JP5273703B2 - Method for producing squid ink pigment particles, organic pigment or dye, and toner for copying machine, water-based ink, oil-based ink or hair dye using the same - Google Patents

Description

  The present invention relates to an organic pigment or dye obtained from a squid ink sachet, a method for producing the same, and a toner for copying machines, water-based ink, oil-based ink or hair dye using the same.

The squid ink sac forms a small bag attached to the squid liver, commonly referred to as “squid goose”, and is a small amount of about 2.5% of the whole squid goose. . It has squid ink in it.
When the squid is used as a food such as salty salt, the squid ink sac is usually removed. However, the squid itself is also used as food only a small part of the squid catch.
On the other hand, there are fewer examples of the use of squid ink sac, and there is a salty spice that is said to be “Kurozukuri” that puts this squid ink in salted salt as an exception, and as a seasoning for Italian cuisine, etc. "It is used to some extent.
In this way, the squid ink sac is almost discarded, like the squid, except for those used for special foods.

The contents of the squid ink sac are approximately 90% pigment particles, excluding moisture, with the remainder being lipid and protein. In addition, a very small amount of polysaccharide is also contained.
The squid ink sac contains melanin and has a bright black or blackish brown color. The black or black-brown melanin pigment particles in the squid ink sac are agglomerated as hundreds or more of strong solid secondary particles in a form that assists one particle with lipids and proteins.

In some cases, the contents of the squid ink sac containing black or black-brown melanin pigment particles are washed and extracted and used as a pigment for special food additives as described above. Thus, the aggregate of several tens of μm aggregated is used as it is, and a wide range of utilization cannot be expected. The above prior art is described in an application filed earlier by the present applicant (see Patent Document 1). Since there is little development of organic pigments or dyes made from squid ink, the prior art is described again.
In view of the above points, the present inventors dried, pulverized and washed the organic pigment or dye of the powder obtained from the squid ink sac consisting of particles having a particle size of 1 μm or less, and the squid ink sac, A method for producing an organic pigment or dye in which squid ink is enzymatically reacted with a proteolytic enzyme has been proposed (see Patent Document 1).

In the technology so far, the technology described in Patent Document 1 proposed by the present inventors has been epoch-making. However, further improvements have been demanded in recent years, and there is a demand for pigment particle diameters on the order of 100 nm or less, and a variety of pigment particle diameters has been demanded.
Pigment-based inks and dye-based inks each have characteristics (advantages and disadvantages), but an intermediate system using these characteristics may be required. For this reason, it is necessary to further reduce the particle size and to select each particle system.
JP-A-2005-97600

 An object of the present invention is to use a squid ink sac and extract organic particles or dyes by extracting fine particles containing black or black-brown melanin pigments without discarding them. To provide a raw material for a toner, water-based ink, oil-based ink or hair dye. In particular, it is an object to provide squid ink pigment particles that can be made finer to a particle size of 100 nm or less and can be selected as a pigment system and a dye system.

 As a result of intensive studies to achieve the above object, the present inventors have found that the contents of the squid ink sac containing black or black-brown melanin pigment particles are several hundred particles per lipid and protein. Finding that the above secondary particles are firmly agglomerated and gaining knowledge that fine and uniform primary particles containing melanin pigment particles can be obtained by removing and separating the lipids and proteins. Thus, the present invention has been completed. Further, the manufacturing process is a multi-stage process to reduce the size of the particles, and at each stage, squid ink pigment particles having a specific particle system are obtained.

That is, the present invention
1) After drying, pulverizing and washing the squid ink sac, the enzyme concentration is in the range of 0.1 to 1% with respect to the dry weight of the squid ink and the pH is in the range of 7 to 10 using squid ink. After performing the first enzyme reaction, it was purified by removing impurities with a 1000 kDa ultrafiltration membrane, and the purified squid ink was increased in concentration and pH compared to the first enzyme reaction. Is subjected to a second enzyme reaction in the range of 5 to 20% with respect to the dry weight of the squid ink and in the range of pH 9 to 11, and further filtered through a 1000 kDa ultrafiltration membrane to obtain a range of 145 to 486 nm. A method for producing squid ink pigment particles, characterized by producing monodisperse particles having a normal distribution at the center 2) An ultrafiltration membrane of 1000 kDa after performing the second enzymatic reaction in 1) above The permeate that has permeated further 10 Filtration through an ultrafiltration membrane of kDa to produce monodisperse particles having a normal distribution centered in the range of 10 to 51 nm. 3) Production method of squid ink pigment particles 3) Above 100 kDa A method for producing squid ink pigment particles, wherein the permeate that has passed through the filtration membrane is further filtered through an ultrafiltration membrane of 30 kDa to produce monodisperse particles having a normal distribution centered in the range of 3 to 9 nm. 4) Normal distribution monodisperse particles having a center in the range of 145 to 486 nm, normal distribution monodisperse particles having a center in the range of 10 to 51 nm, and 3 to 9 nm obtained by the steps 1) to 3) A method for producing squid ink pigment particles characterized by mixing at least one kind of normally dispersed monodisperse particles having a center in the range. 5) It is composed of squid ink pigment particles, and is in the range of 145 to 486 nm. Normal distribution monodisperse particles having a normal distribution, normal distribution monodisperse particles having a center in the range of 10 to 51 nm, or normal distribution monodisperse particles having a center in the range of 3 to 9 nm, or any of these monodisperse particles 6) Organic pigments or dyes composed of squid ink pigment particles of the above mixture 6) Toners for copying machines, water-based inks, oil-based inks or hair dyes using the organic pigments or dyes of 5) above.

The squid ink sack, which has been almost discarded in the past, is not only used as a mere food additive or sauce, but also by obtaining black or black-brown particles that can be extracted therefrom, it can be effectively used as a pigment or as a dye. It has the effect.
Further, the uniform particles having melanin pigments of monodispersed particles having various particle size distributions obtained in this way are natural organic pigments or dyes, and may contaminate the environment after use. There is no material. As described above, the pigment or dye of the present invention has an extremely excellent effect that the ink sac of squid that has been handled as an industrial waste in some regions can be effectively used.
Furthermore, the squid ink pigment particles having a specific particle system can be obtained at each stage while making the particles finer to a particle diameter of 100 nm or less using a multi-step manufacturing process. In particular, it has a remarkable effect that each particle system can be selected by taking advantage of the characteristics (advantages and disadvantages) of pigment-based ink and dye-based ink.

As described above, the present invention relates to a technique for controlling the particle diameter of squid ink pigment particles in each range from the nm order to the 100 nm order, and the squid ink pigment particles obtained thereby. The ability to control the particle size of the dye is a technology that dramatically expands the application of products, that is, dramatically increases marketability.
In order to facilitate understanding of the superior utility of the present invention, pigments and dyes will be briefly described below. There are two types of pigments: dyes and pigments. Although there is a slight difference between the two categories depending on the industry, the classification is basically based on whether the dye is a dye that dissolves in a solvent or a pigment that is in a dispersed state as a solid.

In the ink industry, an ink having a pigment of several tens to several hundreds of nm is called a pigment-based ink. Although the expression that the dye dissolves in the solvent is considered, when the meaning of dissolution is considered, it means that the dye is uniformly dispersed at the molecular level, and the organic dye is estimated from the molecular weight of the single molecule. The particle diameter of the dispersed particles is considered to be several nm or less.
The squid ink pigment is insoluble because it is a melanin pigment, but when dispersed at several nm or less, it can be handled in the same manner as the dye. In this sense, it can be said that squid ink has two faces (functions) of dye and pigment by controlling the particle diameter. In other words, it is possible to have an intermediate function or both functions at the same time.

A typical ink that uses both a dye and a pigment is an ink for an ink jet printer. The difference between these characteristics can be briefly described as “dye system with good color development and excellent image quality” and “pigment system with excellent water resistance and light resistance”. A dye-based ink in which a pigment is dissolved in a solvent (particles having a molecular size) soaks into the paper and develops color.
Since it is possible to express fine colors by overlaying ink, it is used when printing photographs and the like with high image quality. However, when water, ultraviolet rays, or the like directly act on the dye molecules, water resistance and light resistance are weak, and there is a drawback that it is easy to bleed when printing on plain paper.

On the other hand, a pigment-based ink in which a pigment is dispersed in a solvent is less likely to bleed and has excellent water resistance and light resistance. However, there is a drawback that it is not suitable for fine color expression as compared with dye-based ink. Therefore, there is a demand for pigment particles that can utilize both pigment-based and dye-based characteristics. In the first place, since pigment-based pigment particles and dye-based pigment particles are made of different materials, there is a problem that it is essentially very difficult to have both characteristics by simple mixing. If the same material can be provided with the properties of pigment and dye, it can be said that it has great potential.
The squid ink pigment particles of the present invention can be said to be one of the few materials that can have the properties of pigment and dye by changing the particle diameter.

When extracting the powder which becomes an organic pigment or dye consisting of particles having a particle size of 1 μm or less from the squid ink sac according to the present invention, the squid ink sac is first dried and pulverized as necessary.
On the other hand, a proteolytic enzyme such as industrial alkaline protease is dissolved in a pH 7-10 buffer solution to prepare an enzyme solution. The amount of enzyme added is in the range of 0.1 to 1% with respect to the dry weight of the squid ink. The lower limit value of 0.1% of the addition amount is an amount necessary for performing an effective enzyme reaction, and even if the addition exceeds 1%, the effect is only saturated, so the upper limit value was set to 1%. . In this case, 1 to 3 times as much enzyme solution as the squid ink volume is used.

Next, the internal components taken out from the squid ink sac are put into the enzyme solution and subjected to an enzyme reaction. The amount of the squid ink sac is usually the same as that of the enzyme solution, but there is no particular problem even if the ratio is changed. As appropriate, it can be changed in consideration of production efficiency.
The enzyme reaction is performed at about 35 to 50 ° C., but this temperature is not particularly limited and can be appropriately changed in consideration of production efficiency.
An electron micrograph of particles present in the squid ink sac is shown in FIG. As shown in FIG. 1, an aggregate having a particle size of several tens of μm is formed. This is a structure in which primary particles are strongly aggregated by proteins and lipids.

It is desirable to stir the enzyme reaction. In particular, it is preferable to vibrate at a rotational speed of 50 to 200 rpm. The yield tends to improve as the stirring is increased. Usually, the enzyme reaction is performed for about 30 minutes to 30 hours.
This is a problem of reaction yield and production efficiency, and is not particularly limited to this time, and can be changed as appropriate. Aggregates of several tens of microns that have been strongly aggregated by proteins and lipids are disassembled and separated by an enzymatic reaction to form a dispersion of primary particles.

  After the enzyme reaction is completed, centrifugation is performed at 5 to 30 ° C. and 150 to 300 G for 5 to 60 minutes. The supernatant of the obtained liquid is filtered with a filter to obtain black or black-brown pigment particles. Depending on the collection of the supernatant liquid, there may be a case of collecting what remains on the 0.1 μm filter and a case of collecting particles that have passed through the 1 μm filter. A powder of particles of 1 μm or less is obtained.

By using an ultrafiltration membrane, centrifugation after the enzyme reaction treatment can be omitted. That is, when this ultrafiltration method is employed, separation, concentration and purification (impurity removal) can be performed simultaneously. This is a feature of the ultrafiltration method.
For example, a concentrated squid ink that has been subjected to enzyme reaction treatment and concentrated using an ultrafiltration membrane with a molecular weight cut off of 1000 kDa using a circulation type filtration device and reduced to 1/5 or less. A pigment particle suspension is obtained. The use conditions of the ultrafiltration membrane can be changed as necessary.

The concentration of the squid ink pigment particle suspension can be increased by repeating the concentration and dilution in which the concentrated solution is diluted with pure water and concentrated again. The repetition is sufficient about three times, but it may be performed more if necessary.
In obtaining the powder, either a step of obtaining a powder by filtering with a filter after ultrafiltration or a step of obtaining a powder by drying after ultrafiltration may be used.
An electron micrograph of the powder obtained as described above is shown in FIG. In either case, as shown in FIG. 2, squid ink pigment particles having a particle size of 1 μm or less, particularly a submicron spherical melanin pigment, are obtained. The permeate contains impurities and is discarded.

In this way, after the first enzymatic reaction, the impurities were removed and purified by a 1000 kDa ultrafiltration membrane, and the purified squid ink was reduced in the amount and pH of the enzyme as compared with the first enzymatic reaction. The second enzyme reaction is carried out by increasing the enzyme concentration, that is, in the range of 5 to 20% of the dry weight of squid ink and in the range of pH 9 to 11. In this case, it is effective for the degradation of the protein to use the optimum pH (pH value at which the maximum activity is obtained) 10.0 or its vicinity. It can be confirmed that alkaline protease acts effectively at this pH.
The reaction temperature is preferably 50 ° C. to 65 ° C., but the temperature is not particularly limited. In order to carry out the effective enzyme reaction, the amount of the enzyme needs to be at least 5%, and the upper limit is 20% from the viewpoint of cost. Usually, an enzyme amount of about 10% is used.
The reaction time is 12 hours or longer. This reaction time varies depending on the enzyme concentration, reaction temperature, and pH. In addition, when the ultrasonic wave of 25 kHz to 40 kHz is intermittently applied during the enzyme reaction, the reaction efficiency is increased. Next, the obtained liquid after the enzyme reaction is filtered through a 1000 kDa ultrafiltration membrane to obtain a concentrate containing normally distributed monodisperse squid ink pigment particles having a center in the range of 145 to 486 nm. The permeate contains fine particles.

Next, after the second enzymatic reaction, the permeate that permeated through the 1000 kDa ultrafiltration membrane was further filtered through a 100 kDa ultrafiltration membrane to obtain a concentrate in the range of 10 to 51 nm. Normal distributed monodisperse particles with centers can be produced. The permeate further contains fine particles.
Next, the permeate that has passed through the ultrafiltration membrane of 100 kDa is further filtered through an ultrafiltration membrane of 30 kDa, and as a concentrate, a monodisperse squid ink pigment particle having a normal distribution centered in the range of 3 to 9 nm Can be obtained.

By each of the above steps, a normal distribution monodisperse particle centered in the range of 145 to 486 nm, a normal distribution monodisperse particle centered in the range of 10 to 51 nm, and a normal distribution centered in the range of 3 to 9 nm. Monodispersed squid ink pigment particles can be obtained. These can be used alone or as a mixture of any one or more thereof, if necessary. It can also be used in combination with other dyes.
The squid ink pigment particles of any one of these monodisperse particles or a mixture thereof can be used as an organic pigment or dye, and toners for copying machines, water-based inks, oil-based inks using these organic pigments or dyes Alternatively, it can be used as a hair dye. The present invention includes all of these.

FIG. 3 shows an example for explaining the pigment purification process for each size (nm order) of the squid ink pigment particles described above. The reaction conditions A and B in FIG. 3 have been described above, but will be described again here.
[Reaction condition A]: The enzyme concentration is in the range of 0.1 to 1% with respect to the dry weight of squid ink. The pH is in the range of 7 to 10, and the enzyme reaction is performed for about 30 minutes to 30 hours.
[Reaction condition B]: The enzyme concentration is in the range of 5 to 20% with respect to the dry weight of the squid ink. Moreover, it is set as the range of pH 9-11, and enzyme reaction is performed for 12 hours or more.

 Next, examples will be described. In addition, this Example is for making an understanding of this invention easy, and is not restrict | limited to this Example. That is, all other aspects or modifications or implementation conditions or examples based on the technical idea of the present invention are included in the present invention.

Example 1
The squid ink sac was dried and crushed as needed. Meanwhile, an industrial alkaline protease, which is a proteolytic enzyme, was dissolved in a pH 7.0 buffer solution to prepare an enzyme solution. The amount of enzyme added was adjusted to 0.25% with respect to the dry weight of squid ink.
Next, the same amount of the built-in material taken out from the squid ink sac was put into this enzyme solution. The enzyme reaction was performed at 50 ° C. for 24 hours with stirring at a rotation speed of 130 rpm.
After terminating the enzyme reaction, ultrafiltration was performed using 1000 kDa. Black or black-brown pigment particles were obtained as a purified product (concentrate). The average particle size was 330 nm.

 This process (process flowchart) is shown in FIG. 4, which is the first stage in FIG. The permeate is an impurity and is discarded. In addition, in order to make it easy to understand that fine particles of nm order exist in the SEM image of Example 4, FIG. 8 shows an SEM image taken without placing anything on the SEM stage.

(Example 2)
In Example 1 above, after the first enzyme reaction was performed, impurities were removed and purified by a 1000 kDa ultrafiltration membrane, and the purified squid ink was more concentrated and pH than the first enzyme reaction. In other words, the second enzyme reaction was carried out with the enzyme concentration in the range of 10% of the dry weight of squid ink and the pH of 10.
The reaction temperature was 50 ° C. The reaction time was 24 hours. During this enzyme reaction, 30 kHz ultrasonic waves were intermittently applied. Next, the obtained liquid after the enzyme reaction was filtered through a 1000 kDa ultrafiltration membrane to obtain a concentrate containing normally distributed monodispersed squid ink pigment particles having a center in the range of 145 to 486 nm. FIG. 5 shows the SEM image and particle size distribution of the squid ink pigment particles thus obtained. It can be said that the particle diameter in this range is in the pigment range.
The average particle size was 316 nm. The permeate further contains fine particles. In the process flowchart of FIG. 4, the process of the second embodiment corresponds to the second stage.

(Example 3)
Next, after the second enzymatic reaction, the permeate that had passed through the 1000 kDa ultrafiltration membrane was further filtered through a 100 kDa ultrafiltration membrane. As a result, normal distribution monodisperse particles having a center in the range of 10 to 51 nm were obtained as a concentrate. The average particle size was 16 nm. FIG. 6 shows the SEM image and particle size distribution of the squid ink pigment particles thus obtained. With a particle size in this range, it can be said that it is in the intermediate range between the pigment system and the dye system. The permeate further contains fine particles. In the process flowchart of FIG. 4, the process of the third embodiment corresponds to the third stage.

Example 4
Next, the permeate that has passed through the ultrafiltration membrane of 100 kDa is further filtered through an ultrafiltration membrane of 30 kDa, and as a concentrate, a monodisperse squid ink pigment particle having a normal distribution centered in the range of 3 to 9 nm Got. The average particle size was 4 nm. FIG. 7 shows the SEM image and particle size distribution of the squid ink pigment particles thus obtained. It can be said that the particle diameter in this range is in the range of the dye system. The permeate becomes an impurity and is discarded. In the process flowchart of FIG. 4, the process of the second embodiment corresponds to the fourth stage.

Through the above steps, the normal distribution monodisperse particles having a center in the range of 145 to 486 nm, the normal distribution monodisperse particles having the center in the range of 10 to 51 nm, and the normal having the center in the range of 3 to 9 nm. It is possible to obtain squid ink pigment particles having a monodisperse particle distribution. These can be used alone or as a mixture of any one or more thereof, if necessary. It can also be used in combination with other dyes.
The squid ink pigment particles of any one of these monodisperse particles or a mixture thereof can be used as an organic pigment or dye, and toners for copying machines, water-based inks, oil-based inks using these organic pigments or dyes Alternatively, it can be used as a hair dye. The present invention includes all of these.

The squid ink sack that has been discarded is not only used as a food additive or sauce, but also by obtaining black or black-brown particles that can be extracted therefrom, thereby providing an excellent effect that it can be effectively used as a pigment or as a dye. Have. Furthermore, the squid ink pigment particles having a specific particle system can be obtained at each stage while making the particles finer to a particle diameter of 100 nm or less using a multi-step manufacturing process. In particular, it has a remarkable effect that each particle system can be selected by taking advantage of the characteristics (advantages and disadvantages) of pigment-based particles and dye-based particles.
Therefore, toner for copying machines, water-based inks, oil-based inks, hair dyes, inkjet pigments, chemical hypersensitivity pigments, cosmetic pigments, harmful light blocking agents, heat ray absorbers, light energy carriers, medical agents, etc. Are useful as various pigments or dyes.

It is an electron micrograph of the particle | grains which exist in the squid ink sac. Electron micrograph of the first stage powder of Example 1 of the present application It is a figure explaining a pigment refining process for every size (nm order) of squid ink pigment particles. It is a figure explaining each process of the Example of this invention briefly (process flowchart). It is a figure which shows the SEM image and particle size distribution of the squid ink pigment particle obtained at the process of Example 2. FIG. It is a figure which shows the SEM image and particle size distribution of the squid ink pigment particle obtained at the process of Example 3. FIG. It is a figure which shows the SEM image and particle size distribution of the squid ink pigment particle obtained at the process of Example 4. FIG. It is a figure which shows the SEM image image | photographed without mounting anything on the SEM stage in order to make it easy to understand that the fine particle of nm order exists in the SEM image of Example 4. FIG.

Claims (4)

  After drying, pulverizing and washing the squid ink sac, the enzyme concentration in the range of 0.1 to 1.0% with respect to the dry weight of the squid ink and the pH in the range of 7 to 10 using proteolytic enzyme After performing the first enzyme reaction, it was purified by removing impurities with a 1000 kDa ultrafiltration membrane, and the purified squid ink was increased in concentration and pH compared to the first enzyme reaction. Is subjected to a second enzyme reaction in the range of 5 to 20% with respect to the dry weight of the squid ink and in the range of pH 9 to 11, and further filtered through a 1000 kDa ultrafiltration membrane to obtain a range of 145 to 486 nm. A method for producing squid ink pigment particles, characterized by producing monodisperse particles having a normal distribution centered on each other.   The permeate that has passed through the 1000 kDa ultrafiltration membrane after the second enzymatic reaction in claim 1 is further filtered through a 100 kDa ultrafiltration membrane, and a normal having a center in the range of 10 to 51 nm. A method for producing squid ink pigment particles, comprising producing monodisperse particles having a distribution.   The permeate that has passed through the 100 kDa ultrafiltration membrane according to claim 2 is further filtered through a 30 kDa ultrafiltration membrane to produce normally distributed monodisperse particles having a center in the range of 3 to 9 nm. A method for producing squid ink pigment particles.   A monodisperse particle having a normal distribution centered in a range of 145 to 486 nm, a monodisperse particle having a normal distribution centered in a range of 10 to 51 nm, and 3 to 9 nm obtained by the steps of claims 1 to 3. A method for producing squid ink pigment particles, comprising mixing at least one of normally distributed monodisperse particles having a center in a range.

Images