KR100517667B1 - A printing ink composite - Google Patents

Abstract

The present invention relates to a water-in-oil type printing ink composition, wherein the water-in-oil type ink composition comprising a binder alkyd resin, a nonvolatile oil, a pigment, a surfactant, a dispersant, water and a water-soluble resin, wherein the alkyd resin is palm oil and polybasic acid. It provides a water-in-oil type printing ink composition characterized in that the palm oil alkyd resin obtained by condensation reaction of the polyhydric alcohol with. When the water-in-oil type printing ink composition is used in a printing device applying a penetration drying method to a printing paper such as a digital rotary copying machine, the penetration drying and storage stability is excellent, and the oxidation drying is performed even after exposure of ink due to prolonged printing stop on the printing press. Even if the film is not formed or the viscosity is changed, and it is restarted after prolonged operation stop, the ink printability of the ink is excellent and the high speed printing can be obtained.

Description

Water-in-oil type printing ink composition {A printing ink composite}

The present invention relates to a water-in-oil type printing ink composition for use in an apparatus for printing by applying a drying method to a printing paper, such as a digital rotary copying machine, and more particularly, excellent permeation quick drying and storage stability as well as long time printing on a printing machine. The present invention relates to a water-in-oil type printing ink composition which is excellent in printability of ink even when it is restarted after prolonged shutdown due to no formation of an oxide dry film or viscosity change due to exposure of the ink due to stoppage.

In general, the digital rotoprinter, which is a device for printing by ink infiltration drying method on printing paper, is a monochromatic small size printing machine for offices, and is capable of mass copying of dozens or more, and is widely used for mass printing purposes such as in-house prints, test papers, and other promotional leaflets.

The ink used in the rotoscopic spinning machine is mainly a water-in-oil type emulsion type to disperse a high content of water to have a high viscosity and yield value, and when the water phase is atomized in the oil phase as a basic ink, the emulsion ink is dispersed. The physical properties of the are suitable for the digital rotational copying machine. More specifically, the ink composition for rotoscopic ink printer includes 20 to 50 wt% of an oil phase containing an alkyd resin as a binder, a pigment, a nonvolatile solvent, a dispersant, a surfactant, and an antioxidant; It consists of 50-80 weight% of water phases containing water, a water-soluble resin, and alcohol.

However, since the ink is an emulsion type, as time passes, the dispersed phase gradually fuses with neighboring dispersed particles, thereby degrading storage stability as the oil phase and the water phase are separated. Thus, when the oil phase and the water phase are separated, the ink viscosity and physical properties are separated. This change causes problems such as bleeding, dragging, smearing, and reflection of ink during printing. This problem is the cause of most of the printing defects that occur in the digital rotation machine.

In addition, it is also important to maintain emulsion stability in a sealed state as most emulsion inks are supplied sealed to ink containers or ink cartridges. Under high shear stress and temperature influence by the inking mechanism, it becomes more difficult to maintain emulsion stability.

To improve this, Korean Patent No. 185529 discloses 5 to 23% by weight of modified alkyd resin, 2 to 10% by weight of pigment, 1 to 5% by weight of surfactant, 2 to 10% by weight of linseed oil, and 2 to 10% by weight of low viscosity machine oil. To provide an ink composition comprising 5 to 12% by weight of mineral oil, 50 to 70% by weight of water, 3 to 8% by weight of ethylene glycol, and 1.08 to 2.1% by weight of silicone oil.

However, since the ink composition includes an alkyd resin containing an unsaturated group and an oil containing a large amount of an unsaturated group, the nozzle is clogged due to the formation of an oxide dry film and the change of viscosity when the ink is exposed due to prolonged printing stop on the printing press. In addition, there is a problem that printing defects such as bleeding, dirt, drag, backing or mirroring when the printer is restarted after a long stop operation.

Accordingly, the present invention is to solve the above-mentioned conventional problems, induces a good dispersion state of the emulsion, excellent storage stability and penetration fast drying property, the formation of an oxide dry film or viscosity change of ink generated during long-term exposure on a printing machine It is an object of the present invention to provide a water-in-oil type printing ink composition which can prevent the clogging of the nozzle and prevents the clogging of the nozzle, and also enables excellent high-speed printing due to excellent printability of the ink even when it is operated again after prolonged shutdown.

The present invention to achieve the above object

In a water-in-oil type ink composition comprising a palm oil alkyd resin as a binder, a nonvolatile oil, a pigment, a surfactant, a dispersant, water and a water-soluble resin, the palm oil alkyd resin is phthalic anhydride and maleic anhydride based on 100 parts by weight of palm oil. 60 to 80 parts by weight of polybasic acid selected from fumaric acid, maleic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, tetrahydrophthalic acid, citric acid, trimellitic acid and trimellitic anhydride Glycerin, Pentaerythritol, Ethylene glycol, Diethylene glycol, Triethylene glycol, Polyethylene glycol, Propylene glycol, Trimethylene glycol, Tetramethylene glycol, Trimethylene propane, Diglycerin, dipentaerythritol, mannitol, 40 to 60 parts by weight of the polyhydric alcohol selected from sorbitol is mixed, and xylene is added to reflux to condensation reaction. Obtained by removing xylene, and having an acid value of 10 or less, a whey of 40 to 60%, a molecular weight of 20,000 to 40,000, and a content of 3 to 9% by weight based on 100% by weight of the total printing ink composition. It provides a water-in-oil type printing ink composition.

Hereinafter, the present invention will be described in more detail.

The present invention is a water-in-oil type printing ink composition for a rotary rotatable spinner including an alkyd resin as a binder, a nonvolatile oil, a pigment, a surfactant, a dispersant, and water, wherein the alkyd resin contains a palm oil alkyd resin. There is this.

When the palm oil alkyd resin prepared using palm oil is used as the binder resin as described above, the oxo value of the palm oil is lowered to about 8 to 10 so that the unsaturation is lowered, thereby preventing the clogging of the nozzle due to the formation of the oxidized dry film. do.

At this time, in order to ensure the ink drying speed and good printability, the palm oil alkyd resin may be a heavy oil having an acid value of 10 or less, a whey of 40 to 60%, and a molecular weight of 20,000 to 40,000. The use of such a palm oil alkyd resin in a water-in-oil type printing ink composition enables a good printing without the bleeding, dirt and smearing of the ink due to the fast drying speed.

In particular, the palm oil alkyd resin used in the present invention is to use a high molecular weight of about 10 times or more than the molecular weight of the alkyd resin used in the conventional ink, in this way, when the high molecular weight alkyd resin is used, The gloss and wear resistance of the ink film are excellent.

The palm oil alkyd resin according to the present invention can be easily obtained by condensation reaction between palm oil, polybasic acid, and polyhydric alcohol.

Palm oil contains lauric acid as its main component and is composed of several compounds with relatively short carbon chains. As palm oil is composed of a compound having a relatively short carbon chain, palm oil alkyd resin prepared by using the same has very good affinity with hydrocarbon-based oils, and thus exhibits good wettability to organic pigments such as carbon black to provide sufficient stability. Can be secured.

In addition, lauric acid, the main component of palm oil, generates a large amount of laurin monoglycerides as a by-product during the manufacture of alkyd resins. The by-products increase lipophilic properties and are compatible with long chain polymers and surfactants. To increase the stability more advantageously. In addition, the produced by-product laurin has a bactericidal property, which adds an effect of preventing rancidity and decay during long-term storage of the emulsion ink.

The polybasic acids participating in the condensation reaction with palm oil include phthalic anhydride, maleic anhydride, fumaric acid, maleic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, tetrahydrophthalic acid and citric acid. , Trimellitic acid or trimellitic anhydride can be used, and preferably phthalic anhydride is used.

In addition, the polyhydric alcohols include glycerin, pentaerythritol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, trimethylene propane, diglycerin, dipenta Erythritol, mannitol, or sorbitol may be selected. Preferably, glycerin or pentaerythritol is preferably used.

The above-mentioned palm oil, polybasic acid and polyalcohol may be mixed to condense to xylene reflux to remove xylene, thereby easily preparing a polymer of non-toxic heavy oil alkyd resin. In the present invention, 60 to 80 parts by weight of polybasic acid and 40 to 60 parts by weight of polyhydric alcohol are mixed with 100 parts by weight of palm oil, condensation reaction is carried out while refluxing with addition of xylene, and then xylene is removed to prepare a palm oil alcard resin.

In this case, it is important that the palm oil alkyd resin has an acid value of less than 10, and has an average molecular weight of 20,000 to 40,000. When the acid value of the produced palm oil alkyd resin exceeds 10, the activity of the carboxylic acid group is increased and various side reactions occur. Since the acid value of the alkyd resin may be less than 10, it is preferable to add an excessive amount of polyhydric alcohol in the above-described range as compared to polybasic acid.

The palm oil alkyd resin is to be included in the range of 3 to 9% by weight based on 100% by weight of the total printing ink composition, when the content of the palm oil alkyd resin is less than 3% by weight, good printing results are not obtained. If the content exceeds 9% by weight, the quick drying is poor, the viscosity of the ink is too high, too poor printability.

In the present invention, non-volatile oils, pigments, surfactants, dispersants, water, and water-soluble resins, which are conventional additives used in water-in-oil printing ink, together with palm oil alkyd resins, are included within a general addition range.

In particular, to prepare a printing ink composition, an oil phase comprising the palm oil alkyd resin and a nonvolatile oil, a pigment, a surfactant, and a dispersant is prepared, and at the same time an aqueous phase including water and a water-soluble resin is prepared, and then they are mixed in a usual manner. It can manufacture by mixing in a range.

First, process oils and spindle oils may be mainly used as components of the oil phase, but paraffin oil, diesel oil, kerosene, machine oil, lubricating oil, mineral oil and palm oil and palm oil may also be used. The oils of the petroleum system have a high content of naphthylene-based hydrocarbons, which are effective for water-in-oil emulsion stability, and stabilize the interface between the water phase and the oil phase. At this time, the palm oil alkyd resin is well dissolved with the hydrocarbon-based oil, but may be further added a coarse solvent if necessary.

The oil content may be added in a 1: 2 to 4 weight ratio with respect to the palm oil alkyd resin, and may be added or subtracted according to the viscosity of the oil phase, which is a desired basic ink. The viscosity of an effective oil ink can be widely used from 10 poise to 100 poise, but better printability is obtained when an oil ink having a viscosity of 30 poise to 60 poise at room temperature is prepared.

As pigments, furnace blacks are mainly used for black, but other carbon blacks for inks such as channel black and lamp black can be used. As the colored pigment, both organic pigments and inorganic pigments can be used.For example, by color, red azored, toruidine red, naphthol red, rhodamine red, quinacritone red, red lake C, carmine 6B, risol red, and resol Lumin, chrome orange, molybdate orange, red chromium, red oxide and the like can be used. Blue phthalocyanine blue, phthalocyanine green, Prussian blue, etc. may be used, and yellow chromium yellow, carbazole yellow, mono arylide yellow, diarylide yellow, diazo yellow, and disazo yellow may be used. .

Sieving pigments can be used for both organic and inorganic materials, and can be used to control the viscosity of oil-based ink and the hiding power of color ink. In addition, the use of fine particles of less than 0.1㎛ can give a steric hindrance effect on the oil and water interface can make a stable emulsion ink. Examples of the extender pigments include inorganic alumina, magnesium oxide, titanium trisilicate, coated titanium dioxide, silica, calcium carbonate, kaolin, barium sulfate, etc., but in order to increase the wetting and dispersion efficiency in the oil-based basic ink. It is more preferable if it is coated with wax or a polymer resin. Examples of organic extender pigments include esters synthesized at high molecular weight and granulated into particles, polyethylene, polypropylene, polyvinyl chromide, polyacrylic ester, paraffin wax, carnauba wax and the like.

The pigments described above may be used after determining the content according to the oil absorption amount and the coloring power, but should be adjusted within the viscosity limit of the oil-based basic ink. Usually, carbon black is used within 7% of 100% by weight of the total printing ink composition, and color pigments are generally used when mixed with the extender pigments of fine particles to compensate for the defects of color pigments having a large particle size. The content may be higher than the black pigment of carbon black as a whole.

To stabilize the pigment in the oily ink, a small amount of a wet dispersant may be added. Depending on the pigment used, a wet dispersant suitable for the oil phase may be, for example, aliphatic carboxylic acid and its salts, higher alcohol esters, alkylsulfonic acid, and the like. Salts, alkyl phosphate esters, polyester- carbonate carbonates, polyamine salts of aliphatic polyester carboxylic acids, aliphatic amine salts, quaternary ammonium salts, polyaminoamides and phosphates thereof. However, it must be physically followed by warming pre-mixing, ripening for some time after premixing, and sufficient meat. In this way, when the basic ink of the oil phase is stably prepared, it is degassed to finish the oily ink by adding an appropriate amount of surfactant, an antioxidant, and other additives for preparing an emulsion.

The aqueous phase is made up of pure water purified by ion exchange resins, and the amount of water-soluble resin is dissolved to adjust the viscosity and specific gravity similar to the oil phase so that the aqueous phase is not physically unstable when emulsified in the oil phase. In addition, the function of the water-soluble resin has a high wettability or has a humidity control to prevent or inhibit the evaporation of water can prevent the clogging of the nozzle due to the drying of the water-soluble resin.

As the water-soluble resin, polyvinyl alcohol, methyl cellulose, carboxyl methyl cellulose, hydromethyl cellulose, polyvinyl pyrrolidone, polyethylene-polyvinyl ether, poly acrylamide, arabic gum, starch, water-soluble polyurethane, gela Chin, collagen, casein, glue and the like can be used.

In addition to water and water-soluble resins, higher alcohols may be formulated as needed in the water phase, and the higher alcohols function as antifreeze agents, water wetting agents, and dispersants to stabilize aqueous water solutions. Examples of the higher alcohols include glycerin and sorbitol, and ethylene glycol, diethylene glycol, and propylene glycol may be used.

In addition, a small amount of electrolyte salt may be used as an emulsion stabilizer in addition to water, water-soluble resin, and higher alcohol, and a long-term stability of the emulsion ink may be achieved by adding a small amount of preservative, fungicide, and the like.

When the oil phase and the water phase having the above-described composition and content are mixed, the water-in-oil printing ink composition according to the present invention can be obtained, and in the present invention, within the mixing ratio of the oil phase of 20 to 50% by weight and the water phase of 50 to 80% by weight. Mixing to obtain a water-in-oil type printing ink composition.

When the printing ink composition thus obtained is used in a printing device such as a digital rotary copying machine by applying the penetrating drying method to the printing paper, it not only has excellent penetration fastness and storage stability but also oxidizes ink even after exposure of the ink due to prolonged printing stop on the printing machine. There is no formation of dry film or change of viscosity, which can prevent the clogging of the nozzle. Even if it is restarted after prolonged operation stop, it is excellent in printability of ink, and high speed printing is possible.

Hereinafter, the present invention will be described in more detail with reference to the following examples, which are only presented to aid the understanding of the present invention, but the present invention is not limited thereto.

<Examples 1 to 3>

Fully primary mix of furnace black pigment, process oil, spindle oil and pigment dispersant, process oil, spindle oil, high boiling point petroleum solvent, sorbitan monooleate, polysinoleate, antioxidant and palm oil The mixture obtained by mixing an alkyd resin is added and fully secondary mixed, and this mixing mixture is ground with a 3-minute roll mill, and oily ink is manufactured.

Water-soluble emulsion was prepared by mixing water-soluble resin, glycerin, electrolyte salt, and preservatives thoroughly with purified water passed through the ion exchange resin to prepare an aqueous phase. The aqueous phase was dispersed in small portions and stirred to gradually disperse the aqueous phase into fine particles. Printing ink was prepared. At this time, the amount of each component added is as shown in Table 1 below.

Comparative Example 1

A water-in-oil emulsion printing ink was prepared according to the above example except that the linseed oil of the dry oil having an unsaturated double bond was added in the ratio shown in Table 1 below.

Comparative Example 2

A water-in-oil emulsion printing ink was prepared according to the above example except that linseed oil-modified alkyd (70% whey) and rosin-modified phenolic resin were added in the ratio shown in Table 1 instead of palm oil alkyd resin.

Comparative Example 3

A water-in-oil type emulsion printing ink was prepared according to the above-mentioned example except that the oil-based palm oil alkyd resin was used and the oil-based palm oil alkyd resin was 35% whey and the molecular weight of 100,000 to 160,000 was used.

Experimental Example 1

The emulsion inks prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were subjected to the film drying test, the viscosity change measurement test and the penetration fastness test in the following manner, and the results are shown in Table 2 below.

-Film Drying Test-

Emulsion ink was formed on the glass plate with a coating layer of 30 µm thickness using a Myco Bar (Gardco Applicaton Rod No. 12), and the film was dried every 12 hours. The drying time was measured with a stick (73 g, white paper attached to a Φ80 mm × 10 mm roller). do. After printing with the ink supply for the first time on the printer, check the print quality, and then leave the ink exposed for one month during operation and then reprint the print quality (print density, bleeding, dirt, jam, backing, back). Review). The quality level is evaluated in five stages, with a good quality of 5 and a very poor quality of 1.

-Viscosity change measurement test-

Immediately after the preparation of the emulsion ink, the viscosity was measured at 25 ° C., and then the ink was stored in a thermostat at 80 ° C. for 5 hours, and then the viscosity was measured at 25 ° C. In addition, the emulsion ink is placed in a thermostat, stored for 24 hours at -10 ℃, maintained at 40 ℃ 24 hours, after another 24 hours at 25 ℃ and the viscosity is measured. Viscometer is measured using Brookfield (RVDV-E).

-Penetration Quick Drying Test-

After printing for 1 month on the printing machine of the digital rotary copying machine, test print the ink stored at 80 ° C for 5 hours at high temperature. After printing 500 sheets at the maximum speed of 130 sheets / minute, check the backing, and check whether the backing occurs as '×', and if it does not occur, evaluate it as '○' to determine quick drying.

As shown in Table 2, the ink compositions of Examples 1 to 3 prepared in the preferred range of the present invention are not only stable emulsion states compared to the ink compositions of Comparative Examples 1 to 3, but also viscosity according to environmental changes. As there is no change, film drying does not occur even after long-term exposure, so it can be confirmed that good quality reprinting is possible. In particular, it can be confirmed that the ink composition according to the present invention also has a good penetration quick-drying.

As described above, the present invention not only has excellent penetration fast-drying and storage stability, but also does not form an oxide dry film or change viscosity even after exposure to ink due to prolonged printing stop on a printing machine. There is a useful effect of providing a water-in-oil type printing ink composition which is excellent in printability of the ink so as to enable good high speed printing.

Claims (4)

delete delete delete In a water-in-oil type ink composition comprising a palm oil alkyd resin as a binder and a nonvolatile oil, a pigment, a surfactant, a dispersant, water, and a water-soluble resin, The palm oil alkyd resin is phthalic anhydride, maleic anhydride, fumaric acid, maleic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, tetrahydrophthalic acid and citric acid based on 100 parts by weight of palm oil. 60 to 80 parts by weight of a polybasic acid selected from trimellitic acid and trimellitic anhydride and glycerin, pentaerythritol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, trimethylene glycol, tetramethylene Obtained by mixing 40 to 60 parts by weight of a polyhydric alcohol selected from glycol, trimethylene propane, diglycerin, dipentaerythritol, mannitol and sorbitol, and adding xylene to reflux to condensation reaction to remove xylene The acid value is 10 or less, the whey is 40 to 60%, the molecular weight is 20,000 to 40,000, the total printing ink composition 100% by weight Water-in-oil type printing ink composition, characterized in that included in the range of 3 to 9% by weight.