KR20180117393A - Environment-friendly Ink composition for offset printing And Manufacturing Method Thereof - Google Patents

Abstract

The present invention provides an ecofriendly offset ink for printing which satisfies printing efficiency without lowering drying and emulsifying against an existing ink even when a harmful hydroquinone-based additive and a petroleum-based organic solvent are not used. The ecofriendly offset ink for printing which does not include the hydroquinone and the petroleum-based organic solvent comprises: a first resin-modified phenol resin vehicle of 20 to 40 wt%; a second resin-modified phenol resin vehicle of 10 to 30 wt%; a third resin-modified phenol resin vehicle of 10 to 30 wt%; a dye of 5 to 25 wt%; a cyclodextrin-metal desiccant of 1 to 3 wt%; and an extra fatty acid methyl ester as a solvent.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an offset ink for offset printing,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an environmentally friendly offset ink for printing and a method of manufacturing the same, and more particularly, to an environmentally friendly offset ink for printing that does not include hydroquinone and a petroleum-based organic solvent, and a method for manufacturing the same.

The composition of the conventional printing ink is composed of pigment, resin, petroleum organic solvent, vegetable oil, and other additives. Such a composition is composed of various kinds of chemical substances, and volatile harmful substances may be continuously released, which may be vulnerable to environmental problems.

In recent years, eco-friendly products such as solvent-free inks, which replace solvents with harmless plant-based pigments, have been continuously developed and marketed. However, since printing inks are composed of mixed chemical compositions of various chemicals, printing is performed in consideration of physical properties and environment- Performance improvement is required to improve process efficiency.

An anti-film forming agent used for the purpose of preventing the film formation of the composition among the additives to be applied to the composition of the printing ink and a metal drying additive in an arbitrary ratio for promoting dryness of the printed material in the printing process and improving the efficiency of the printing process .

Adjuvants such as an anti-film formation agent are generally used as hydroquinone-based additives, and there is a concern about the carcinogenicity thereof, which is treated as a limitation, but substitution is necessary.

In addition, since petroleum-based organic solvents are volatile compounds harmful to human body, it is also necessary to substitute them because it is harmful to workers who are actually in touch with the working environment such as printing companies and ink manufacturers.

In order to solve the above-described problems, when a metal drying agent is prepared in a single composition without an additive such as an anti-film forming agent, the drying property of the printing ink is deteriorated due to the dried coating,

Likewise, printing inks containing no petroleum-based organic solvent may be dried and set dry, poor water resistance, and printing defects may occur, thus reducing the efficiency of the printing process. Therefore, there is a need to develop eco-friendly inks that satisfy the printing efficiency without deteriorating physical properties including drying properties without using hydroquinone-based additives and petroleum-based organic solvents at the same time.

Accordingly, the present invention has been made in view of the above problems, and it is an object of the present invention to provide a process for producing a hydroquinone- To provide an environmentally friendly offset ink for printing.

Another object of the present invention is to provide a process for the production of vegetable oil, which comprises applying a vegetable oil, a cyclodextrin-metal drying agent and a fatty acid methyl ester to produce a hydroquinone- And a method of producing an eco-friendly offset ink for printing which satisfies at the same time an efficient aspect.

The eco-friendly offset ink for printing for realizing the above object of the present invention contains 20 to 40% by weight of the first rosin-modified phenolic resin vehicle, 10 to 30% of the second rosin-modified phenolic resin vehicle without hydroquinone and petroleum- 10 to 30% by weight of a third rosin-modified phenolic resin vehicle, 5 to 25% by weight of a pigment, 1 to 3% by weight of a cyclodextrin-metal desiccant and an excess fatty acid methyl ester as a solvent.

In one embodiment, the first rosin-modified phenolic resin vehicle is formed by introducing a vegetable oil into a rosin-modified phenolic resin and dissolving at a first temperature condition (180 ° C to 190 ° C), and the second rosin- And the third rosin-modified phenolic resin vehicle is formed by dissolving the vegetable oil in rosin-modified phenol resin at a second temperature condition (190 ° C to 200 ° C) higher than the first temperature condition and then gelling, And is melted at a third temperature condition (220 캜 to 240 캜) higher than the second temperature, followed by gelation.

In one embodiment, the rosin-modified phenolic resin has a weight average molecular weight in the range of 120,000 to 170,000, a softening point in the range of 160 ° C to 185 ° C, an acid value of 25 mg KOH / g or less, a Gardner viscosity of U to X, Heptane dilution property and a color number of 14 or less can be used.

In one embodiment, the first rosin-modified phenolic resin vehicle comprises 20 to 40 parts by weight of a rosin-modified phenolic resin and 10 to 30 parts by weight of a vegetable oil, stirring the mixture to maintain the temperature at 170 to 190 ° C, Followed by cooling to 140 캜 or less after the addition.

In one embodiment, the second rosin-modified phenolic resin vehicle comprises 20 to 60 parts by weight of a rosin-modified phenolic resin and 10 to 30 parts by weight of a vegetable oil, stirring the mixture and maintaining the temperature at 180 to 200 ° C, And 0.1 to 5 parts by weight of a gelling agent at a temperature of 150 to 170 ° C. and cooling the mixture to 140 ° C. or less.

In one embodiment, the third rosin-modified phenolic resin vehicle comprises 20 to 60 parts by weight of a rosin-modified phenolic resin and 10 to 30 parts by weight of a vegetable oil, stirring the mixture and maintaining the temperature at 220 to 240 ° C, And 0.1 to 5 parts by weight of a gelling agent at a temperature of 150 to 170 DEG C and cooling to 140 DEG C or less.

In one embodiment, the cyclodextrin-metal desiccant is prepared by mixing a metal desiccant-containing solution 40-76 wt%, cyclodextrin 15-40 wt%, and excess water to form a metal desiccant mixture, And a cyclodextrin having an annular structure containing a metal desiccant and a part of the metal desiccant and bound to one side of the metal desiccant.

In one embodiment, the offset ink for environmentally friendly printing may further comprise 1 to 6% by weight of an additive comprising wax and an emulsion stabilizer.

In order to produce the eco-offset ink for printing for realizing another object of the present invention described above, the first rosin-modified phenol resin vehicle, the second rosin-modified phenol resin vehicle and the third rosin-modified phenol resin vehicle are respectively provided. Next, 20 to 40% by weight of the first rosin-modified phenolic resin vehicle, 10 to 30% by weight of the second rosin-modified phenolic resin vehicle; 10 to 30% by weight of the third rosin-modified phenolic resin vehicle; 5 to 25% by weight of pigment; 1 to 3% by weight of the cyclodextrin-metal drying agent and the extra fatty acid methyl ester are mixed.

The eco-friendly offset ink for printing produced by the composition and the method described above satisfactorily satisfies physical properties such as emulsification suitability, and can sufficiently delay the formation of the coating film of offset ink for printing even without using hydroquinone or petroleum organic solvent. In addition, since it does not contain harmful components to the human body, it is possible to improve the working environment in addition to environmental prints.

Hereinafter, the present invention will be described in more detail. While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are further described in the text. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

In this application, the terms "comprises" or "having", etc. are intended to specify the presence of stated features, components, steps, processes, compositions, or combinations thereof in the specification, and not to limit the presence or addition of one or more other features or components, Steps, processes, compositions, or combinations thereof, which are not intended to be limiting.

Also, unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.

Eco-friendly offset ink for printing

The eco-friendly offset ink for printing according to the present invention does not use harmful hydroquinone-based additives and petroleum-based organic solvents but, instead of using a mixture temperature condition of the rosin-modified phenolic resin and the vegetable oil or the application of the emulsifier, Modified phenolic resin vehicle, cyclodextrin-metal desiccant, and fatty acid methyl ester.

Specifically, the printing environmentally friendly offset ink that simultaneously satisfies the environmentally friendly printing efficiency without deteriorating the drying property and the emulsification suitability against the conventional ink, comprises 20 to 40% by weight of the first rosin denatured phenol resin vehicle, 10 to 40% by weight of the second rosin denatured phenolic resin vehicle 10 To 10% by weight of a third rosin-modified phenolic resin vehicle, from 5% to 25% by weight of a pigment, from 1% to 3% by weight of a cyclodextrin-metal desiccant and an extra fatty acid methyl ester as a solvent.

In one embodiment, the first rosin-modified phenolic resin vehicle has a rosin-modified phenolic resin in the form of a solid phase, so that the first rosin-modified phenolic resin vehicle can be prepared by adding vegetable oil (drying oil, semi-drying oil) ). More specifically, the first rosin-modified phenolic resin vehicle is prepared by mixing 20 to 60 parts by weight of a rosin-modified phenolic resin and 10 to 30 parts by weight of a vegetable oil with stirring to maintain the temperature at 170 to 190 DEG C, Lt; RTI ID = 0.0 > 140 C < / RTI >

As an example, the rosin-modified phenolic resin to be used for preparing the first to third rosin-modified phenolic resin vehicles may be prepared by reacting an intermediate obtained by esterification reaction of a mixture containing rosin and a petroleum resin with a polyhydric alcohol, Aldehyde. ≪ / RTI >

Wherein the rosin-modified phenolic resin has a weight average molecular weight of about 120,000 to about 170,000 and has an acid value of about 25 mg KOH / g or less besides the softening point of about 160 ° C to about 185 ° C and has n-heptane dilutability of 1 to 20 or less , A Gardner viscosity of about U to about X, and a Gardner color number of about 14 or less.

When the weight average molecular weight of the rosin-modified phenolic resin is less than about 120,000, set drying is slow and thermal stability is poor. On the other hand, when the weight average molecular weight exceeds about 170,000, the variation of the viscosity is large and the metastability is deteriorated. Therefore, the weight average molecular weight of the rosin-modified phenolic resin is preferably about 120,000 to about 170,000.

If the softening point is less than about 160 ° C, the set drying is slow and the viscoelasticity is poor. When the softening point is more than about 185 ° C, the viscosity is changed with time and the metastability is deteriorated. Therefore, it is preferable that the softening point has a value within a range of 160 占 폚 to 180 占 폚.

N-heptane dilution was determined by diluting 1 g of the resin in a beaker and dissolving 2 g of toluene in a beaker, adding n-heptane dropwise at room temperature until the solution became opaque and the newspaper under the beaker could not be identified g), and the N-heptane diluting property preferably has a value in the range of 1 to 20. [

The second rosin-modified phenolic resin vehicle has a rosin-modified phenolic resin in a solid form, and therefore, the rosin-modified phenol resin is added to the rosin-modified phenol resin under a second temperature condition (190 ° C to 200 ° C ) And then using a gelling agent such as an aluminum chelate. Specifically, the second rosin-modified phenolic resin vehicle is prepared by mixing 20 to 60 parts by weight of a rosin-modified phenolic resin and 10 to 30 parts by weight of a vegetable oil with stirring to maintain the temperature of the mixture at 180 to 200 ° C (dissolution step) (Gelation step) at a temperature of 150 to 170 ° C and cooling the solution to 140 ° C or less.

Since the rosin-modified phenolic resin has a hard solid form, the third rosin-modified phenol resin vehicle may be added to the third rosin-modified phenol resin vehicle under a third temperature condition (220 캜 to 240 캜 ) And then using a gelling agent such as an aluminum chelate. More specifically, 20 to 60 parts by weight of a rosin-modified phenol resin and 10 to 30 parts by weight of a vegetable oil are stirred and maintained at a temperature of 220 to 240 DEG C, 10 to 30 parts by weight of a vegetable oil and 0.1 to 5 parts by weight of a gelling agent Followed by a maintenance reaction at a temperature of 150 to 170 DEG C and a step of cooling to 140 DEG C or less.

As an example, it is preferable that the modified phenolic resin is used in the range of 20 to 60 parts by weight in the production of the first to third rosin-modified phenolic resin vehicles. When the amount is less than 20 parts by weight, the viscosity of the vehicle is low, resulting in poor viscoelasticity and causing non-fouling. If the amount of the modified phenol resin used exceeds 60 parts by weight with respect to 100 parts by weight of the whole vehicle, the viscosity may become high, which may cause a transition failure.

As an example, vegetable fats applied in the production of the first to third rosin-modified phenolic resin vehicles include dry oils, semi-synthetic radial oils or mixtures thereof, having an iodine value of 100 to 250 and a saponification value of 170 to 210 desirable. Examples of the vegetable oils include vegetable oils such as soybean oil and linseed oil, which may be used alone or in combination.

In one embodiment, when the amount of the first rosin-modified phenolic resin vehicle used in the printing environmentally friendly offset ink of the present invention is less than 20% by weight, wettability with the pigment is deteriorated to deteriorate dispersibility. When the amount is more than 40% by weight, The rate is increased to make it difficult to form halftone dots, resulting in poor printability. Accordingly, the printing environmentally friendly offset ink of the present invention preferably comprises 20 to 40% by weight of the first rosin-modified phenolic resin vehicle.

If the amount of the second rosin-modified phenolic resin vehicle is less than 10% by weight, the viscoelasticity of the ink composition is lowered as the viscosity is lowered. When the amount is more than 30% by weight, the viscosity of the ink composition is increased and the metastability is lowered. Accordingly, the printing environmentally friendly offset ink of the present invention preferably comprises 10 to 30% by weight of the second rosin-modified phenolic resin vehicle.

When the amount of the third rosin-modified phenolic resin vehicle is less than 10% by weight, the printability becomes poor. When the amount of the third rosin-modified phenolic resin vehicle is more than 30% by weight, the viscoelasticity is decreased. Accordingly, the printing environmentally friendly offset ink of the present invention preferably comprises 10 to 30% by weight of the third rosin-modified phenolic resin vehicle.

In one embodiment, the cyclodextrin-metal desiccant is prepared by mixing a metal desiccant-containing solution 40-76 wt%, cyclodextrin 15-40 wt%, and excess water to form a metal desiccant mixture, And a cyclodextrin having an annular structure containing a metal desiccant and a part of the metal desiccant and bound to one side of the metal desiccant.

As an example, examples of the metal desiccant applied to the cyclodextrin-metal desiccant include metal acetic acid salts such as cobalt, manganese, zirconium, iron and calcium, metal nitrate, metal nitrite, metal sulfate, metal sulfite, metal chloride, Organic metal salts, organometallic compounds, and the like. These may be used singly or in a mixture of two or more.

In addition, cyclodextrin-metal desiccants are not soluble in dry or semi-drying oils such as vegetable oils, and are soluble only in lower alcohols and water. With this characteristic, the cyclodextrin-metal drying agent is not activated in the offset ink for printing, so that the film delay effect is obtained without the hydroquinone-based additive, and in the printing process, it is dissolved by the wetting water to improve the drying property of the printing ink.

If the amount of the cyclodextrin-metal drying agent used is less than 0.5% by weight, the drying efficiency of the printed material is lowered and further composition of the ink composition is required. When the amount of the cyclodextrin-metal drying agent is more than 3% by weight, So that the workability may be deteriorated. Accordingly, the printing environmentally friendly offset ink of the present invention preferably comprises 1 to 3% by weight of cyclodextrin-metal drying agent.

As an example, the fatty acid methyl ester is a methyl ester prepared by using a waste cooking oil as a raw material, and its main components are oleic acid salt and linoleic acid salt, and has an iodine value of 110 to 115. It is made by transesterification method in which glycerol is separated from triglyceride in which glycerol is bonded to trivalent fatty acid by using methanol, and fatty acid ester is produced. It is an eco-friendly solvent that can replace petroleum-based organic solvents.

If the amount of the fatty acid methyl ester used is less than 5% by weight, the viscosity may increase and the fluidity may decrease and gloss failure may occur. If the amount is more than 15% by weight, the viscosity is lowered, and the water resistance is lowered and ink bleeding phenomenon may occur. Accordingly, the printing environmentally friendly offset ink of the present invention preferably contains 5 to 15% by weight of fatty acid methyl ester.

In one embodiment, the offset ink for eco-friendly printing may further comprise 1 to 6% by weight of conventional additives including wax and an emulsion stabilizer. As the above additives, additives commonly used in general oily inks can be used.

Method of manufacturing offset ink for environmentally friendly printing.

In order to produce an offset ink for environmentally friendly printing according to an embodiment of the present invention, the first rosin-modified phenol resin vehicle, the second rosin-modified phenol resin vehicle, and the third rosin-modified phenol resin vehicle are provided, respectively.

The first rosin-modified phenolic resin vehicle is formed by dissolving the rosin-modified phenolic resin in a first temperature condition (180 ° C to 190 ° C) by adding vegetable oil (drying oil, semi-drying oil) or the like because the rosin- .

More specifically, the first rosin-modified phenolic resin vehicle is prepared by mixing 20 to 60 parts by weight of a rosin-modified phenolic resin and 10 to 30 parts by weight of a vegetable oil with stirring to maintain the temperature of the mixture at 170 to 190 DEG C (dissolution step) Followed by cooling to 140 DEG C or less after the addition of the weight part.

The second rosin-modified phenolic resin vehicle has a rosin-modified phenolic resin in a solid form, and therefore, the rosin-modified phenol resin is added to the rosin-modified phenol resin under a second temperature condition (190 ° C to 200 ° C ) And then using a gelling agent such as an aluminum chelate.

More specifically, the second rosin-modified phenolic resin vehicle is prepared by mixing 20 to 60 parts by weight of a rosin-modified phenolic resin and 10 to 30 parts by weight of a vegetable oil with stirring to maintain the temperature of the mixture at 180 to 200 DEG C (dissolution step) (Gelation step) at 150 to 170 ° C and cooling the solution to 140 ° C or less.

Since the rosin-modified phenolic resin has a hard solid form, the third rosin-modified phenol resin vehicle may contain a vegetable oil (drying oil, semi-drying oil) or the like and may be added under a third temperature condition (220 캜 to 240 캜 ) And then using a gelling agent such as an aluminum chelate.

More specifically, 20 to 60 parts by weight of a rosin-modified phenolic resin and 10 to 30 parts by weight of a vegetable oil are stirred and heated to 220 to 240 ° C. (dissolution step), 10 to 30 parts by weight of a vegetable oil, 5 to 5 parts by weight of the reaction mixture is maintained at a temperature of 150 to 170 DEG C, and cooling to 140 DEG C or less.

The detailed description of the rosin-modified phenol resin, vegetable oil, and the vegetable oil applied to the first to third rosin-modified phenol resin vehicles has been described in detail above and is omitted in order to avoid redundancy.

A second rosin-modified phenolic resin vehicle, 10 to 30 wt% of the third rosin-modified phenolic resin vehicle, 5 to 25 wt% of the pigment, , 1 to 3% by weight of a cyclodextrin-metal drying agent and 1 to 3% by weight of an excess fatty acid methyl ester to produce an eco-friendly offset ink for printing which simultaneously satisfies environmentally friendly printing efficiency have.

In another embodiment, the first rosin-modified phenolic resin vehicle comprises 20 to 40 wt%, the second rosin-modified phenolic resin vehicle 10 to 30 wt%, the third rosin-modified phenolic resin vehicle 10 to 30 wt% 1 to 6% by weight of a cyclodextrin-metal drying agent, 1 to 3% by weight of a cyclodextrin-metal drying agent, 1 to 6% by weight of an additive comprising a wax and an emulsifying stabilizer and an extra fatty acid methyl ester, It is possible to manufacture an environmentally friendly offset ink for printing which simultaneously satisfies environmentally friendly printing efficiency.

The eco-friendly offset ink for printing produced by the above-described method can sufficiently delay the formation of the coating film of offset ink for printing even without using hydroquinone and a petroleum-based organic solvent, and satisfies physical properties such as emulsification suitability. In addition, since it does not contain harmful components to the human body, it is possible to improve the working environment in addition to environmental prints.

Hereinafter, the present invention will be described in more detail with reference to specific examples and comparative examples. It is to be understood by those skilled in the art that these examples are for illustrative purposes only and that the scope of the present invention is not limited by these examples without departing from the gist of the present invention.

Production Example 1) Production of the first rosin-modified phenolic resin vehicle

42 parts by weight of rosin-modified phenolic resin and 24 parts by weight of vegetable oil (drying oil / semi-drying oil) were put in a four-necked flask, and a stirrer, a thermometer and a water separator were connected to each other. . Subsequently, 20% by weight of vegetable oil (mixed with drying oil and semi-drying oil) was added and cooled to 140 ° C. Then, 3 parts by weight of vegetable oil was further added to obtain a first rosin-denatured phenol resin vehicle (Vehicle I).

Production Example 2) Production of second rosin-modified phenol resin vehicle

41 parts by weight of rosin-denatured phenol resin and 24 parts by weight of vegetable oil (drying oil) were added to a four-necked flask, and a stirrer, a thermometer and a water separator were connected to each other. Thereafter, 20% by weight of vegetable oil (drying oil) was added to lower the temperature, and the gelling agent was added at 160 DEG C for 1 hour. The oil was then cooled to 140 DEG C and 3% by weight of dry oil was added thereto to prepare a second rosin- II).

Production Example 3) Production of a third rosin-modified phenol resin vehicle

43 parts by weight of rosin-modified phenol resin and 24 parts by weight of vegetable oil (mixed with drying oil / semi-drying oil) were put into a four-necked flask, and the mixture was heated to 230 DEG C by connecting a stirrer, a thermometer and a water separator, Respectively. Then, the temperature was lowered by adding 20% by weight of vegetable oil (mixed with drying oil / semi-drying oil), and the gelling agent was added at 160 DEG C for 1 hour and then cooled to 140 DEG C to obtain 3% by weight of vegetable oil (mixed with drying oil and semi-drying oil) And further added to obtain a third rosin-modified phenolic resin vehicle (Vehicle III). The composition and design conditions of the rosin-modified phenol resin vehicle prepared in Preparation Examples 1 to 3 are shown in Table 1.

[Table 1]

Printable Offset  Ink manufacture Examples

[Example 1]

32 parts by weight of Vehicle I prepared in Synthesis Example 1, 20 parts by weight of Vehicle II prepared in Synthesis Example 2, 3 parts by weight of Synthesis Example 3 , 20 parts by weight of Vehicle III, 13 parts by weight of yellow pigment, 1.15 parts by weight of cyclodextrin-metal drying agent, 10 parts by weight of fatty acid methyl ester solvent and 4 parts by weight of other additives were mixed and then passed three times to prepare printing offset ink .

[Example 2]

32 parts by weight of the Vehicle I prepared in Synthesis Example 1, 20 parts by weight of the Vehicle II prepared in Synthesis Example 2, 2 parts by weight of the synthetic resin (Synthesis Example 2) were dispersed in a roll mill dispersed at the same rotation speed as that used in Example 1 at a speed of 1: 3: 20 parts by weight of Vehicle III prepared in Example 3, 13 parts by weight of a yellow pigment, 2.8 parts by weight of a cyclodextrin-metal drying agent, 10 parts by weight of a fatty acid methyl ester solvent and 4 parts by weight of other additives were mixed and passed three times, .

[Example 3]

32 parts by weight of the Vehicle I prepared in Synthesis Example 1, 20 parts by weight of the Vehicle II prepared in Synthesis Example 2, 2 parts by weight of the synthetic resin (Synthesis Example 2) were dispersed in a roll mill dispersed at the same rotation speed as that used in Example 1 at a speed of 1: 3: 20 parts by weight of Vehicle III produced in Example 3, 13 parts by weight of a yellow pigment, 1.5 parts by weight of a cyclodextrin-metal drying agent, 10 parts by weight of a fatty acid methyl ester solvent and 4 parts by weight of other additives were mixed, .

[Example 4]

32 parts by weight of the Vehicle I prepared in Synthesis Example 1, 20 parts by weight of the Vehicle II prepared in Synthesis Example 2, 2 parts by weight of the synthetic resin (Synthesis Example 2) were dispersed in a roll mill dispersed at the same rotation speed as that used in Example 1 at a speed of 1: 3: 20 parts by weight of Vehicle III prepared in Example 3, 13 parts by weight of a yellow pigment, 0.8 part by weight of a cyclodextrin-metal drying agent, 10 parts by weight of a fatty acid methyl ester solvent and 4 parts by weight of other additives were mixed and passed three times, .

[Example 5]

30 parts by weight of Vehicle I prepared in Synthesis Example 1, 20 parts by weight of Vehicle II prepared in Synthesis Example 2, 3 parts by weight of Synthesis Example 3 (manufactured by Mitsui Chemicals, Inc.) were added to a roll mill dispersed at the same rotation speed as that used in Example 1 at a speed of 1: 3: 20 parts by weight of Vehicle III, 16 parts by weight of a red pigment, 0.4 part by weight of a cyclodextrin-metal drying agent, 9.6 parts by weight of a fatty acid methyl ester solvent and 4 parts by weight of other additives were mixed and then passed three times to prepare offset ink for printing .

[Example 6]

30 parts by weight of Vehicle I prepared in Synthesis Example 1, 20 parts by weight of Vehicle II prepared in Synthesis Example 2, 3 parts by weight of Synthesis Example 3 (manufactured by Mitsui Chemicals, Inc.) were added to a roll mill dispersed at the same rotation speed as that used in Example 1 at a speed of 1: 3: 20 parts by weight of Vehicle III, 16 parts by weight of a red pigment, 0.55 part by weight of a cyclodextrin-metal drying agent, 9.6 parts by weight of a fatty acid methyl ester solvent and 4 parts by weight of other additives were mixed and then passed three times to prepare offset ink for printing Respectively.

[Example 7]

30 parts by weight of Vehicle I prepared in Synthesis Example 1, 20 parts by weight of Vehicle II prepared in Synthesis Example 2, 3 parts by weight of Synthesis Example 3 (manufactured by Mitsui Chemicals, Inc.) were added to a roll mill dispersed at the same rotation speed as that used in Example 1 at a speed of 1: 3: 20 parts by weight of Vehicle III, 16 parts by weight of a red pigment, 0.75 part by weight of a cyclodextrin-metal drying agent, 9.6 parts by weight of a fatty acid methyl ester solvent and 4 parts by weight of other additives were mixed and then passed three times to prepare offset ink for printing Respectively.

[Example 8]

30 parts by weight of Vehicle I prepared in Synthesis Example 1, 20 parts by weight of Vehicle II prepared in Synthesis Example 2, 3 parts by weight of Synthesis Example 3 (manufactured by Mitsui Chemicals, Inc.) were added to a roll mill dispersed at the same rotation speed as that used in Example 1 at a speed of 1: 3: 20 parts by weight of Vehicle III, 16 parts by weight of a red pigment, 1.15 parts by weight of a cyclodextrin-metal drying agent, 9.6 parts by weight of a fatty acid methyl ester solvent and 4 parts by weight of other additives were mixed and then passed three times to prepare offset ink for printing .

[Example 9]

30 parts by weight of Vehicle I prepared in Synthesis Example 1, 20 parts by weight of Vehicle II prepared in Synthesis Example 2, 20 parts by weight of Synthesis Example 2, 20 parts by weight of Vehicle III prepared in Example 3, 18 parts by weight of a blue pigment, 0.4 part by weight of a cyclodextrin-metal drying agent, 7 parts by weight of a fatty acid methyl ester solvent and 4.6 parts by weight of other additives were mixed and passed three times, .

[Example 10]

30 parts by weight of Vehicle I prepared in Synthesis Example 1, 20 parts by weight of Vehicle II prepared in Synthesis Example 2, 20 parts by weight of Synthesis Example 2, 20 parts by weight of Vehicle III prepared in Example 3, 18 parts by weight of a blue pigment, 0.55 parts by weight of a cyclodextrin-metal drying agent, 7 parts by weight of a fatty acid methyl ester solvent and 4.6 parts by weight of other additives were added, .

[Example 11]

30 parts by weight of Vehicle I prepared in Synthesis Example 1, 20 parts by weight of Vehicle II prepared in Synthesis Example 2, 20 parts by weight of Synthesis Example 2, 20 parts by weight of Vehicle III prepared in Example 3, 18 parts by weight of a blue pigment, 0.75 part by weight of a cyclodextrin-metal drying agent, 7 parts by weight of a fatty acid methyl ester solvent and 4.6 parts by weight of other additives were added, .

[Example 12]

30 parts by weight of Vehicle I prepared in Synthesis Example 1, 20 parts by weight of Vehicle II prepared in Synthesis Example 2, 20 parts by weight of Synthesis Example 2, 20 parts by weight of Vehicle III prepared in Example 3, 18 parts by weight of a blue pigment, 1.15 parts by weight of a cyclodextrin-metal drying agent, 7 parts by weight of a fatty acid methyl ester solvent, and 4.6 parts by weight of other additives were added, .

[Example 13]

30 parts by weight of Vehicle I prepared in Synthesis Example 1, 17 parts by weight of Vehicle II prepared in Synthesis Example 2, 5 parts by weight of Synthesis Example 2, 20 parts by weight of Vehicle III prepared in Example 3, 19 parts by weight of a black pigment, 1.15 parts by weight of a cyclodextrin-metal drying agent, 8 parts by weight of a fatty acid methyl ester solvent and 5 parts by weight of other additives were mixed and passed three times, .

[Example 14]

30 parts by weight of Vehicle I prepared in Synthesis Example 1, 17 parts by weight of Vehicle II prepared in Synthesis Example 2, 5 parts by weight of Synthesis Example 2, 20 parts by weight of Vehicle III prepared in Example 3, 19 parts by weight of a black pigment, 2.8 parts by weight of a cyclodextrin-metal drying agent, 8 parts by weight of other additives, and 5 parts by weight of other additives were mixed and then passed three times to prepare offset ink for printing

[Example 15]

30 parts by weight of Vehicle I prepared in Synthesis Example 1, 17 parts by weight of Vehicle II prepared in Synthesis Example 2, 5 parts by weight of Synthesis Example 2, 20 parts by weight of Vehicle III prepared in Example 3, 19 parts by weight of a black pigment, 1.5 parts by weight of a cyclodextrin-metal drying agent, 8 parts by weight of a fatty acid methyl ester solvent, and 5 parts by weight of other additives were mixed and passed three times, .

[Example 16]

30 parts by weight of Vehicle I prepared in Synthesis Example 1, 17 parts by weight of Vehicle II prepared in Synthesis Example 2, 5 parts by weight of Synthesis Example 2, 20 parts by weight of Vehicle III prepared in Example 3, 19 parts by weight of a black pigment, 0.8 part by weight of a cyclodextrin-metal drying agent, 8 parts by weight of a fatty acid methyl ester solvent and 5 parts by weight of other additives were mixed and passed three times, .

[Comparative Example 1]

72 parts by weight of a rosin-modified phenol resin, 13 parts by weight of a yellow pigment, 1.2 parts by weight of hydroquinone, 8.5 parts by weight of a petroleum-based organic solvent 8.5 And 5.3 parts by weight of other additives were mixed and then passed through three times to prepare offset ink for printing.

[Comparative Example 2]

70 parts by weight of a rosin-modified phenol resin, 16 parts by weight of a red pigment, 1 part by weight of hydroquinone, 9 parts by weight of a petroleum-based organic solvent 9 And 4 parts by weight of other additives were mixed and passed three times to prepare offset ink for printing.

[Comparative Example 3]

70 parts by weight of a rosin-modified phenol resin, 18 parts by weight of a blue pigment, 1.2 parts by weight of hydroquinone, 6.8 parts by weight of a petroleum-based organic solvent 6.8 parts by weight, And 4 parts by weight of other additives were mixed and passed three times to prepare offset ink for printing.

[Comparative Example 4]

67 parts by weight of a rosin-modified phenol resin, 19 parts by weight of a black pigment, 0.8 parts by weight of hydroquinone, and 8 parts by weight of a petroleum resin were dispersed in a roll mill dispersed at a speed of 1: 3: 9, , And 5.2 parts by weight of other additives were mixed and passed three times to prepare offset ink for printing.

[Experimental Evaluation]

The drying delay and drying improvement performance of the printing ink before and after emulsification of the printing ink composition according to the above Comparative Examples and Examples were evaluated by a skinning test by hot air drying. The results are shown in Tables 2 and 3 below.

* The skinning test was carried out using an applicator, and an ink coating film was formed in a thickness of 60 μm and stored in a 50 ° C hot air dryer.

In the emulsification condition, 50 g of the printing ink composition prepared above was stirred at a stirring speed of 5,000 rpm, and 12.5 ml of the dampening water used in the printing process was emulsified while being slowly added to the stirring printing ink, and dried by a skinning test under the same conditions as above Respectively.

* The gloss evaluation was conducted by transferring the printing ink composition prepared according to the comparative example and the example to a 120 g art paper in a coloring machine using a four-division roller at 0.1 cc, And evaluated.

In the high-speed development, 0.2 cc of the printing ink composition prepared in Comparative Examples and Examples was transferred to 120 g of art paper together with wetting water using a high-speed printing tester, and the state of the printed matter was visually observed and evaluated.

* In case of HQ detection and VOCs, an inspection was commissioned to an external accredited testing laboratory and evaluated with test results.

[Table 2]

[Table 3]

Claims (14)

In environmentally-friendly offset inks that do not contain hydroquinone and petroleum-based organic solvents,
20 to 40% by weight of the first rosin-modified phenolic resin vehicle,
10 to 30% by weight of a second rosin-modified phenolic resin vehicle;
10 to 30% by weight of a third rosin-modified phenolic resin vehicle;
5 to 25% by weight of pigment;
1 to 3% by weight of a cyclodextrin-metal drying agent; And
Environmentally friendly offset ink containing extra fatty acid methyl esters. The method of claim 1, wherein the first rosin-modified phenolic resin vehicle is formed by dissolving a vegetable oil in a rosin-modified phenol resin at a first temperature condition (180 ° C to 190 ° C), and the second rosin- And the third rosin-modified phenolic resin vehicle is formed by injecting vegetable oil into the rosin-modified phenolic resin to dissolve the rosin-modified phenolic resin at a second temperature higher than the first temperature condition, Wherein the ink is formed by dissolving at a higher third temperature condition and then gelling. The rosin-modified phenolic resin of claim 2, wherein the rosin-modified phenolic resin has a weight average molecular weight in the range of 120,000 to 170,000, a softening point in the range of 160 DEG C to 185 DEG C, an acid value of 25 mg KOH / g or less, a Gardner viscosity of U to X, -Heptane dilution property and a color number of 14 or less. The offset ink for eco-friendly printing as claimed in claim 2, wherein the vegetable oil comprises a drying oil and a semi-drying oil and has an iodine value of 100 to 250 and a saponification value of 170 to 210. The method of claim 1, wherein the first rosin-modified phenolic resin vehicle
20 to 60 parts by weight of a rosin-modified phenol resin and 10 to 30 parts by weight of a vegetable oil are stirred and maintained at 170 to 190 DEG C; And
10 to 30 parts by weight of vegetable oil is added and then cooled to 140 占 폚 or less, whereby an offset ink for environmentally friendly printing is obtained. The method of claim 1, wherein the second rosin-modified phenolic resin vehicle
20 to 60 parts by weight of a rosin-modified phenolic resin and 10 to 30 parts by weight of a vegetable oil are stirred and maintained at a temperature of 180 to 200 캜; And
10 to 30 parts by weight of a vegetable oil and 0.1 to 5 parts by weight of a gelling agent are added and maintained at a temperature of 150 to 170 DEG C; And
And cooling it to 140 DEG C or lower. The method of claim 1, wherein the third rosin-modified phenolic resin vehicle
20 to 60 parts by weight of a rosin-modified phenolic resin and 10 to 30 parts by weight of a vegetable oil are stirred and maintained at 220 to 240 캜;
10 to 30 parts by weight of a vegetable oil and 0.1 to 5 parts by weight of a gelling agent are added and maintained at a temperature of 150 to 170 DEG C; And
And cooling it to 140 DEG C or lower. The method of claim 1, wherein the cyclodextrin-
A metal desiccant-containing solution is prepared by mixing 40 to 76% by weight of the metal desiccant-containing solution, 15 to 40% by weight of the cyclodextrin and extra water to form a metal desiccant mixture, and drying the metal desiccant mixture. An offset ink for eco-friendly printing having an annular structure and comprising cyclotrhein bound to one side of the metal desiccant. The offset ink for eco-friendly printing according to claim 1, further comprising 1 to 6% by weight of an additive comprising wax and an emulsion stabilizer. Providing a first rosin-modified phenolic resin vehicle, a second rosin-modified phenolic resin vehicle, and a third rosin-modified phenolic resin vehicle, respectively; And
Wherein the first rosin-modified phenolic resin vehicle comprises 20 to 40 wt%, the second rosin-modified phenolic resin vehicle comprises 10 to 30 wt%, the third rosin-modified phenolic resin vehicle comprises 10 to 30 wt%, the pigment is 5 to 25 wt% 1 to 3% by weight of a dextrin-metal drying agent and an excess fatty acid methyl ester. 11. The composition of claim 10 wherein the first rosin-modified phenolic resin vehicle comprises
20 to 60 parts by weight of a rosin-modified phenolic resin and 10 to 30 parts by weight of a vegetable oil are stirred and maintained at 170 to 190 DEG C; And
10 to 30 parts by weight of vegetable oil is added, and then cooled to 140 DEG C or less to obtain an offset ink for environmentally friendly printing. The method of claim 10, wherein the second rosin-modified phenolic resin vehicle
20 to 60 parts by weight of a rosin-modified phenolic resin and 10 to 30 parts by weight of a vegetable oil are stirred and maintained at a temperature of 180 to 200 캜;
10 to 30 parts by weight of a vegetable oil and 0.1 to 5 parts by weight of a gelling agent are added and maintained at a temperature of 150 to 170 DEG C; And
And cooling the resulting mixture to 140 DEG C or lower. 11. The composition of claim 10, wherein the third rosin-modified phenolic resin vehicle comprises
20 to 60 parts by weight of a rosin-modified phenolic resin and 10 to 30 parts by weight of a vegetable oil are stirred and maintained at 220 to 240 캜;
10 to 30 parts by weight of a vegetable oil and 0.1 to 5 parts by weight of a gelling agent are added and maintained at a temperature of 150 to 170 DEG C; And
And cooling the resulting mixture to 140 DEG C or lower. The method according to claim 10, further comprising 1 to 6% by weight of an additive comprising wax and an emulsion stabilizer.