KR100246246B1 - Ink compositions containing processed carbon black and process thereof - Google Patents

Abstract

Carbon black treated with a treating agent comprising at least one compound having at least one long chain alkenyl or alkyl group and at least one amine group. Optionally the compound contains one or more chemical functional groups for linking the long chain alkenyl or alkyl and amine groups. Moreover, this invention discloses the ink composition which mixed process carbon black, and the manufacturing method of this composition.

Description

[Name of invention]

Ink composition containing processed carbon black and its manufacturing method

[Technical Field]

The present invention relates to processed carbon blacks having improved dispersing properties, which are suitable for various uses, particularly for ink compositions. This application is a partial continuing application of US patent application Ser. No. 07 / 504,215, filed April 4,1990.

[Background]

Carbon black is generally produced by a method of obtaining a combustion product containing carbon black particles by pyrolyzing a hydrocarbon raw material using a hot combustion gas in a furnace type reactor.

Carbon black is a pigment, filler, reinforcement, and can be used for many other purposes. For example, carbon black is widely used as a pigment in preparations of ink compositions, paints, etc. In this case, it is generally preferable to use a carbon black pigment that can be easily dispersed.

Newspaper ink compositions are prepared in two steps, for example. First, a dispersing excipient composed of a resin, an additive, and an oil or a solvent is mixed with a carbon black pigment to prepare a “premix”, and then this premix (eg, in a shot mill) ) To completely disperse the carbon black in the ink composition. Dispersion of the carbon black pigment in the ink composition occurs during premix formation and during premix grinding. Easily dispersed carbon black pigments bring economic benefits by reducing the time it takes for ink manufacturers to produce ink. For this and other reasons, it is advantageous to produce carbon black pigments that are readily dispersible.

It is also desirable to produce ink compositions that are less likely to be erased from printed paper and stick to the hands, clothes, and / or furniture of the reader. For example, it is desirable that newspaper inks generally used for printing newspapers have little tendency to be erased by friction. One way to reduce erasure is to use carbon black pigments with a low structure, ie, low dibutyl phthalate absorption. Unfortunately, such carbon blacks are difficult to disperse. Therefore, there has been a need for carbon black that is easily dispersed and reduces the erasure in the ink composition. By modifying the carbon black having good erasure but poor dispersibility according to the present invention, it is possible to produce a processed carbon black having improved dispersibility while maintaining similar erasure.

One method of dispersing carbon black in ink formulations is described in Plow, Matsunaga and Fowkes, "Low Dielectric Constants", Voloids and Surfaces, Volume 7 (1983), pages 183-207. Dispersibility and Stability of Carbon Black in Medium. 1.The Dispersibility and Stability of Carbon Black in Media of Low Dielectric Constant. 1. Electrostatic and Steric Contributions to Colloidal Stability. Together, the dispersant is added to oil or valor. The presence of dispersants in oils or solvents increases the dispersibility of carbon black.

Summary of the Invention

The present inventors pretreated the carbon black with an effective amount of a treatment agent sufficient to improve the dispersibility of the carbon black, and then pelletized the carbon black to form a processed carbon black, if necessary, so that the dispersibility of the carbon black is advantageous. I found it to be increased further. All carbon blacks can be used as starting materials, but 35-130 cc / 100 g of DBPA (dibutyl phthalate absorption) and 25-150 mg I ₂ / g of I ₂ (iodine adsorption number) Carbon black having is preferred.

Treatment agents suitable for use in the present invention contain one or more compounds having at least one long chain alkenyl or alkyl group and at least one amine group. The alkenyl or alkyl group preferably has 50 to 100 carbon atoms, more preferably 60 to 70 carbon atoms. In some cases, the compound may contain one or more chemical functional groups suitable for linking alkenyl or alkyl groups with amine groups.

The amount of treatment agent used in the present invention is an effective amount sufficient to allow carbon black to still be free-flowing and subsequently pelletizing, while increasing the dispersibility of the carbon black. Generally, the amount is such that the resulting carbon black will have 0.25 to 20% by weight of the treating agent. Preferably, the carbon black of the present invention is treated with an amount of the treating agent such that the resulting carbon black contains 0.5 to 8% by weight of the treating agent. In preparing the treated carbon blacks, conventional ingredients may be further added. In all cases, the processed carbon black is substantially dry and free flowing because the weight fraction of carbon black in the processed carbon black is greater than 100 / (DBPA of 100 + carbon black).

In addition, the inventors have invented a novel ink composition containing processed carbon black.

The carbon black used to prepare the processed carbon black of the present invention may be prepared in a furnace type carbon black reactor having a first (combustion) zone, a transition zone and a reaction zone. Carbon black forming raw materials are injected into the hot combustion gas stream by methods known in the art. The product mixture of raw materials and hot combustion gases is sent to the reaction zone. The pyrolysis of the carbon black forming raw material is stopped by quenching the mixture when carbon black is formed. Preferably, the pyrolysis is stopped by a quench method in which a quench fluid is injected.

In preparing the processed carbon black of the present invention, the carbon black is contacted with the treating agent described herein by any means. For example, with or without pelletizing oil, the treating agent is sprayed onto the fluffy carbon black and the resulting mixture is stirred if necessary. The resulting mixture can be used in a floppy state or assembled in the same way as, for example, using a dry drum pelletizer. Alternatively, the treating agent may be sprayed completely onto the floppy carbon black and then granulated oil may be added to the mixture of the carbon black and the treating agent. It is also possible to add coarse oil to the floppy carbon black, followed by the addition of the treating agent. Alternatively, an aqueous solution or emulsion of the treating agent may be prepared and then mixed with carbon black.

Compositions in which the novel processed carbon black of the present invention is effective as a pigment include inks, paints, liquid toners, and the like. However, the novel processed carbon blacks are particularly effective for producing newspaper ink compositions and web offset gloss heatset (WOGHS) ink compositions.

Generally, newspaper ink compositions comprise about 5 to about 35 parts by weight of carbon black pigment, 0 to about 40 parts by weight of resin or resin mixture, about 30 to about 95 parts by weight of oil (s) or solvent (s), and 0 to about 25 parts by weight of additive (s). Suitable resins are, for example, hydrocarbon resins and rosin-modified phenolics. Suitable oils and solvents are, for example, vegetable oils such as aromatic mineral oils, paraffinic mineral oils, naphthalene mineral oils, hydrocarbon solvents, or castor oils. Suitable additives are, for example, viscosity stabilizers, dispersants, blue toners, waxes, asphalt composites such as gilsonite, and fillers such as clays.

Generally, the WOGHS ink composition comprises about 5 to about 60 parts by weight of carbon black pigment, about 20 to about 60 parts by weight of resin (s), about 20 to about 60 parts by weight of oil (s) or solvent (s), and 0 to It contains about 20 parts by weight of additive (s). Suitable resins are, for example, hydrocarbon resins, phenolic modified resin esters, alkyd resins and rosin. Suitable oils and solvents are, for example, hydrocarbon solvents, mineral oils and vegetable oils such as linseed oil or soybean oil. Suitable additives are, for example, plasticizers, clays, gilsonites, waxes, desiccants, blue toners, silicas or dispersants.

An advantage of the processed carbon black of the present invention is that the carbon black is easily dispersed. Thus, carbon black, which has good erasure properties but is very difficult to disperse in practice, can be modified and made available.

The ink composition containing the processed carbon black of the present invention has another advantage that it can be produced more quickly.

Another advantage of the present invention is that the carbon black pellets produced by the present invention have excellent dispersibility. The advantages of pelletized carbon black over floppy forms are well known in the industry, including high bulk density, economical for shipping and storage, easier bulk handling, and less dust. do.

Another advantage is that the gloss of the WOGHS ink composition containing the processed carbon black of the present invention is high.

Other advantages of the present invention will become apparent from the following detailed description of the invention.

Detailed description of the invention

Unique products of the present invention are carbon blacks that have free flow and are treated with an effective amount of a treatment agent sufficient to improve their dispersing properties, or carbon blacks that are subsequently assembled if necessary to form processed carbon blacks. Any carbon black may be used as starting material, but carbon blacks having a DBPA (dibutyl phthalate absorber) of 35-130 cc / 100g and I ₂ (iodine adsorption) of 25-150 mg I ₂ / g are preferred.

Treatment agents suitable for use in the present invention contain one or more compounds having at least one long chain alkenyl or alkyl group and at least one amine group. The alkenyl or alkyl group preferably has 50 to 100 carbon atoms, more preferably 60 to 70 carbon atoms.

Optionally, the compound may contain one or more chemical functional groups suitable for linking alkenyl or alkyl groups to amine groups. In preparing carbon blacks that can be easily dispersed, any known kind can be used as long as the resulting compound can retain utility as a treating agent as the chemical functional group used as the binding element. Examples of suitable chemical bond groups are succinimide bonds, succinoyl bonds, glutarimide bonds and oxyalkylene bonds. If the compound has one or more chemical bonding groups, these groups may be the same or different from each other.

Compounds suitable for use as treating agents in the present invention include alkenyl or alkyl succinimides of polyamines, alkenyl or alkyl succinimides of polyamines, alkenyl or alkylamides of polyamines, alkenyl or alkyl polyamines, and alkenyl or alkyl Esters of succinic acid and hydroxy alkylpolyamines. Also suitable are oligomeric materials containing alkenyl or alkyl succinimides of polyamines between nitrogen atoms connected by C (═O) CH ₂ CH (R) C═O bonds. As alkenyl and alkyl groups, polymers of isobutene or propene having 50 to 100 carbon atoms are preferable, and polymers of isobutene having 60 to 70 carbon atoms are more preferable. As polyamine, the polyalkylene polyamine of the following general formula (I) or the cyclic homologue of general formula (I) is preferable. Wherein R ₁ is alkylene, R ₂ and R ₃ are H or alkyl and a is 1-6. When a polyamine of formula (I) is used to prepare a compound of formula (II), (III) or (IV), R ₁ is C ₂ H ₄ , R ₂ and R ₃ are H and a is a polyamine having 1 to 5 More preferred compound. Preferred hydroxyalkylpolyamines are hydroxyalkyl polyalkylene polyamines of formula V wherein R ₁ and R ₄ are alkylene, R ₂ , R ₃ and R ₅ are H or alkyl and e is 0-4, It can be used to prepare compounds of VI. More preferred hydroxyalkylpolyamines are compounds in which R ₁ and R ₄ are C ₂ H ₄ , R ₂ , R ₃ and R ₅ are CH ₃ or C ₂ H ₅ , and e is 0-2.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

Specific examples of suitable treatment agents include

1. a compound of formula II wherein R is a polyiso butenyl group having 60 to 70 carbon atoms, R ₁ is C ₂ H ₄ , R ₂ and R ₃ are H, b is 1 to 5,

2. a compound of formula III wherein R and R 'are a polyisobutenyl group having 60 to 70 carbon atoms, R ₁ is C ₂ H ₄ , R ₂ is H, c is 1-4,

3. a compound of formula IV wherein R is a polyiso butenyl group having 60 to 70 carbon atoms, R ₁ is C ₂ H ₄ , R ₂ and R ₃ are H and d is 1 to 5,

4. There are compounds in formula VI wherein R is a polyiso butenyl group having 60 to 70 carbon atoms, A is O or NH and f is 0 to 2.

Representative treatment agents include, but are not limited to, OLOA 1200 dispersants (40-50% C ₇₀ polyisobutenyl succinimide solution of polyamines in mineral oil, commercially available from Chevron Corporation of Richmond, CA). ; And Lubrizol 2165 dispersant (60% C ₆₀ polyisobutenyl succinimide solution of tetraethylene pentamine (TEPA) in mineral oil, a product sold by Lubrizol Corporation, Wycliffe, Ohio). .

The amount of treatment agent used in the present invention is sufficient to improve the dispersibility of the carbon black and is added in an amount that can be assembled later if the carbon black is still free flowing or required. Generally, the amount is such that the resulting carbon black will contain 0.25 to 20% by weight of the treating agent. Preferably, the carbon black of the present invention is treated in an amount such that the resulting carbon black contains 0.5 to 8% by weight of the treating agent. In preparing the processed carbon black, conventional ingredients may be further added. In all cases the carbon black weight fraction in the processed carbon black is greater than 100 / (DBPA of 100 + carbon black), so the processed carbon black is substantially dry and free flowing.

The inventors have also discovered a novel ink composition containing carbon black.

The treated carbon blacks of the present invention may be produced in very different ways. The method for producing the treated carbon black of the present invention is as follows.

The carbon black is contacted with a mixture of coarse oil and dentifrice in equal proportions. The amount of mixture used will be sufficient to produce the processed carbon black that has reached the desired processing level. In the present invention, the processed carbon black preferably contains about 0.25 to 20% by weight of the carbon black weight, more preferably 0.5 to 8% by weight of the treating agent. Contact of the carbon black with the treating agent may occur at any downstream point of the cooling stream where the treating agent is thermally stable.

After the carbon black is contacted with the treating agent, the resulting mixture is any suitable method, such as conventional rotary drums or pin type granulators of the type disclosed in, for example, US Pat. Nos. 2,120,540 and 2,306,698, which are incorporated herein by reference. It may also be stirred until a pellet of the desired quality is formed. Suitable granulating oils for use in the present invention are all granulating oils known in the art. However, granulated oils which are nonvolatile, nonpolymerizable organic liquids are preferred for ink compositions, which are miscible with the ink compositions. More preferred coarse oil is mineral oil or modified mineral oil. A general description of the method of assembly and the types of granulation oils suitable for use in the present invention are described in US Pat. No. 3,011,902, which is incorporated herein by reference.

The following test methods are used for the characterization of the carbon black of the present invention and for the measurement and evaluation of the physical properties of the ink compositions containing the carbon black of the present invention.

The I ₂ value of each of the carbon blacks was measured by ASTM D1510. DBPA of each of the carbon blacks was measured by the method set forth in ASTM D2414.

The I ₂ SA (iodine surface area) of each of the carbon blacks was measured by ASTM D1510, modified as follows. Two additional devices were used: a muffle furnace that could be maintained at 927 ° C. and a size 0 porcelain crucible and a lid. Method A of ASTM D1510 was used but modified as follows. Replace step 9.1 of the ASTM D1510 method with the following steps:

1. Fill carbon black up to the top rim of a size 0 self-cleaning crucible without cracks. Press the lid against the rim.

2. Place the crucible in an indirect furnace at 927 ° C. for 7 minutes.

3. Take out the crucible from the indirect furnace and cool it to room temperature in the dryer.

4. Remove the crucible from the dryer. Remove and discard approximately 1/2 inch of the top of the unvolatile volatilized carbon black.

Replace step 9.2 of ASTM D1510 with the following steps.

1. Weigh almost 0.0001 g of unvolatile carbon black and place in a glass bottle. The sample mass measured from the expected iodine surface area is used as shown in the table below (Table 9.2 of ASTM D1510). If the product is below or above the range indicated for that sample size, a retest using the sample weight as a table for the range to which the product belongs is specified. In 9.2, replace the first column of the table with the following column.

Replace step 9.4 of the ASTM D1510 method with the following steps:

1. Shake the vial vigorously for 10 minutes at 120 strokes / minute or more.

Then calculate I ₂ SA according to the following formula:

SA = [10 (B-T) -4.57] /1.3375 × 0.8 / SW

SA = I ₂ surface area (㎡ / g)

B = titrate volume for blank (ml)

T = volume for the sample (ml)

SW = actual sample weight (g)

This method corresponds to Cabot Corporation test method 23.2 for measuring I ₂ SA.

The effects and advantages of the present invention will be illustrated by the following examples.

Example 1

This example illustrates the novel process carbon black production process of the present invention. Fluffy carbon black with 77cc / 100g DBPA and 46 m2 / g I ₂ SA was treated with approximately 3.2% by weight of the floppy carbon black treatment agent, in this case a 50/50 mixture of OLOA 1200 dispersant and Sunthene 450 oil. It was. Sunthene 450 oil is a product of Sun Oil Co. of Philadelphia, PA. It has a SUS viscosity of 502 (measured by ASTM D2161 at 100 ° F) and a total aromatic content of 43.2% by weight (ASTM D2007). Measure). The 50/50 mixture is sprayed onto the floppy carbon black just prior to introduction to the pin granulator. The resulting mixture was then stirred and dry granulated to produce processed carbon black with 1.6 wt% of treatment.

Example 2

The details of the method of Example 1 were followed except that the treatment mixture was used at 5.2% by weight. The resulting processed carbon black contains 2.5% by weight of treatment.

In the following examples, the processed carbon black of the present invention is used to prepare newspaper ink compositions. Newspaper ink compositions are prepared by the following method.

Mix oils, solvents, resins and additives and sand like sand on a NPIRI product grinderometer G2 in a rotor-stator mill or high speed impeller mixer Or mixed for at least about 30 minutes until no scratches were observed to prepare excipients.

280 g of excipient, 70 g of carbon black and any additional additives were combined and placed in a 1 quarter container and mixed for 30 minutes using a high speed impeller mixer. Take 70 g of the premix sample and leave it for testing. Subsequently, 900 g of steel shot was added, and the premix was short milled with a disk attached to the end of the rotating mandrel while stirring the premix. Short mill grinding was terminated if no scratches and 20 micron grains were read on the NPIRI Product Polisher G2. The ink was then filtered to separate the shots, packed and labeled.

In the examples below, the "residue premix" was measured as follows. 25 g of the premix were weighed in a 4 oz glass jar with a rotary top lid. Mineral volatiles were added to about 3/4 of the vessel capacity. The vessel and contents were stirred in a paint stirrer for 5 minutes. The vessel contents were filtered through a clean 325-mesh sieve and the vessel was rinsed cleanly over the sieve with a mineral volatile solvent stream in a squeeze bottle. The residue on the sieve was rinsed with mineral volatile solvent until the rinse cleared. The sieve was dried in an oven at 120 ° C. for 20 minutes. Subsequently, the residue was carefully brushed into a pre-weighed 1 ounce can and the mass of this material was referred to as the residual premix.

In the following examples, the method for measuring the "short mill grinding time" was as follows. The grinding is stopped every 2 minutes during the short mill grinding, a small amount of ink sample is removed and filtered to remove the short, and placed in the deep end of the channel on the NPIRI Product Polisher G2. The ink is drawn down the channel using a straight end steel tool. Be careful of scratches on the ink layer. Also note the point where sandy particles are defined, which are defined as small dots that appear to protrude from the ink surface. The depth of the channel at this point was read from the grind meter side and recorded in microns. Grinding continued until the channel depth was 20 microns or less, until no scratches and no grit were observed. The time to reach a 20 micron grit-like particle reading was recorded as the shot mill grinding time.

Example 3

This example describes a method for producing a newspaper ink composition containing the processed carbon black of the present invention. This example also illustrates the advantages caused by using the processed carbon black of the present invention in a newspaper ink composition.

To compare the newspaper ink composition of the present invention with conventional newspaper ink compositions, 5.6% Sunthene 450 oil was sprayed onto granulated carbon black made of floppy carbon black with 77cc / 100g DBPA and 46 m ₂ / g I ₂ SA. The conventional newspaper ink composition A was prepared. Newspaper Ink Composition B was prepared from the carbon black of Example 1 treated with a mixture of treating agent and oil. Newspaper ink composition C was prepared from the carbon black of Example 2 which was treated with a high concentration mixture of the treating agent and the oil.

Newspaper ink compositions A, B and C were prepared by adding each of the carbon black samples to the newspaper ink compositions described in Table 1 below.

TABLE 1

PICCO 5140 resin is a high softening hydrocarbon resin and is commercially available from Hercules Incorporated, Wilmington, Delaware.

Sunthene 480 oil is a product of Sun Oil Co. of Philadelphia, PA, and has an SUS viscosity of 760 (measured by ASTM D2161 at 100 ° F) and a total aromatic content of 42.4% by weight (ASTM D 2007) Has

MAGIE SOL 47 oil is a solvent oil that is essentially a 100% saturated hydrocarbon and is Maggie Bros., 60131 Franklin Park, Illinois. The product is marketed by Magie Bros. Oil Company, Pennzoil Company Division.

EXX-PRINT 991 oil is a residual oil which is approximately 41% aromatics and is marketed by Exxon Corporation of Houston, Texas.

The shot mill grinding time and residual premix of these newspaper inks were then measured according to the method described herein. the results are as follow:

This result indicates that by containing the processed carbon black of the present invention in the newspaper ink composition, the residual premix and short mill grinding time are reduced compared to the newspaper ink composition using the raw carbon black. Reduction of residual premix indicates that it takes less time to reach a certain level of residue in the premixing step. This will bring economic benefits to ink manufacturers. Likewise, the reduction of short mill grinding time brings economic benefits. The results of this example show that higher treatment agent concentration on carbon black may be more effective.

Example 4

In this Example, the present invention treated with the treatment agent will be described in comparison with the improvement in the case where the black ink composition contains the carbon black as compared with that containing the untreated carbon black and the same treatment agent as separate components.

Newspaper Ink Composition A is Composition A in Example 3 prepared without adding the treating agent to the raw carbon black. Newspaper ink composition D contains a processing agent in an excipient and is made of the same raw carbon black as used in newsprint ink composition A. Newspaper ink composition E was prepared from the carbon black of Example 2 treated with a mixture of treatment agent and oil. Newspaper ink compositions D and E were prepared by adding each carbon black to the newspaper ink composition shown in Table 2 below.

TABLE 2

The shot mill grinding time and residual premix of the newspaper ink compositions A, D and E were then measured according to the method described herein. the results are as follow:

These results indicate that by containing the processed carbon black of the present invention in the newspaper ink composition, the residual premix and the short mill grinding time were shorter than when the same amount of the same carbon black in the same unprocessed form and the same treatment agent were separately contained. Decrease to a significant extent.

Reduction of residual premix indicates that it takes less time to reach a certain level of residue in the premixing step. Reduction of the shot mill grinding time similarly indicates that it may take less time to reach the desired final degree of dispersion in the shot mill step. These factors, in particular when taken together, result in lower energy costs per unit of ink produced and / or increase the processing capacity at certain ink manufacturing plants while bringing economic benefits to ink manufacturers.

From these results, it can be seen that some of the advantages that can be obtained by separately containing the raw carbon black and the processing agent in the newspaper ink composition. More importantly, however, these results clearly show that greater benefits can be obtained by including the processed carbon black of the present invention in the newspaper ink composition.

Example 5

This example illustrates the improvement by containing the carbon black of the present invention in a newspaper ink composition having a higher viscosity than the newspaper ink composition of Example 4.

Newspaper ink composition F was prepared from the carbon black of Example 2 treated with a 50/50 mixture of OLOA 1200 dispersant and Sunthene 450 oil. Newspaper ink compositions G and H were made from carbon black without the same treatment agent used in newsprint ink composition A. Newspaper ink composition G contains a treatment agent added separately to the excipient. Newspaper ink composition H does not contain a treatment agent. Newspaper ink compositions F, G, and H can be prepared by containing the respective carbon blacks in the newspaper ink composition shown in Table 3 below. The amount of Sunthene oil was chosen to produce an ink of a certain viscosity.

TABLE 3

Sunthene 4240 oil is a product of the Sun Oil Company of Philadelphia, PA, having an SUS viscosity of 2300 (measured by ASTM D2161 at 100 ° F.) and an aromatic total content of 46.7% by weight (measured by ASTM D2007).

The short mill grinding time and residual premix of the newspaper ink compositions F, G and H were then measured according to the method described herein. the results are as follow:

These results show that by containing the inventive carbon black of the invention in the newspaper ink composition, the residual premix and short mill grinding time are reduced as compared to the raw carbon black in the newspaper ink composition. These results also show that by containing the processed carbon black of the present invention in the newspaper ink composition, the residual premix and short mill grinding time are lower than when the same unprocessed carbon black is contained and when the same treating agent is contained in the newspaper ink composition. Decrease to a greater extent.

As described in Example 4, the reduction of residual premix and short mill grinding time brings greater economic benefits to ink manufacturers.

Example 6

This example illustrates the advantages caused by using two processed newspaper blacks of the present invention with additional newspaper ink compositions having a combination of resin and additives different from the composition of Example 5.

Newspaper ink compositions J and K were prepared using carbon black pellets made of floppy carbon black with 76 cc / 100 g DBPA and 51 m ₂ / g I ₂ SA sprayed with 6.5% Sunthene 450 oil. Newspaper ink compositions L and M were prepared from the carbon black of Example 2, which was a similar carbon black treated with a 50/50 mixture of OLOA 1200 dispersant and Sunthene 450 oil.

Newspaper ink compositions J, K, L and M were prepared by incorporating each carbon black sample in the newspaper ink composition shown in Table 4 below. The amount of Sunthene oil was chosen to produce an ink of constant viscosity.

TABLE 4

ZECO 11 Gilsonite is a product sold by Ziegler Chemical and Mineral Corporation, based in Jericho, New York.

The short mill grinding time and residual premix of the newspaper ink compositions J, K, L and M were then measured according to the methods described herein. the results are as follow:

This result indicates that by containing the processed carbon black of the present invention in the newspaper ink composition, the residual premix and short mill grinding time in various different newspaper ink compositions are reduced.

Example 7

This example illustrates the advantages arising from treating carbon blacks having good erasure properties but poor dispersion properties with the treatment agents according to the invention.

Newspaper Ink Composition N was prepared from the same raw carbon black used in Newspaper Ink Compositions J and K. This carbon black has good erase characteristics but poor dispersion characteristics. Newspaper ink composition P was prepared from the processed carbon black of Example 2 which is a similar carbon black treated with a 50/50 mixture of OLOA 1200 dispersant and Sunthene 450 oil. Newspaper ink composition Q is ELFTEX PELLETS 115 carbon black (115cc / 100g DBPA and 67mgI ₂ /) from Cabot Corporation, Waltham, Mass., Which is carbon black typically used in newspaper ink compositions. g of I ₂ ). This carbon black has good dispersibility but poor erase characteristics.

Newspaper ink compositions N, P and Q were prepared by adding each carbon black to the newspaper ink compositions shown in Table 5 below. The amount of Sunthene oil added is chosen so that an ink of constant viscosity is produced.

TABLE 5

The shot mill grinding time and residual premix of the newspaper ink compositions N, P and Q were then measured according to the method described herein. Erasability was measured as follows. For each ink, several 1 inch by 8.5 inch prints on newspapers were prepared with different optical densities. A few minutes after printing, the optical density was measured with a densitometer. One hour after printing, the tissue was removed by pulling a tissue of 2 inches in diameter and 3 pounds in weight over the length of the substrate for 10 seconds. The blackness of the spot on each tissue was measured using a Hunter colorimeter and compared to the L value of clean tissue. The difference in L value is expressed as "delta L value". A logarithmic plot of the delta L value from the colorimeter versus the optical density of the original print is shown. In the case where the optical density is 1, eraseability is expressed as the logarithm of the delta L value from this line. The higher this value, the darker the tissue and the poorer the eraser. The result is as follows:

This result indicates that by adding the processed carbon black of the present invention to the newspaper ink composition, the residual premix and short mill grinding time are reduced compared to the newspaper ink composition containing the similar carbon black in the raw form. This result also shows that ELFTEX PELLETS 115 with excellent dispersing properties, as measured by the balance of shot mill pulverization time and residual premix by treating carbon black having good erasing properties and poor dispersibility with the treatment agent according to the invention. Comparable to the dispersion characteristics of carbon black. In addition, this result is comparable to the erasability of the ink made of the carbon black of the present invention comparable to that of the ink made of the similar carbon black of the unprocessed form, all of which are better than that of the ink made of ELFTEX PELLETS 115 carbon black. It is excellent.

Example 8

This example shows the potency of several different compounds as treatment agents according to the invention. Also similar compounds with shorter hydrocarbon chains are ineffective.

The processed carbon black used in this example is prepared as follows. Carbon black product of REGAL 250-R Carbon Black (46cc / 100g of the I ₂ of DBPA and 68mgI ₂ / g) approximately 10 inches with a 150g one end of the sealing diameter of the Cabot-based materials Corporation, Massachusetts Walt Ham It was placed in a small tumble drum 12 inches long. A solution of 10 wt% treating agent in xylene or hexane was prepared. While tumbling carbon black, 45 g of solution was sprayed into the drum through a hole at one end. The carbon black and the solution were further tumbling for 45 minutes to mix. The treated carbon black was then dried overnight in a vacuum oven at 80 ° C. to remove the solvent. This carbon black was not granulated.

Newspaper ink compositions of this example were prepared using a rotor-stator mill. 713 g of a test excipient (96.5 parts by weight of Sunthene 450 oil and 3.5 parts by weight of EXX-PRINT 991 oil) were placed in a two-quarter container on the rotor-stator mill. And operated at about 40% power. 62 g of carbon black were added over 3 minutes. The power was increased by 90% for 25 minutes. The final ink composition is 8.0 parts by weight of carbon black, 88.8 parts by weight of Sunthene 450 oil and 3.2 parts by weight of EXX-PRINT 991 oil.

The finished ink was poured into the hopper of the test unit. Where it was pumped into a plastic container at a constant volumetric flow rate through a 325 mesh screen. The increase in pressure drop through the screen was measured and recorded using a strip chart recorder. The time taken to increase the pressure to 1, 5, 10 and 20 psig was investigated. The longer time to reach the characteristic pressure level indicates that the carbon black can be easily dispersed.

Newspaper ink compositions U, V, W, X, Z, A1, B1, C1 and Dl were prepared using REGAL 250R carbon black treated as described above with the treatment compound shown in the table below. Newspaper ink compositions U and Cl were included for comparison taking into account the detrimental effects of wetting or tumbling behavior of carbon black by solvent. Newspaper ink composition U was included as a control for newspaper ink compositions V, W, Z, A1 and Bl. Newspaper Ink Composition Cl was included as a control against Newspaper Ink Composition Dl. Each carbon black sample was added to the following newspaper ink composition to prepare a newspaper ink composition.

VV is a polyisobutenyl group in which R and R 'have 60 carbon atoms in the formula (III), R ₁ is C ₂ H ₄ , R ₂ is H, and c is 3.

WW is a compound formed by combining the amine groups in the compound of composition VV with a C (═O) CH ₂ CHRC═ (O) group wherein R is a polyisobutyl group having 60 carbon atoms.

XX is a compound in which R is a polyisobutenyl group having 60 carbon atoms, A is an oxygen atom and f is 0 in the above formula (VI).

AA1 is a compound of formula (III) wherein R and R 'are polyisobuteryl groups having 24 carbon atoms, R ₁ is C ₂ H ₄ , R ₂ is H, and c is 3.

BB1 is a compound in which R and R 'in formula (III) are polypropenyl groups having 12 carbon atoms, R ₁ is C ₂ H ₄ , R ₂ is H, and c is 3.

DD1 is a polyisobutenyl group in which R is 60 carbon atoms in formula (II), R ₁ is C ₂ H ₄ , R ₂ and R ₃ are H and b is 1.

The newspaper ink compositions U, V, W, X, Z, A1, B1, C1 and Dl were then tested as described above. The time at which each pressure was reached was measured. the results are as follow:

The results of V, W, X, Z, C1 and Dl indicate that carbon blacks treated with the various treatment agents of the present invention can be more easily dispersed than U of the same raw carbon black. In addition, the results of U, A1 and B1 indicate that the dispersibility of the processed carbon black is not applied to the same carbon black when the carbon black is treated with a compound similar to the treatment agent of the present invention except that the hydrocarbon chain is shorter. It does not improve compared to.

Example 9

This example illustrates another method of making the novel processed carbon black of the present invention.

REGAL 500R carbon black with 65 cc / 100 g of DBPA and 88 mgI ₂ / g of I ₂ valence, marketed by Cabot Corporation, Waltham, Mass., Was treated as an emulsion in water (in this case, OLOA 1200 dispersant). Treated. This emulsion was prepared as follows. A solution of 3 g of Witconate P10-59 amine alkylarylsulfonate solubilizer, a Witco Corporation product from New York, NY, dissolved in 20 g of OLOA 1200 dispersant, was added to 100 g of water and heated to 80 ° C. Sonication was performed for 5 minutes using a portable ultrasonic probe. 175 g of water were then added in triplicates and sonicated for 3 minutes after each addition. After the tailings were removed from the emulsion, 114 g of this emulsion were added to 110 g of carbon black in the mixing vessel while stirring at 148 rpm with an electric mixer. The product was further stirred for 5 minutes and dried overnight in an oven at 120 ° C. The resulting product is carbon black treated with OLOA 1200 dispersant and solubilizer.

Example 10

This example shows the improvement resulting from the inclusion of the carbon black of the present invention in a thermosetting glossy ink composition.

Thermosetting gloss ink E1 was prepared from the worked carbon black of Example 9. Thermosetting gloss ink F1 was prepared using wet granulated carbon black made from the same raw floppy carbon black used in Example 9.

Slowly add 1470 g of -10 mesh Pentalyn K resin to 1530 g of Magie 470 oil at 170 ° F., then stir for at least 1 hour using a high speed impeller and then pass through these three roll mills Master batches were prepared. Pentaline K resin is a pentaerythritol ester of dimer rosin acid and is a product of Hercules Incorporated, Wilmington, Delaware. Mag 470 oil is a product of the Mag Bros Oil Company, Fenjoil Company Division, Franklin Park, Illinois, with 8.7% aromatics and 3.7% olefins.

Ink is prepared as follows. 49.8 g of carbon black were mixed with 281.8 g of master batch for 15 ounces in a 150 ° F. high speed impeller mixer. Take 70 g of the premix sample and store it for testing. 1225 g of steel coal were added and the premix was short milled by a disc attached to the end of a rotating mandrel while stirring. Ink samples were removed 5 and 10 minutes after the shot mill grinding. This ink was finished 15 minutes after the shot mill pulverization.

5.0 g of the premix was combined with 50 ml of mineral volatile solvent in a glass vessel and stirred for 1 minute to determine the residual premix. This mixture was then passed through a 325 mesh screen with suction and rinsed until the filtrate became clear. The screen was then dried at 105 ° C. for 10 minutes and the residue was brushed and weighed. The fineness of the mill was measured with a NPIRI product polisher G2. Gloss was measured at 60 ° using a gloss meter on an ink sample that was printed on one coated white paper and cured at 275 ° F. for 7 seconds. the results are as follow :

This result indicates that by adding the carbon black of the present invention having a treating agent and a solubilizer to the heat curable gloss ink composition, the amount of residual premix and particulates such as sand is reduced in comparison with the thermosetting varnish ink using raw carbon black. This brings economic benefits to ink manufacturers. In addition, the results show that the carbon black of the present invention having the treating agent and the solubilizer is added to the thermosetting glossy ink composition, so that the gloss is superior to the thermosetting glossy ink using the unprocessed carbon black. In addition, better gloss brings economic benefits to ink manufacturers.

The forms of the invention described herein are for illustration only and are not intended to limit the scope of the invention.

Claims (10)

From about 5 to about 35 parts by weight of processed carbon black treated with a treating agent consisting of at least one compound having at least 50 to 100 carbon atoms or at least one compound having at least one alkyl group and at least one amine group; From about 30 to about 95 parts by weight of oil (s) or solvent (s); And mixing and dispersing 40 parts by weight or less of the resin (s). The method of claim 1, wherein the compound further has at least one chemical functional group which binds an alkenyl or alkyl group having 50 to 100 carbon atoms to the amine group. About 5 to about 60 parts by weight of processed carbon black treated with a treating agent consisting of one or more compounds having at least one alkenyl group or alkyl group having 50 to 100 carbon atoms and at least one amine group; About 20 to about 60 parts by weight of resin (s); And about 20 to about 60 parts by weight of oil (s) or solvent (s). 4. The glossy ink composition of claim 3, wherein the compound further has at least one chemical functional group that binds an alkenyl or alkyl group having 50 to 100 carbon atoms to the amine group. About 5 to about 60 parts by weight of processed carbon black treated with a treating agent consisting of one or more compounds having at least one alkenyl group or alkyl group having 50 to 100 carbon atoms and at least one amine group; About 20 to about 60 parts by weight of resin (s); And mixing and dispersing about 20 to about 60 parts by weight of oil (s) or solvent (s). The method of claim 5, wherein the compound further has at least one chemical functional group which binds an alkenyl group or alkyl group having 50 to 100 carbon atoms to an amine group. The method of claim 1 wherein the composition further comprises up to 25 parts by weight of an additive. From about 5 to about 35 parts by weight of processed carbon black treated with a treating agent consisting of at least one compound having at least 50 to 100 carbon atoms or at least one compound having at least one alkyl group and at least one amine group; From about 30 to about 95 parts by weight of oil (s) or solvent (s); And mixing and dispersing up to 25 parts by weight of an additive. The composition of claim 3 further comprising up to 20 parts by weight of the additive (s). The method of claim 5, wherein the composition further comprises mixing up to 20 parts by weight of the additive (s).