JPH11140364A - Synthetic resin for printing ink, production thereof, and printing ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a printing ink which hardly leaves behind an org. solvent in prints and is excellent in gloss and dryability by using a synthetic resin having a specified molecular structure. SOLUTION: This synthetic resin is represented by formula I and has a number average mol.wt. of 400-5,000. In the formula, M1 is a tri- or tetravalent metal; R1 is at least one kind residue selected from among a rosin-modified phenol resin residue, an α,β-monoethylenically unsatd. carboxylic acid-added rosin residue, and a rosin residue; X is a difunctional group representd by formula II or III (wherein R2 is an α,β-monoethylenically unsatd. carboxylic acid-added rosin residue; R3 is a rosin-modified phenol resin residue; and M2 is a divalent metal); m is 1-30; and n is 3-4. The resin is produced by reacting rosin with an α,β-monoethylenically unsatd. carboxylic acid, mixing the resultant carboxyl- contg. rosin with a rosin-modified phenol resin, and reacting the mixture with a divalent metal compd. and then with a tri- or tetravalent metal compd. (e.g. titanium alcoholate).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a synthetic resin useful as a binder for printing ink, especially a binder for gravure printing ink, a method for producing the same, and a printing ink containing the synthetic resin as an essential component.

[0002]

2. Description of the Related Art Synthetic resins for printing inks obtained from rosin and / or a derivative thereof and a metal compound are known for forming ink films having a high softening point and excellent drying properties. It is widely used as a binder.

A synthetic resin in which phenols are introduced into rosin and / or a derivative thereof and a metal compound has been proposed for an intaglio printing ink (JP-A-8-41152). In addition, not only phenols but also synthetic resins in which a fatty acid ester and an ethylenically unsaturated hydrocarbon resin are introduced into rosin and / or a derivative thereof and a metal compound as required (Japanese Patent Application Laid-Open No. 9-09, 1993) have been proposed. No. 3406). Further, U.S. Pat. No. 4,250,066 proposes a calcium resinate of a maleic anhydride adduct to a rosin-modified phenol / formaldehyde condensate and an .alpha.-olefin, or a partially esterified product thereof. However, these conventional synthetic resins tend to have an organic solvent remaining in the printed matter printed by inking, and lack a balance between glossiness and dryness of the printed matter. It does not satisfy chemical needs.

If a large amount of an organic solvent such as toluene remains in a printed matter, the organic solvent scatters in the air, which is not preferable in terms of environmental protection. In addition, with recent high-speed printing presses,
A new problem arises in that the balance between gloss and dryness of printed matter is lacking, and a synthetic resin that can follow this high-speed printing is demanded.

[0005]

DISCLOSURE OF THE INVENTION The present invention relates to a synthetic resin for a printing ink, which can provide a printed matter having a small amount of an organic solvent remaining in the printed matter and excellent balance between gloss and dryness, and a method for producing the same. , And a printing ink containing the printing ink synthetic resin as an essential component,
An object of the present invention is to provide an ink for gravure printing.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies on the above-mentioned problems, and as a result, have found that a divalent metal compound such as calcium hydroxide, a rosin-modified phenol resin and rosin, and / or α, β-monoethylenically unsaturated carboxylic acid addition rosin (hereinafter abbreviated as addition rosin)
And further reacting a trivalent or tetravalent, especially trivalent metal alcoholate compound, to solve the above-mentioned problems, and completed the present invention.

That is, the present invention provides a synthetic resin for a printing ink represented by the following structural formula and having a number average molecular weight of 400 to 5,000.

[0008]

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[Wherein M1 is a trivalent or tetravalent metal;
₁ represents one or more residues selected from the group consisting of rosin-modified phenolic resin residues, α, β-monoethylenically unsaturated carboxylic acid-added rosin residues, and rosin residues.
X represents a divalent functional group represented by Structural Formula (1) or Structural Formula (2), m is an integer of 1 to 30, and n is 3 to 4
Is an integer.

[0010]

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[0011]

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[0012] (wherein, R2 is alpha, represents a β over monoethylenically unsaturated carboxylic acid addition rosin residues, R ₃ is a rosin-modified phenol -. Le resin residues, M2 is representative of a divalent metal) is preferably In the above formula, there is provided a synthetic resin for a printing ink, wherein M1 is one or more selected from the group consisting of aluminum, zirconium and titanium.

A carboxyl group-containing rosin obtained by reacting an α, β-monoethylenically unsaturated carboxylic acid with a rosin and a rosin-modified phenol resin or a rosin ester with a divalent metal compound; Then, a method for producing a synthetic resin for a printing ink characterized by reacting a trivalent or tetravalent metal compound is provided. Preferably, the trivalent or tetravalent metal compound is aluminum alcoholate, zirconium. The present invention provides the above-mentioned production method, which is one or more selected from the group consisting of alcoholates and titanium alcoholates.

Further, the present invention provides a printing ink containing the above synthetic resin for a printing ink and a pigment.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The synthetic resin for a printing ink of the present invention is represented by the following general formula.

[0016]

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X represents a divalent functional group represented by the structural formula (1) or (2).

[0018]

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[0019]

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In the structural formulas (1) and (2), M1 is a trivalent to tetravalent metal, for example, aluminum, zirconium, titanium and the like. Among them, 3 is preferred from the viewpoint of availability. Valent aluminum is more preferred.

M2 is a divalent metal, such as calcium, magnesium, zinc, barium, and manganese. R ₁ is a rosin-modified phenol resin residue,
Rosin ester residue, α, β-monoethylenically unsaturated carboxylic acid addition rosin residue Represents one or more residues selected from the group consisting of rosin residues.

R ₂ represents an additional rosin residue. n shows the numerical value corresponding to the valence of M1, and is an integer of 3-4. m is an integer of 1 to 30, and among these, 1 to 20 is preferable from the viewpoint of gloss.

R ₃ represents a rosin-modified phenol resin residue.

The synthetic resin for printing ink of the present invention is a resin having a number average molecular weight of 400 to 5,000. The number average molecular weight referred to in the present invention refers to a molecular weight indicated by a value measured by gel permeation chromatography (GPC), and the numerical value is a value in terms of polystyrene. If the number average molecular weight of the synthetic resin of the present invention is less than 400, the drying property is poor, and if it exceeds 5,000, the solvent solubility is undesirably reduced.

The viscosity of the synthetic resin of the present invention is preferably 5,000 cps or less in view of handling of the synthetic resin for printing ink. The viscosity of this resin can be measured with a rotational viscometer (B-type viscometer).

Further, the acid value of the synthetic resin for printing ink of the present invention is 20 to 150 KOHm
g / g is preferable. If the acid value is less than 20, there is a problem in pigment dispersibility, and if it exceeds 150, there is a problem in solvent solubility, which is not preferable.

Next, a method for producing the synthetic resin for printing ink of the present invention will be described. That is, as raw materials, 1) rosin-modified phenolic resin, 2) α, β-monoethylenically unsaturated carboxylic acid, 3) rosin, 4) divalent metal compound, and 5) 3-4 tetravalent The synthetic resin for a printing ink of the present invention can be obtained by sequentially reacting these using the metal compounds of the above.

The reaction sequence is as follows: 2) and 3) are reacted, 1) mixed, 4) is reacted, and 5)
Or 2) and 3) are reacted, 1) is mixed, 5) is reacted, and 4) is reacted. After reacting 2) and 3), a method of mixing 1), reacting 4), and then reacting 5) is preferable in that the structure of the product is controlled.

In the present invention, the reactions 4) and 5) are carried out in a solvent. On the other hand, it is possible to carry out the reactions 4) and 5) in a lump (without solvent), but unreacted metal compounds remain, and the resulting resin is not easily uniform, which is not preferable.

The rosin-modified phenolic resin referred to in the present invention is synthesized from phenols and rosin by a known method.
Phenols include phenol and C1 to C1.
Any known and commonly used ones such as alkylphenols having two side chains can be used. For example, phenol, cresols, xylenols, para-tert-butylphenol, para-shariaylphenol, paraoctylphenol, paranonylphenol, cumylphenol
Phenol, paraphenylphenol, bisphenol A and the like. Among these, phenol or an alkylphenol having a side chain having 1 to 4 carbon atoms is particularly preferable from the viewpoint of the balance between the residual amount of the organic solvent and the drying property.

As the rosin, any commonly used rosin can be used. If only typical ones are exemplified, gum rosin, tall oil rosin, wood rosin or polymerized rosin such as dimerized rosin can be mentioned. These may be used alone or as a mixture, and the mixing ratio is not particularly limited.

As the α, β-monoethylenically unsaturated carboxylic acid used for preparing the addition rosin of the present invention, any known and commonly used one can be used. If only typical ones are exemplified, unsaturated dicarboxylic acids such as (anhydride) maleic acid, fumaric acid or itaconic acid may be mentioned.

Next, a divalent metal compound is reacted with the obtained added rosin. As the divalent metal compound, any of those usually used in this type of introduction reaction can be used. If only typical ones are exemplified, oxides, hydroxides or organic acid salts of various metals such as calcium, magnesium, zinc, barium and manganese may be mentioned.

The amount of the metal compound used is suitably in the range of 2 to 20% by weight based on 100 parts of rosin used as a raw material.

Next, the reaction for introducing a trivalent or tetravalent metal into the above-mentioned additional rosin is carried out in the presence of an organic solvent. The reaction temperature is 200 ° C or lower, preferably 50 to 150 ° C.
Is more preferable. When the reaction is performed at a temperature higher than 200 ° C., the progress of the reaction is inevitably too fast, and it is difficult to control the reaction. If the temperature is lower than 50 ° C., the reaction does not proceed sufficiently, which is not preferable.

As the trivalent or tetravalent metal compound, any of the commonly used metal alcoholates and metal chelates can be used, but metal alcoholates are preferred. As the metal alcoholates, particularly typical ones among them are aluminum ethlyate, zirconium tetraethylate, titanium tetraethylate, magnesium di (iso) propylate, aluminum tri ( Iso) propyl, zirconium tetra (iso) propyl, titanium tetra (iso) propyl, aluminum tri (iso, secondary, tar
Representative examples include butyrate, zirconium tetra (iso, secondary, tertiary) butyrate, titanium tetra (iso, secondary, tertiary) butyrate, and monosecondary butoxyaluminum diisopropylate. As described above, those having two to three types of alcohol groups in one molecule are exemplified.

Further, ethyl acetoacetate aluminum diethylate, ethyl acetoacetate aluminum di (iso) propylate, ethyl acetoacetate aluminum di (iso, secondary, tertiary) butyrate
, Aluminum triethylacetoacetate, aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum tri (acetylacetonate)
G). Of these metal alcoholates, aluminum alcoholate, zirconium alcoholate, and titanium alcoholate are preferable, and aluminum alcoholate is particularly preferable. Of these alone,
Alternatively, two or more kinds can be used.

The amount of the trivalent to tetravalent metal used is preferably at least 0.05 part, more preferably 0.1 to 3 parts, per 100 parts of rosin used as a raw material. If the amount is less than 0.05 part, the organic solvent tends to remain on the printed matter, and if it exceeds 3 parts, a gel is easily generated in the resin, which is not preferable.

The reaction of introducing a divalent metal compound into a rosin-modified phenol resin, a rosin ester, an added rosin, or a rosin is carried out in the presence of water and an organic solvent. The reaction temperature is 100 ° C. or less, preferably 50 ° C.
The range of -80 ° C is appropriate. When the reaction is carried out at a temperature higher than 100 ° C., evaporation of water and other coexisting organic solvents is likely to occur in a state where the reaction does not proceed sufficiently. Then, the unreacted metal compound is likely to remain, and the introduction reaction of the metal compound is not sufficiently performed, which is not preferable.

The reaction for introducing the divalent metal compound is carried out for 0.5 to 10 hours, preferably 2 to 7 hours. A rosin-modified phenol resin of such a divalent metal compound, a rosin ester, an added rosin,
In the case of the reaction for introduction into rosin,
It is a matter of controlling the heat of reaction. That is, since the reaction of rosin or addition rosin with a metal compound in the presence of water is accompanied by intense heat generation, it is necessary to pay sufficient attention to bumping of the reaction contents.

The organic solvent is not particularly limited as long as it does not dissolve in water. Particularly representative examples include aromatic hydrocarbons such as toluene or xylene, esters such as ethyl acetate or butyl acetate, and ketone solvents such as methyl (iso) butyl ketone. Further, toluene or xylene may be used alone or in combination of two or more.

The synthetic resin for a printing ink of the present invention comprises, based on 100 parts of rosin, 1 to 30 parts of an α, β-monoethylenically unsaturated carboxylic acid and 1 to 1 part of a rosin-modified phenol resin.
It is obtained by reacting 00 parts, 2 to 20 parts of a divalent metal compound, and 0.05 parts or more of a trivalent or tetravalent metal. Among these, a more preferred composition is based on 100 parts of rosin, α, β-monoethylenically unsaturated carboxylic acid 3 to 3 parts.
The reaction is conducted by reacting 15 parts with 2 to 30 parts of a rosin-modified phenol resin, 4 to 15 parts of a divalent metal compound, and 0.1 to 3 parts of a trivalent or tetravalent metal compound.

The printing ink of the present invention can be obtained by blending a coloring agent or the like with the synthetic resin obtained above. The general composition of the printing ink is 10 to 50 parts by weight of the synthetic resin for printing ink of the present invention (solid content), and 3 to 50 parts by weight of the coloring agent.
35 parts, a filler of 0 to 20 parts, and a solvent of 40 to 75 parts, of which 15 to 35 parts of a synthetic resin for printing ink (solid), 5 to 20 parts of a coloring agent, and 5-15
And an ink composition containing 45 to 60 parts by weight of a solvent.

As the colorant used in the printing ink of the present invention, there may be mentioned known and commonly used ones used in ordinary inks such as inorganic or organic pigments and dyes. Preference is given to using pigments.

Specific examples of the organic pigment include, for example, Carmine 6B, Lake Red C, Permanent Red 2B, Disazo Yellow, Pyrazolone Orange, Carmine FB,
Chromophtal yellow, chromophtal red, phthalocyanine blue, phthalocyanine green, dioxazine violet, quinacridone magenta, quinacridone red, indanthrone blue, pyrimidine yellow, thioindigo bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone Yellow, aniline black, daylight fluorescent pigments and the like.

Specific examples of the inorganic pigments include, for example, carbon black, aluminum powder, bronze powder, chrome vermillion, graphite, cadmium yellow, cadmium red, ultramarine, navy blue, red iron oxide, yellow iron oxide, iron black, titanium oxide, Zinc oxide and the like can be mentioned.

Specific examples of the dye include tartrazine lake, rhodamine 6G lake, Victoria Pure Blue Lake, alkali blue G toner, brilliant green lake, and the like, and coal tar can also be used.

As the filler, those used in ordinary inks may be used alone or in combination of two or more. Specific examples include carbonates such as calcium carbonate and magnesium carbonate, sulfates such as precipitated barium sulfate, and silicates such as silica and talc. Further, as additives, waxes, pigment dispersants, defoamers, and other known additives can be used.

As the solvent, the above-mentioned organic solvents can be used.

Although the printing ink of the present invention can be widely used for printing, it is particularly preferably used as a gravure ink for publication.

[0051]

Next, the present invention will be described based on Examples and Comparative Examples.
This will be described more specifically. In the following, “parts” means “parts by weight” unless otherwise specified.

(Example 1) Into a 3 L four-necked flask equipped with a stirrer, a thermometer and a decanter, 500 parts of trol oil rosin and 40 parts of fumaric acid were charged, and heated at 250 ° C.
For 1 hour to obtain a mixture of rosin and fumaric acid-added rosin.

Subsequently, a rosin-modified phenol resin [Beckasite F-171 manufactured by Dainippon Ink and Chemicals, Inc.]
100 parts of toluene and 950 parts of toluene were added to the reaction product and dissolved,
While maintaining the temperature at 70 ° C., 80 parts of ion-exchanged water, 10 parts of calcium hydroxide and 30 parts of zinc oxide were added over 3 hours to carry out the reaction. Subsequently, 22 parts of magnesium oxide was added at the same temperature, and the reaction was carried out for 3 hours. Then, the temperature was maintained at 110 ° C. for 3 hours, and water was removed by a decanter.

Subsequently, a mixture of 5 parts of aluminum triisopropylate and 20 parts of toluene was added at a temperature of 110.degree.
Five parts were charged and the reaction was carried out for 2 hours. Further, filtration was performed under pressure using a filter paper.

The appearance of the obtained synthetic resin was transparent, and various characteristic values of the synthetic resin were as follows. Acid value (solid content converted acid value, the same applies hereinafter): 86 KOH mg / g Viscosity (measured by a B-type viscometer, the same applies hereinafter): 1000 cps Number average molecular weight (GPC, polystyrene conversion; the same applies hereinafter): 800 Min: 46%

The structure of the obtained synthetic resin is represented by an infrared absorption spectrum (hereinafter, abbreviated as an IR spectrum.
Indicated by ), C ¹³ NMR spectrum and fluorescent X-ray spectrum were as follows.

From the IR spectrum of FIG.

[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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The characteristic absorption band of 1550-1610c
near m- ¹ ,

[0065]

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[0066]

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[0067]

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The characteristic absorption band of 1680-1700c
An absorption around m ^-1 was observed. In addition, absorption around 1710 to 1750 cm ^−1, which is the characteristic absorption band of the ester of rosin and polyhydric alcohol in the rosin-modified phenol resin, was remarkably observed.

From the ¹³ C NMR spectrum of FIG.
A characteristic spectrum of para-tert-butylphenol was remarkably observed at around 6 ppm. Further, from the fluorescent X-ray spectrum of FIG. 3, the diffraction angle (2θ) is 144 to 146 (degrees).
A characteristic spectrum of aluminum was remarkably observed in the vicinity.

Next, 45 parts of the obtained synthetic resin, 7 parts of red pigment (Carmine 6B), 30 parts of calcium carbonate and toluene were dispersed in a pigment disperser (paint shaker) for 1 hour.
Subsequently, the viscosity was measured with a viscometer (Zerncup No. 3, 3).
In seconds, adjustment was made using toluene to obtain a red ink composition.

(Example 2) 500 parts of gum rosin and 35 parts of maleic anhydride were charged into a 3 L four-necked flask similar to that of Example 1, and the mixture was kept at 170 ° C for 1 hour to carry out a reaction. A mixture with maleic anhydride-added rosin was obtained.

Subsequently, the mixture was added to rosin-modified phenol
And 25 parts of toluene and 652 parts of toluene were added and dissolved, and the mixture was further kept at a temperature of 80 ° C. to remove 80 parts of ion-exchanged water.
A mixture consisting of 3 parts of calcium hydroxide and 33 parts of zinc oxide was added over 2 hours and reacted at the same temperature. Next, 20 parts of magnesium oxide was added over 1 hour, and the mixture was kept at 110 ° C. for 3 hours, and water was removed by a decanter.

Subsequently, 20 parts of a mixture of 4 parts of aluminum triethylate and 16 parts of toluene were charged at a temperature of 110 ° C., and the reaction was carried out for 2 hours. Further, filtration was performed under pressure using a filter paper.

The appearance of the obtained synthetic resin was transparent, and the properties of the synthetic resin were as follows. Acid value: 93 KOH mg / g Viscosity: 900 cps Number average molecular weight: 700 Non-volatile content: 48% Next, the obtained synthetic resin was mixed with the same composition as in Example 1,
The same operation was performed to obtain a red ink having a viscosity of 12.5 seconds.

(Example 3) Next, 500 parts of tall oil rosin and 50 parts of maleic anhydride were charged into a 2 L four-necked flask similar to that of Example 1, and kept at 170 ° C for 1 hour. The reaction was performed to obtain a mixture of rosin and maleic anhydride-added rosin.

Subsequently, the mixture was added to rosin-modified phenol
Resin (Dainippon Ink & Chemicals, Inc. Beccasite 1)
126 HV) 50 parts and 770 parts of toluene were added and dissolved, and the mixture was further kept at a temperature of 80 ° C.
And a mixture of 46 parts of zinc oxide was added over 2 hours and reacted at the same temperature. Next, 15 parts of magnesium oxide was added over 1 hour, and the mixture was kept at 110 ° C. for 3 hours, and water was removed by a decanter. Continued
Aluminum triisopropylate at a temperature of 110 ° C.
7.5 parts of a mixture of 5 parts and 6 parts of toluene were charged and reacted for 2 hours. Further, filtration was performed under pressure using a filter paper.

The appearance of the obtained synthetic resin was transparent, and the characteristics of the synthetic resin were as follows.

Acid value: 96 KOH mg / g Viscosity: 1000 cps Number average molecular weight: 750 Non-volatile content: 42% Next, the obtained synthetic resin was mixed with the same composition as in Example 1,
The same operation was performed to obtain a red ink having a viscosity of 12 seconds.

(Comparative Example 1) 500 parts of trol oil and 40 parts of fumaric acid were charged into a 2 L four-necked flask similar to that in Example 1, and kept at 250 ° C for 1 hour to carry out a reaction. Run to obtain a mixture of rosin and fumaric acid-added rosin. Subsequently, 540 parts of toluene were added to this mixture, and the mixture was maintained at a temperature of 70 ° C., and 80 parts of ion-exchanged water was added.
2 parts of aluminum hydroxide and calcium hydroxide 10
And 20 parts of magnesium oxide were added over 3 hours to carry out the reaction. Then, add 25 parts of zinc oxide,
After performing the reaction for 3 hours, the temperature was maintained at 110 ° C. for 3 hours, and water was removed by a decanter. Further, filtration was performed under pressure using a filter paper.

The appearance of the obtained synthetic resin was transparent, and various characteristic values of the synthetic resin were as follows. Acid value: 100 KOH mg / g Viscosity: 600 cps Number average molecular weight: 480 Non-volatile content: 51%

As shown in the fluorescent X-ray spectrum of FIG. 3, the characteristic spectrum of aluminum was not observed in the obtained synthetic resin. Then, the obtained synthetic resin was used in Example 1
By carrying out the same composition and the same operation as in the above, a red ink having a viscosity of 12 seconds was obtained.

(Comparative Example 2) 500 parts of gum rosin and 35 parts of maleic anhydride were charged into the same two-L four-necked flask as in Example 1, and reacted at 170 ° C for 1 hour. And a mixture of maleic anhydride-added rosin. Subsequently, 535 parts of toluene was added to the mixture, and the mixture was further maintained at a temperature of 80 ° C., and a mixture consisting of 80 parts of ion-exchanged water, 3 parts of calcium hydroxide, and 33 parts of zinc oxide was added to 2 parts of the mixture. The reaction was carried out at the same temperature over time.

Then, 20 parts of magnesium oxide was added over 1 hour to carry out a reaction, and the mixture was kept at 110 ° C. for 3 hours to remove water by a decanter. Further, filtration was performed under pressure using a filter paper. The appearance of the obtained synthetic resin was transparent, and various characteristic values of the synthetic resin were as follows.

Acid value: 105 KOH mg / g Viscosity: 700 cps Number average molecular weight: 500 Non-volatile content: 52% Next, the obtained synthetic resin was mixed with the same composition as in Example 1,
The same operation was performed to obtain a red ink having a viscosity of 12 seconds.

(Comparative Example 3) In a reaction vessel similar to that of Example 1, 500 parts of the toluin rosin and 50 parts of maleic anhydride were charged, and kept at 170 ° C for 1 hour to carry out the reaction. And a mixture of maleic anhydride-added rosin. Subsequently, 550 parts of toluene was added to the mixture, and the mixture was maintained at a temperature of 70 ° C.
And 46 parts of zinc oxide were added over 3 hours to carry out the reaction. Subsequently, 15 parts of magnesium oxide was added over 1 hour, and the reaction was carried out for 2 hours.
The mixture was kept at 0 ° C. for 3 hours, and water was removed by a decanter. Further, filtration was performed under pressure using a filter paper.

The appearance of the obtained synthetic resin was transparent, and the characteristic values of the synthetic resin were as follows. Acid value: 120 KOH mg / g Viscosity: 580 cps Number average molecular weight: 520 Nonvolatile content: 52% Next, by the same operation as in Example 1, a red ink having a viscosity of 12 seconds was obtained.

(Application Evaluation Examples) Examples 1 to 3 and Comparative Examples 1 to
The ink composition obtained in 3 was printed on printing paper using a baby printing machine manufactured by Higashitani Ironworks Co., Ltd., and the residual amount of the organic solvent in the printed matter, the drying property of the ink, and the gloss of the printed matter were measured. .

The residual amount of the organic solvent was determined by drying the printed matter printed on the printing paper at 20 ° C. for 4 days, and performing gas chromatography (G
In C), the amount of the organic solvent (toluene) remaining in the printed matter was measured. The dryness of the ink is measured by using a heat seal tester manufactured by Tester Sangyo Co., Ltd. at a pressure of 4 kg / cm ² , overlapping the printed paper with the printed paper and pressing the same, and the time until the ink no longer adheres to the printed paper. Was the drying time. The gloss was measured by drying the printed matter printed on printing paper at 20 ° C. for 24 hours,
The degree of reflection was measured using a gloss meter. Table 1 shows the evaluation results.

[0089]

[Table 1]

[0090]

Industrial Applicability The synthetic resin for printing of the present invention has a small amount of an organic solvent in a printed matter, and a printed matter using this resin is excellent in gloss and dryness, and is useful as a gravure ink for publication.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of a synthetic resin obtained in Example 1.

FIG. 2 is a ¹³ C NMR spectrum of the synthetic resin obtained in Example 1.

FIG. 3 is a fluorescent X-ray spectrum diagram of the synthetic resin obtained in Example 1.

Claims (5)

[Claims] 1. A compound represented by the following structural formula and having a number average molecular weight of 4
A synthetic resin for printing ink, which has a molecular weight of from 00 to 5,000. Embedded image Wherein, M1 is a 3-4 valent metal, R ₁ is a rosin-modified phenol - Le resin residues, alpha, beta chromatography monoethylenically unsaturated carboxylic acid addition rosin residues or, selected from the group consisting of rosin residues Represents one or more residues. X represents a divalent functional group represented by the structural formula (1) or (2), m is an integer of 1 to 30, and n is an integer of 3 to 4. Embedded image Embedded image (In the formulas (1) and (2), R ₂ is an α, β-monoethylenically unsaturated carboxylic acid-added rosin residue;
₃ is a rosin-modified phenol resin residue, and M2 is a divalent metal. )] 2. The synthetic resin according to claim 1, wherein M1 is one or more selected from the group consisting of aluminum, zirconium and titanium. 3. A rosin-modified phenol resin is mixed with a carboxyl group-containing rosin obtained by reacting an α, β-monoethylenically unsaturated carboxylic acid with a rosin,
A method for producing a synthetic resin for printing ink, comprising reacting a trivalent metal compound and then reacting a trivalent or tetravalent metal compound. 4. The method according to claim 3, wherein the trivalent or tetravalent metal compound is at least one member selected from the group consisting of aluminum alcoholate, zirconium alcoholate and titanium alcoholate. . 5. A printing ink comprising the synthetic resin for a printing ink according to claim 1 and a pigment.