continuously applied to one bon black, and energy (for example, mechanical shearing force) is continuously applied to enlarge the cracked part, and the organic compound is grafted to the cracked part. Finally, the basic particles become primary particles. At the time of separation, there is almost no agglomerated portion, and primary particles can be stably present. In this case, since the same mechanical shear force is imparted to the added organic compound, the organic compound itself is also activated by the mechanical shear force, and grafting is promoted.

The “carbon black grafted with an organic compound” as used herein refers to carbon black in which an organic compound portion is grafted onto a carbon black portion. Furthermore, as used herein, “grafting” is defined by Jean-Baptiste Donnet et al. In his book “Carbon Black” (published on May 1, 1978 by Kodansha). An irreversible addition of an organic compound to a substrate such as carbon black.

The grafting step is a step of grafting at least a force having an active free radical at the cracked portion or an organic compound that can be generated, but a graph toy wrinkle may simultaneously occur in addition to the cracked portion. Also, it may be executed simultaneously or as a separate process during the progress of the surface treatment process.

[0023] Means for causing the above cracks include irradiation of electromagnetic waves such as ultrasonic waves, microwaves, ultraviolet rays, and infrared rays, ozone action, action of oxidant, chemical action, and mechanical shear force action. Various forms are possible.

In the present invention, it is preferable to cause a crack by applying at least a mechanical shearing force. It is desirable to place the carbon black (structure) surface-treated with an organic compound in a place where mechanical shearing force is applied and to adjust the surface-treated carbon black from the structure to primary particles. When applying this mechanical shearing force, other means for causing cracks described above may be used in combination.

The mechanical shearing force here is preferably a shearing force similar to the mechanical shearing force in the surface treatment step described above.

[0024] As described above, the action of mechanical shearing force may generate active free radicals by breaking the chain inside carbon black, which is not a force when carbon black is atomized from aggregates to primary particles. Is possible. The organic compounds having or capable of generating free radicals used in the present invention may be cleaved under the action of, for example, mechanical shear force fields or generate forces having active free radicals. Contains possible organic compounds. When active free radicals cannot be formed sufficiently under the action of mechanical shearing force, they are exposed to electromagnetic waves such as ultrasonic waves, microphone mouth waves, ultraviolet rays, and infrared rays, under the action of ozone, or under the action of oxidizing agents. Can supplement the number of active free radicals.

[0025] Polylab system mixer (manufactured by Thermo Electron), refiner, single screw extruder, twin screw extruder, planetary screw extruder, cone screw extruder, continuous kneading machine, etc. Machines, sealed mixers, Z-types, etc. can be used. The conditions for applying the mechanical cutting force are preferably the same as those for the surface treatment described above from the viewpoint of effectively applying the mechanical shearing force. In addition, by using these devices, mechanical energy can be imparted to the entire particle uniformly effectively and continuously, so that grafting can be performed efficiently and uniformly. Is preferable.

[0026] In the surface treatment step and the grafting step, the organic compound to be added may be gradually or intermittently added so that the organic compound becomes a predetermined amount. Add a certain amount in advance at the start of the surface process, and run until the grafting process! /.

[0027] The organic compound used in the grafting process as the material to be grafted with the organic compound used in the surface treatment process as the surface treatment material may be the same or different. Yes.

[0028] The grafting step described above is preferably carried out under conditions that are not lower than the melting point of the organic compound used. The upper limit of the temperature condition is particularly preferably within the melting point of the organic compound + 200 ° C., more preferably within the melting point + 150 ° C., from the viewpoint of promoting the graft reaction and fragmentation of the primary particles. When a plurality of types of organic compounds are mixed, it is preferable that the temperature is set with respect to the melting point of the organic compound having the highest melting point.

[0029] The mechanical shearing force application time described above depends on the amount and scale of the sample, but in order to fully execute the process, it is 1 minute or more and within 100 minutes to improve the uniformity of the reaction. It is preferable from the viewpoint.

[0030] In the production method of the present invention described above, it is preferable to apply mechanical shear force by mixing carbon black and an organic compound described later without using a solvent. As the reaction gives a shearing force at or above the melting temperature of the organic compound, the organic compound becomes liquid, so that it can evenly fit on the surface of the solid carbon black and effectively advance the reaction. . When a solvent is used, the uniformity is improved, but the energy transfer when applying a mechanical shearing force is reduced, so the level of activity is reduced and the graphing is effective. It is estimated that it will be difficult to proceed.

[0031] 2) Carbon black

Examples of the carbon black that can be used include carbon black having a force aggregate structure that can be used for any commercially available one such as furnace black, channel black, acetylene black, and lamp black. The aggregate structure means a carbon black formed into secondary particles, which is formed by agglomerating primary particles, which are basic particles, and has a structure structure, and also has a so-called aggregate force of primary particles. In addition, in order to facilitate the grafting reaction of the organic compound on the carbon black surface, sufficient carbon-containing functional groups such as carboxyl groups, quinone groups, phenol groups, and rataton groups on the surface of the carbon black and the layer surface periphery. It is desirable that there are many active hydrogen atoms. Therefore, the carbon black used in the present invention preferably has an oxygen content of 0.1% or more and a hydrogen content of 0.2% or more. In particular, the oxygen content is 10% or less and the hydrogen content is 1% or less. Where oxygen content, hydrogen content are Respectively, it is obtained by dividing the number of oxygen elements or hydrogen elements by the total number of elements (sum of carbon, oxygen and hydrogen elements).

By selecting such a range, the surface treatment of the organic compound onto the carbon black can facilitate the graft reaction.

[0032] Further, by selecting the above-mentioned range, it is possible to reliably graft an organic compound having a free radical! /, Or generating force, and the reaggregation preventing effect is enhanced. When the oxygen content and hydrogen content on the surface of carbon black are below the above ranges, gas phase oxidation such as heated air oxidation or ozone oxidation, or nitric acid, hydrogen peroxide, potassium permanganate, sodium hypochlorite Alternatively, the oxygen content and hydrogen content of carbon black may be increased by a liquid phase acid treatment with bromine water or the like.

[0033] 3) Organic compounds

The organic compound used to surface-treat carbon black in the surface treatment process or to graft onto the carbon black in the grafting process is a force with free radicals or an organic compound that can be generated. .

In an organic compound capable of generating a free radical, the conditions for generating the free radical are not particularly limited. However, in the case of the organic compound used in the present invention, a free radical is present during the grafting process. It is necessary to be in a state. The organic compound includes at least a compound capable of generating a free radical by electron transfer, a compound capable of generating a free radical by thermal decomposition, and a compound capable of generating a free radical as a result of the structure of the compound being cleaved by shearing force or the like. preferable.

[0034] Regarding the force having a free radical used in the present invention or an organic compound that can be generated, the molecular weight is preferably 50 or more, and the upper limit is preferably 1500 or less. . By adopting an organic compound having such a molecular weight range, it is possible to obtain a carbon black whose surface is substituted with an organic compound having a somewhat large molecular weight, and re-aggregation of the formed primary particles can be suppressed. In addition, by setting the molecular weight to 1500 or less, the characteristics of the carbon black itself, which does not cause excessive surface modification and the characteristics of the organic compound grafted on the surface, are sufficiently exhibited. Can be demonstrated. [0035] The organic compounds used in the surface treatment step and the grafting step may be the same or different, and plural types of organic compounds may be added to each step. In order to control the reaction temperature and simplify other conditions, it is desirable that the organic compounds used in the surface treatment step and the grafting step be the same.

[0036] Examples of the organic compound include organic compounds capable of capturing free radicals on the carbon black surface of phenolic compounds, amine compounds, phosphate ester compounds, and thioether compounds. it can.

[0037] As these organic compounds, so-called anti-oxidation agents and light stabilizers are preferable. More preferably, a hindered phenol and a hindered amine system can be mentioned. Moreover, antioxidants of phosphate ester compounds, thiol compounds, and thioether compounds can also be used. A plurality of these organic compounds may be used in combination. Depending on the combination, various surface treatment characteristics can be exhibited.

These organic compounds preferably do not have an isocyanate group in order to reliably control the reaction. That is, when an organic compound having excessive reactivity is used, a uniform grafting reaction is difficult to be formed, and it may be necessary to use a large amount of reaction time and amount of the organic compound. The reason for this is not clear, but when an organic compound with high reactivity as described above is used, the reaction proceeds in addition to the surface active sites and is formed by the mechanical shear force that is the original purpose. It is presumed that the reaction to the active point is insufficient.

[0038] Specific examples of the organic compound are shown below.

[0039] Phenolic compounds

(Organic compounds 1-88)

(Organic compound 1)

CH ₃

HO— C- CH ₃

CH ₃

(Organic compound 2)

(Organic compound 3)

(Organic compound 4)

(Organic compound 5)

(Organic compound 6)

(Organic compound 7)

(Organic compound 8)

(Organic compound 9)

(Organic compound 11)

(Organic compound 14)

(Organic compound 15)

(Organic compound 16)

(Organic compound 17)

(Organic compound 18)

(Organic compound 19)

(Organic compound 20)

(Organic compound 21)

(Organic compound 22)

(Organic compound 23)

(Organic compound 24)) 2

(Organic compound 25)

(Organic compound 26)

(Organic compound 27)

C (CH ₃ ) ₃ C (CH ₃ ) ₃ (Organic compound 29)

(Organic compound 30)

(Organic compound 31)

(Organic compound 33)

(Organic Compound 34)

(Organic compound 35)

(Organic compound 37)

(Organic compound 38)

(Organic compound 39)

(Organic compound 40)

(Organic compound 42)

(Organic compound 44) 0164

(Organic compound 46)

(Organic compound 47)

(Organic compound 48)

(Organic compound 49)

(Organic compound 50)

(Organic compound 51) a OH

OH

(Organic compound 52)

(Organic compound 53)

(Organic compound 54)

(Organic compound 55)

(Organic compound 56)

(Organic compound 57)

(Organic compound 58)

(Organic compound 59)

(Organic compound 60)

(Organic compound 61)

(Organic Compound 62)

(Organic compound 63)

R = ^C 9 ^H 19

(Organic compound 64)

(Organic compound 65)

(Organic compound 66)

(Organic compound 67)

(Organic compound 68)

(Organic Compound 69)

(Organic compound 70)

(Organic compound 71)

(Organic compound 72)

(Organic compound 73)

(Organic compound 74)

(Organic compound 75)

(Organic compound 76)

(Organic compound 78)

(Organic compound 79)

(Organic compound 81)

CH

(Organic compound 82)

(Organic compound 83)

(Organic compound 84)

(Organic compound 85)

(Organic compound 87)

(Organic compounds 89-144) (Organic compounds 89)

(Organic compound 90)

(Organic compound 91)

(Organic compound 92)

(Organic compound 93)

R = C ₇ H ₁₅ (Organic compound 94)

R = C _S H ₁₇ (Organic compound 95)

R = C ₉ H ₁ (Organic compound 96)

R = 10H21 (Organic compound 97)

(Organic compound 98)

(Organic compound 99)

(Organic compound 100)

(Organic compound 101)

(Organic compound 102)

(Organic compound 103)

(Organic compound 104)

(Organic compound 105)

(Organic compound 106)

R = C ₇ H ₁₅

(Organic compound 107)

R = C _S H ₁₇

(Organic compound 108)

(^^) — NH— (? ^^^) — NHR

R = C ₉ H ₁₉

(Organic compound 109)

(Organic compound 110)

(Organic compound 111)

(Organic compound 112)

(Organic compound 113)

(Organic compound 114) > i— N H- (CH ₂ ) ₃ -NH ~

(Organic compound 115)

(Organic compound 116)

(Organic compound 117)

(Organic compound 118)

(Organic compound 119)

(Organic compound 120)

(Organic compound 121)

CH ₃ I

○ ○ -N HCH CHCH ₂ ○ CC = CH ₂

II

OH 〇

(Organic compound 122)

(Organic compound 123)

(Organic compound 124)

CH ₃

(Organic compound 125)

(Organic Compound 127)

(Organic Compound 128)

(Organic compound 129)

(Organic compound 130)

(Organic Compound 131)

(Organic Compound 132)

(Organic compound 135)

(Organic compound 136)

(Organic compound 137)

(Organic compound 138)

(Organic Compound 139)

(Organic compound 140)

(Organic compound 141) N \ NN

R = — NHC ₆ H ₄ NHC ₆ H ₅

(Organic compound C RI

142)

(Organic compound 143)

(Organic compound 144)

Thiol and thioether compounds

(Organic compounds 145-153)

(Organic compound 145)

(Organic compound 146)

CS-Zn-SC (Organic compound 147)

(Organic compound 148)

(Organic compound 149)

(Organic compound 150)

(Organic Compound 151)

(Organic Compound 152)

CH ₂ -CH2-COO -C _{1 2} H ₁₅ S

CH 2 H 2-COO-C- | 2H-| 5

(Organic compound 153)

CH 1 CH 2 1 37 s

CH ₂ -CH ₂ -COO-C _{1 s} H ₃₇ Phosphate compounds (Organic compound 154 160) (Organic compound 154)

(Organic compound 155)

(Organic compound 156)

(Organic compound 157)

(Organic compound 158)

(Organic compound 159)

(Organic compound 160)

Phenolic organic compounds (Organic compound 161)

[0040] The number average particle diameter of the ferret diameter of the carbon black used in the present invention is preferably 20 to 500 nm. Further, the carbon black obtained by the present invention preferably has a ferret diameter number average particle diameter in the range of 5 to 300 nm. Preferably, 10 to: LOOnm. By taking such a range, it becomes possible to remarkably obtain the mechanical characteristics when a resin molding, a rubber composition, or the like is formed.

Here, the measurement target of the number average particle diameter of the ferret diameter is primary particles and secondary particles of carbon black that exist stably. In the case of carbon black existing as an aggregate, the aggregate is an object to be measured, and the basic particles in the aggregate are not measured.

In addition, the number average particle diameter of the primary diameter of the primary particles is preferably 2 to: L00 nm, and particularly preferably 3 to 80 nm.

In order to control this number average particle size, the carbon black existing as aggregates is appropriately selected so that the basic particle diameter of the carbon black falls within the above range, or the aggregate is divided into primary particles. This can be achieved by changing the time conditions.

[0041] The number average particle diameter of the ferret diameter can be observed with an electron microscope.

When calculating the number average particle size of the Frere diameter from a single carbon black, the image is magnified 100,000 times with a scanning electron microscope (SEM), and 100 particles are appropriately selected and calculated.

When determining the average particle size of carbon black, such as resin moldings and rubber compositions, take a picture with a transmission electron microscope (TEM) at a magnification of 100,000, and select 100 particles as appropriate. It may be calculated.

The ferret diameter used in the present invention represents the maximum length in any one direction of each carbon black particle in the plurality of carbon black particles photographed by the electron microscope. The maximum length is the distance between parallel lines when two parallel lines that are perpendicular to one of the above directions and touch the outer diameter of the particle are drawn. For example, in FIG. 1, an arbitrary direction 201 is defined for a photograph 300 of a carbon black particle 200 taken with an electron microscope. The distance between the two straight lines 202 perpendicular to the arbitrary one direction 201 and in contact with each force single bon black particle 200 is the free diameter 203.

[0043] The carbon black obtained by the production method of the present invention can be applied to compositions in various fields. In addition, the carbon black of the present invention is excellent in dispersibility in various vehicles, and at the same time has primary particles. Therefore, these various compositions also have extremely excellent characteristics. Furthermore, since excellent mechanical properties are drawn out, an excellent rubber composition can be obtained, and a resin composition that is hardly deteriorated can be obtained.

[0044] In order to obtain compositions in various fields, a desired composition can be prepared by employing various known methods except for containing the carbon black of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

[0045] In the following, the present invention will be further described based on examples. This example does not limit the present invention.

[Example 1]

100 parts by weight of carbon black (N220, manufactured by Mitsubishi Chemical Co., Ltd .: secondary particle size = 210 nm) and 50 parts by weight of organic compound 48 (molecular weight = 741, melting point = 125 ° C) to the same carbon black And put into a twin screw extruder. This twin-screw extruder was mixed with two screws, and PCM-30 (manufactured by Ikegai Seisakusho) was used. It was not modified so that it could be kneaded continuously, but was modified so that it could be stirred with two screws while the outlet was sealed.

[0047] First processing condition

After both were put into a twin screw extruder, stirring was performed in a state where the first temperature condition (Tpl) was heated to 150 ° C. (melting point + 25 ° C.). Both materials were put into the apparatus so that the degree of fullness was 94% during stirring. The rotation speed (Svl) was set at 30 rotations per minute by screw rotation, and the treatment time (T1) was set at 10 minutes, and stirring was performed. Sampling was performed in this state, and the state of grafting was confirmed by extraction with Sotasley. It was found that the grafting rate was about 30%. That is, it is confirmed that the grafted wrinkles are progressing on the surface. [0048] Second processing condition

Next, the number of revolutions (Sv2) is set to 50 revolutions per minute, the second temperature condition (Tp2) is set to 170 ° C (melting point + 45 ° C), and the mechanical shear force is higher. The processing time (T2) was changed to 30 minutes. Then, it was cooled and the treated carbon black was taken out. The organic compound is grafted on the surface of the carved black at a grafting rate of 81%, the number average particle size of the Fred diameter is 80 nm, and secondary particles are crushed. It was confirmed. This carbon black is referred to as “carbon black 1 of the present invention”.

(Graft ratio measurement method)

The reaction product of carbon black and organic compound obtained above is put into a Soxhlet extractor, extracted with toluene for 72 hours, unreacted organic compound is extracted, and the grafting rate is calculated. Here, the graft ratio is expressed as ((Υ-Ζ) ΖΥ) ΧΧ (%), where Y is the amount of organic compound before the reaction and the extracted organic compound is taken.

[0049] [Example 2]

Carbon black (Ν220, manufactured by Mitsubishi Chemical Co., Ltd.) 100 parts by weight and 100 parts by weight of the same carbon black 100 parts by weight of organic compound 47 (molecular weight = 784, melting point = 221 ° C) 80 parts by weight with a fullness of 94 Both materials were put into the apparatus so as to be%. Stirring was performed while the temperature inside the apparatus was heated to the first temperature condition (Tpl) of 231 ° C. (melting point + 10 ° C.). The number of revolutions (Svl) was set to 30 revolutions per minute (Svl) by screw rotation, and the treatment time (T1) was set to 10 minutes, and stirring treatment was performed. Sampling in this state and confirmation of the state of grafting by Soxhlet extraction revealed that the grafting rate was about 27%. In other words, it was confirmed that Darafuto candy was in progress on the surface. Next, the screw speed (Sv2) was set to 50 rpm, the second temperature condition (Tp2) was set to 260 ° C (melting point + 39 ° C), and the mechanical shear force was changed to a higher condition. Processing was performed with a processing time (T2) of 30 minutes. Thereafter, it was cooled and the treated carbon black was taken out. The organic compound is grafted on the surface of the carved black with a graft ratio of 67%, and the number average particle diameter of the ferret diameter is also reduced to 80 nm. It was confirmed that This carbon black is referred to as “present invention carbon black 2”. [0050] [Example 3]

In Example 1, instead of the organic compound 48, the organic compound 88 (molecular weight = 545, melting point = 186 ° C.) was used, and the other conditions were changed as shown in Tables 1 and 2 in the same manner. Carbon black 3 was obtained.

[0051] [Example 4]

In Example 1, the organic compound 115 (molecular weight = 481, melting point = 84 ° C.) was used instead of the organic compound 48, and the other conditions were the same except that the conditions were as shown in Tables 1 and 2. Carbon black 4 was obtained.

[0052] [Example 5]

In Example 1, the organic compound 127 (molecular weight = 659, melting point = 195 ° C) was used instead of the organic compound 48, and the other conditions were the same except that the conditions were as shown in Tables 1 and 2. Carbon black 5 was obtained.

[0053] [Example 6]

In Example 1, organic compound 128 (molecular weight = 791, melting point = 132 ° C.) was used instead of organic compound 48, and the other conditions were the same except that the conditions were as shown in Tables 1 and 2. Carbon black 6 was obtained.

[0054] [Example 7]

In Example 1, instead of carbon black (N220, manufactured by Mitsubishi Chemical Co., Ltd.), Ra venl035 (manufactured by Columbia Chemical Industry Co., Ltd.) was used, and other conditions were the same as shown in Table 1 and Table 2. Thus, carbon black 7 of the present invention was obtained.

[0055] [Example 8]

In Example 2, instead of carbon black (N220, manufactured by Mitsubishi Chemical Co., Ltd.), Ra venl035 (manufactured by Columbia Chemical Industry Co., Ltd.) was used, and other conditions were the same as shown in Tables 1 and 2. Thus, carbon black 8 of the present invention was obtained.

[0056] [Comparative Example 1]

Carbon black (N220, manufactured by Mitsubishi Chemical Corporation), which has undergone the surface treatment and grafting process, is referred to as “Comparative Carbon Black 1”.

[0057] [Comparative Example 2] In Example 1, after the processing time T1 passed 1 minute, the sample of the apparatus force was also taken out. This is referred to as “Comparison Carbon Black 2”.

[0058] [Comparative Example 3]

In Example 1, the organic compound was treated in the same manner except that it was changed to stearic acid (molecular weight = 284, melting point = 70 ° C.) (Comparative Compound 1) in which no free radical was generated. This is designated as “Comparison Carbon Black 3”.

[0059] [Table 1]

Second organic compound

Organic compound Rotation speed Processing time

The melting point of the temperature condition and the

Melting point of organic compound (number of revolutions / min) (min) Graft rate

(¾) 2 temperature conditions

(¾) T2

Tp2 difference (° c)

Example 1 48 125 170 45 50 30 81 Example 2 47 221 260 39 50 30 67 Example 3 88 186 256 70 50 40 80 Example 4 115 84 164 80 50 40 89 Implementation 5 127 195 255 60 50 40 91 Example 6 128 132 200 68 50 40 82 Example 7 48 125 180 55 55 40 92 Example 8 47 125 250 125 55 40 87 Comparative Example 1 None ― ― ― ― ― ― Comparative Example 2 48 125 ― _ ―

Comparative Example 3 Comparative Compound 1 70 115 45 50 30 0

[0061] [Evaluation]

Evaluation 1) Dispersibility

Take 1 part by weight of each of the above “Invention Carbon Black 1 to 11” and “Comparative Carbon Black 1 to 3”, add 100 parts by weight of acetone, and add 10 parts at a temperature of 25 ° C. Each of the carbon black dispersions was obtained by ultrasonic dispersion for a minute. Thereafter, 5 ml of the dispersion was sampled, and a centrifugal sedimentation experiment was performed at 4000 rpm using a centrifuge. Centrifugation was performed for 60 minutes, and the centrifuge was stopped every 10 minutes during the process, and the dispersion state of the dispersion was visually judged.

Table 3 shows the time when sedimentation was observed even when centrifugation was performed for 60 minutes.

[0062] Evaluation 2) —Existence of secondary particles

Appropriate amounts of the above “invention carbon blacks 1 to 8” and “comparative carbon blacks 1 to 3” were sampled, and the presence or absence of primary particles was observed with a scanning electron microscope (SEM).

[0063] These results are shown in Table 3.

[Table 3] Dispersion te —the presence of secondary particles

Example 1 With A

Example 2 With A

Example 3 With A

Example 4 With A

Example 5 With A

Example 6 A Yes

Example 7 A Yes

Implemented 8 A Yes

Comparative Example 1 10 minutes None

Comparative Example 2 20 minutes None

Comparative Example 3 10 minutes ίίίΕ

[0064] In "Invention carbon blacks 1 to 8", uniform dispersibility was well maintained even after a 60-minute centrifugal sedimentation experiment, whereas in comparative carbon blacks 1, 2, and 3, The carbon black settled in 10 minutes, 20 minutes, and 10 minutes, and the carbon blacks 1, 2, and 3 for comparison showed excellent dispersibility.

[0065] In addition, it was confirmed that the "primary carbon blacks 1 to 8 of the present invention" have stable primary particles, whereas the comparative carbon blacks 1, 2, and 3 each have their own primary particles. My body was not confirmed.

[0066] [Effect of the invention]

In the present invention, it has become possible to stably present primary particles that could not be achieved conventionally. This makes it possible to apply to various industrial fields. In addition, the carbon black of the present invention has relatively good dispersibility and compatibility and can be used in many areas such as transparent conductive materials, radiation prevention materials, oil-based inks, powder inks, paints, etc. Is possible. The carbon black production method is simple in process, low in cost and free from contamination. It can be used for continuous production of large lots.

Brief Description of Drawings

[0067] [Fig.1] Explanation of flange diameter

[Figure 2] Explanatory diagram of secondary particles and basic particles [Figure 3] —Explanation of secondary particles

[Figure 4] Illustration of conventional carbon black

Claims

The scope of the claims

[1] a surface treatment step of treating the surface of carbon black containing secondary particles that have active free radicals or an organic compound that can be produced and that also have at least basic particle agglomeration (structure) force; Secondary particle force A method for producing carbon black, comprising a grafting step of grafting the organic compound onto a separated separation surface.

[2] The method for producing carbon black according to [1], wherein at least the surface treatment step or the grafting step has a step of imparting a mechanical shearing force.

[3] The method for producing carbon black according to [2], wherein the step of applying the mechanical shearing force is at least a temperature equal to or higher than a melting point of the organic compound.

[4] The method for producing carbon black according to [1], [2] or [3], wherein the organic compound contains at least a phenol compound and / or an amine compound.

[5] The method for producing carbon black according to claim 1, wherein 5 to 300 parts by weight of the organic compound is added to 100 parts by weight of carbon black.