JP5546091B2 - Pigment coating agent, coated pigment, and printing ink composition - Google Patents

Description

The present invention relates to a pigment coating agent, a coated pigment, and a printing ink composition.

Conventionally, pigments are often surface treated with rosins to improve various performances of printing inks (offset printing, newspaper printing inks, etc.) (clearness, coloring, color tone, dispersibility, water resistance, etc.) As a pigment coating agent, a rosin-modified phenolic resin is awarded for its performance. For example, Patent Document 1 proposes a coated pigment obtained by dry pulverizing a rosin modified phenolic resin together with a pigment.

However, the rosin-modified phenolic resin generally has a potential danger such that it is easily oxidized and deteriorated in the air, or the coated pigment self-heats during storage or transportation. Further, when an oxidized or deteriorated coated pigment is used, problems arise in terms of quality, such as poor color tone of the printing ink obtained.

Therefore, for example, as in Patent Document 2 and Patent Document 3, a method of performing the dry pulverization in an inert gas atmosphere is conceivable, but the obtained coated pigment does not touch the atmosphere at all in the subsequent distribution process or work site. Since there is no guarantee, this method has not led to an essential solution of the above problem from the viewpoint of long-term storage and transportation.

  On the other hand, in order to avoid the problem of self-heating, the pigment is surface-treated with an aqueous dispersion of rosin-modified phenolic resin and rosin soap (rosin calcium salt, etc.) as in the technique of Patent Document 4, for example, and a water-based coated pigment A method of using (rake pigment) is also conceivable. However, since the coated pigment is water-based, it has a strong water absorption and causes various problems. For example, when the coated pigment is used for offset printing, the ink is excessively emulsified by the fountain solution, and various troubles occur during the printing operation.

In addition, rosin-modified phenolic resins use phenols that are suspected of being an environmental hormone as the raw material phenol-formaldehyde condensate and formaldehyde, which is one of the causes of sick house syndrome. There is great concern.

Japanese Patent No. 3159049 Japanese Patent No. 3159048 Japanese Patent No. 3292646 Japanese Patent No. 3303458

The present invention provides a novel pigment coating agent that does not use phenols or formaldehyde as a raw material, hardly generates self-heating due to oxidation, and can provide a coating pigment that can improve various performances of printing ink. Is the main purpose.

The present inventor has found that the above-mentioned problems can be solved by the following specific pigment coating agent.

That is, the present invention comprises an α, β-unsaturated carboxylic acid-modified rosin and / or polymerized rosin (a) of 10 to 90% by weight, glycerin and / or pentaerythritol (b) of 1 to 30% by weight, and a carbon number of 10 to 40. Alkyl (anhydrous) succinic acid and / or alkenyl (anhydrous) succinic acid having 10 to 40 carbon atoms (c) 3 to 40% by weight, and if necessary, aromatic polybasic acids (d) and / or polar group-containing petroleum The calorific value (mJ) and the solid content weight (mg) corresponding to the calorific peak area obtained by reacting the raw material containing the resin (e) with a scanning differential calorimeter in the presence of air. the coated pigment; coated pigment using the pigment coating agent; and a ratio [mJ / mg] is the pigment coating agent containing a rosin-based polyester resin, characterized in that 15 or less The printing ink composition to contain.

Since the pigment coating agent according to the present invention contains the rosin-based polyester resin, self-heating due to oxidation hardly occurs. Therefore, when the pigment coating agent is used, a coated pigment excellent in quality control, such as being able to be safely stored and transported over a long period of time, can be obtained. Further, since the pigment coating agent does not use phenols or formaldehyde as raw materials, it has little influence on the environment and the human body.

Moreover, according to the coating pigment which concerns on this invention, the various performances (clearness, coloring property, dispersibility, water resistance, etc.) of printing ink can be improved. Therefore, the said covering pigment can be used suitably as a pigment of a newspaper printing ink composition, a relief printing ink composition, a gravure printing ink composition, especially an offset printing ink composition.

  Moreover, since the printing ink composition which concerns on this invention contains the said coating pigment, it is excellent in various performances, such as sharpness, coloring property, dispersibility, and the water resistance of a film. In addition, the printing ink composition has an advantage that over-emulsification with a fountain solution hardly occurs particularly when used as an offset printing ink composition.

[About pigment coating agents]
The rosin-based polyester resin contained in the pigment coating agent of the present invention is characterized in that it hardly generates self-heating due to oxidation in the atmosphere. Further, this compound phenol - a formaldehyde-free, specifically phenol and formaldehyde, or phenol - have a not use formaldehyde condensates as a raw material.

As the α, β-unsaturated carboxylic acid-modified rosin and / or polymerized rosin (a), various known ones can be used without particular limitation. Specifically, these are derivatives of natural rosin [gum rosin, tall oil rosin, wood rosin, etc.] . For example, the α, β-unsaturated carboxylic acid-modified rosin is an α, β-unsaturated carboxylic acid (acrylic acid, A rosin obtained by Diels-Alder modification of natural rosin with methacrylic acid, (anhydrous) maleic acid, fumaric acid, etc. (for example, acrylic acid modified rosin, maleic acid modified rosin, maleic anhydride modified rosin, fumaric acid modified rosin, etc.) . These can be used alone or in combination of two or more.
The physical properties of the rosins (a) are not particularly limited, but the acid value is usually about 130 to 350 mgKOH / g, and the softening point is usually about 60 to 200 ° C.
alpha, beta-unsaturated carboxylic acid-modified rosin and / or polymerized rosin, easily increasing the molecular weight and the softening point of the rosin-based polyester resin, also preferably because contamination was less likely to occur in the coating apparatus in coating pigments.
The amount of rosins (a) used is usually about 10 to 90% by weight in all raw materials of the rosin polyester resin.

Glycerin and / or pentaerythritol (b) is preferable because it easily adjusts the molecular weight and softening point of the rosin-based polyester resin. Incidentally, in addition to these, various known dihydric alcohol Ethylene glycol, diethylene glycol, triethylene glycol, tripropylene glycol, etc.]; other trihydric alcohols [trimethylol pull bread, trimethylolethane, etc.]; other tetravalent Alcohol [ diglycerin , ditrimethylolpropane, ditrimethylolethane, etc.]; hexavalent alcohol [dipentaerythritol, etc.] can be used in combination , and these can be used alone or in combination of two or more. .
The amount of glycerin and / or pentaerythritol (b) used is usually about 1 to 30% by weight in all raw materials of the rosin polyester resin.

Alkyl (anhydrous) succinic acid having 10 to 40 carbon atoms and / or alkenyl (anhydrous) succinic acid (c) having 10 to 40 carbon atoms is mainly used for the purpose of enhancing the solubility of rosin-based polyester resins in ink solvents. use. In addition, low molecular weight aliphatic compounds such as other aliphatic basic acids, aliphatic alcohols, aliphatic monoamines, aliphatic monoepoxies; α, β-unsaturated carboxylic acid and hydrophobic polymerizable unsaturated compound And a polymer aliphatic compound such as a resin obtained by partially reacting a polymer having a reactivity with a carboxylic acid in the polymer, and these can be used alone. Alternatively, two or more kinds can be used in combination.
The amount of the alkyl (anhydride) succinic acid having 10 to 40 carbon atoms and / or the alkenyl (anhydrous) succinic acid (c) having 10 to 40 carbon atoms is usually 3 to 40% by weight in the total raw materials of the rosin polyester resin. Degree.

Examples of the alkyl (anhydrous) succinic acid having 10 to 40 carbon atoms include octyl (anhydrous) succinic acid, dodecyl (anhydrous) succinic acid, triakotyl (anhydrous) succinic acid, tetraconti (anhydrous) succinic acid, and the like. Examples of 40 alkenyl (anhydrous) succinic acid include octenyl (anhydrous) succinic acid, dodecenyl (anhydrous) succinic acid, triacontenyl (anhydrous) succinic acid, tetracontenyl (anhydrous) succinic acid and the like. As other low molecular weight aliphatic compound, and an aliphatic bases acids, specifically, for example, straight-chain fatty acids [capric acid about 10 to 40 carbon atoms, stearic acid, oleic acid, linolenic acid Branched fatty acid having about 10 to 40 carbon atoms [iso acid, tuberculostearic acid, etc.]; Cyclic fatty acid [malvalic acid, shawl muglycic acid, etc.] ; α, ω-dicarboxylic acid having about 10 to 40 carbon atoms [ Sebacic acid, eicosane diacid, triacontane diacid, etc.]; α, β-unsaturated carboxylic acid and (semi) drying oil (linseed oil, soybean oil, dehydrated castor oil, etc.); α, β-unsaturated Compound consisting of carboxylic acid and olefin oligomer; dimer acid can be exemplified.
Examples thereof include ethyl acid, butyl acetate and the like.

  Specific examples of the aliphatic alcohols include monoalcohols having about 10 to 40 carbon atoms (decyl alcohol, icosanol, triacontanol, tetracontanol and the like); diols having about 10 to 40 carbon atoms [1 , 2-octadecanediol, decanediol, icosanediol, triacontanediol, tetracontanediol, etc.]; diols obtained by hydrogenating dimer acid can be exemplified.

Specific examples of the aliphatic monoamines include monoamines having about 10 to 40 carbon atoms (decylamine, icosylamine, triacontylamine, tetracontylamine and the like); animals and plant-derived amines having about 10 to 40 carbon atoms [tallow Alkylamine, soybean alkylamine, etc.].

Specific examples of the aliphatic monoepoxies include aliphatic monoepoxies having about 10 to 40 carbon atoms [for example, 1,2-epoxyhexane, 1,2-epoxyoctane, 1,2-epoxydecane. 1,2-epoxydodecane, 1,2-epoxytetradecane, 1,2-epoxyhexadecane, 1,2-epoxyoctadecane, ethylhexyl glycidyl ether] and the like.

  As the polymer aliphatic compound, for example, a resin described in Japanese Patent No. 3446728 can be used.

As the aromatic polybasic acid (d), various known ones can be arbitrarily used mainly for the purpose of increasing the softening point of the rosin-based polyester resin. Specifically, for example, aromatic polybasic acids [(anhydrous) phthalic acid, isophthalic acid, terephthalic acid, (anhydrous) trimellitic acid, pyromellitic acid, etc.]; monoalkyl esters corresponding to the aromatic polybasic acids [Monomethyl ester, monoethyl ester, dimethyl ester, diethyl ester and the like] can be exemplified, and these can be used alone or in combination of two or more. The usage-amount of aromatic polybasic acid (d) is about 0 to 20 weight% normally in all the raw materials of a rosin-type polyester resin.

As the polar group-containing petroleum resin (e), various known resins can be arbitrarily used mainly for the purpose of increasing the molecular weight and softening point of the rosin-based polyester resin. Specifically, what introduced polar groups, such as a carboxyl group and a hydroxyl group, into various known petroleum resins by various known means can be used (for example, refer to patent 3446728).
Examples of the petroleum resin include DCPD petroleum resins (for example, cyclopentadiene and dicyclopentadiene are used as raw materials); C5 petroleum resins (for example, pentene, cyclopentene, pentadiene and isoprene are used as raw materials); C9 petroleum resins [For example, methylbutene, indene, methylindene, vinyltoluene, styrene, α-methylstyrene, β-methylstyrene are used as raw materials]; Copolymer petroleum consisting of a raw material of the DCPD petroleum resin and a raw material of the C5 petroleum resin Resin; Copolymer petroleum resin composed of C5 petroleum resin raw material and C9 petroleum resin raw material; Copolymer petroleum resin composed of DCPD petroleum resin raw material and C9 petroleum resin raw material; DCPD From the raw material of the petroleum-based petroleum resin, the raw material of the C5-based petroleum resin, and the raw material of the C9-based petroleum resin And a copolymerized petroleum resin.
In addition, as a method for introducing a polar group into a petroleum resin, for example, when introducing a carboxyl group, (1) the α, β-unsaturated carboxylic acid and the petroleum resin are mixed with various known radical reaction initiators. And (2) a method of subjecting the α, β-unsaturated carboxylic acid and the petroleum resin to an ene reaction.
For example, when a hydroxyl group is introduced, (3) a method of thermally polymerizing a compound having a double bond and a hydroxyl group in the molecule such as allyl alcohol to the petroleum resin can be exemplified.
The physical properties of the polar group-containing petroleum resin (e) are not particularly limited, but the weight average molecular weight is usually about 4,000 to 30,000. When the polar group-containing petroleum resin (e) has a carboxyl group, the theoretical acid value is usually about 5 to 102 mgKOH / g.
The amount of the polar group-containing petroleum resin (e) used is usually about 0 to 66% by weight in all raw materials of the rosin polyester resin.

  The production method of the rosin polyester resin is not particularly limited, and various known ester methods can be employed. Specifically, for example, a predetermined amount of the raw material is charged into a reaction vessel equipped with a stirrer, a reflux condenser with a water separator, a thermometer, and the like, and the ester is esterified at a temperature of about 100 to 300 ° C. for about 1 to 20 hours. What is necessary is just to advance reaction. The reaction system is preferably an inert gas atmosphere such as nitrogen.

In addition, although the use weight of each raw material is as above-mentioned, ratio (Xeq) of the total equivalent (Xeq) of the hydroxyl group and amino group contained in the raw material to be used, and the total equivalent (Yeq) of the carboxyl group contained in the raw material to be used ( When X / Y) is usually adjusted to be in the range of about 0.5 to 1.1, the overemulsification resistance of the printing ink composition according to the present invention is further improved, which is preferable. Therefore, the printing ink composition can be suitably used particularly for offset printing applications.

  In the ester reaction, various known esterification catalysts can be used. Specifically, for example, an acid catalyst [hydrochloric acid, sulfuric acid, methanesulfonic acid, paratoluenesulfonic acid, dodecylbenzenesulfonic acid, etc.]; alkali metal hydroxide [lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.]; Examples include alkaline earth metal hydroxides [calcium hydroxide, magnesium hydroxide, etc.]; metal oxides [calcium oxide, magnesium oxide, zinc oxide, etc.]; acetate metal salts [calcium acetate, magnesium acetate, zinc acetate, etc.] it can.

  In the ester reaction, various known organic solvents can be used. Specifically, for example, aromatic solvents [toluene, xylene, etc.], alicyclic solvents [methylcyclohexane, ethylcyclohexane, Nippon Oil AF Solvent No. 4, Nippon Oil AF Solvent No. 5, Nippon Oil AF solvent No. 6, Shin Nippon Petroleum AF solvent No. 7, etc.], ester solvents (for example, ethyl acetate, butyl acetate, etc.) and the like can be exemplified.

The physical properties of the obtained rosin-based polyester resin are not particularly limited, but in order to maintain the solubility of the rosin-based polyester resin in the printing ink solvent, the drying property of the coating film of the printing ink composition, and the setability, the softening point Is usually about 140 to 200 ° C., and the weight average molecular weight is usually about 30,000 to 400,000 (preferably 50,000 to 200,000). Moreover, the 33% linseed oil viscosity of a rosin-type polyester resin is about 2-15 normally. (Here, 33% linseed oil viscosity refers to the viscosity of a one-to-two mixture of polyester resin and linseed oil measured at 25 ° C. with a cone and plate viscometer (manufactured by Nippon Rheology Equipment Co., Ltd.)). (The same applies hereinafter.)

The rosin-based polyester resin according to the present invention has a feature that almost no self-heating due to oxidation occurs in the atmosphere.
Here, “substantially no self-heating” specifically corresponds to “a calorific peak area obtained by measuring the rosin polyester resin in the presence of air using a scanning differential calorimeter”. The ratio [mJ / mg] consisting of “calorific value (mJ)” and “solid weight of the rosin polyester resin (mg)” is usually 15 or less, preferably 10 or less, particularly preferably 5 or less, more preferably It means substantially zero.
The calorific peak area is obtained by using various known scanning differential calorimeters under the conditions of a temperature rising rate of about 10 ° C./min, a measuring temperature range of room temperature to about 200 ° C., and a measuring atmosphere in the air. Area.

[Coated pigment]
The coated pigment according to the present invention can be obtained by subjecting various known printing ink pigments to surface treatment (coating) using the rosin polyester resin.
The rosin-based polyester resin may be used usually in the range of about 1 to 200% by weight with respect to the pigment.

The coating means is not particularly limited, and any one of a dry method and a wet method may be used. For example, in the case of dry coating, the pigment may be dry pulverized in the presence of a rosin polyester resin in various known pulverizers (attritor, ball mill, vibration mill, etc.). The pulverization is preferably performed in an atmosphere in which oxygen is not present (for example, a nitrogen atmosphere). The grinding temperature is usually about 80 to 170 ° C. The pulverization time may be appropriately set according to the type of pulverizer and the desired pigment particle size. Moreover, you may use the above-mentioned organic solvent suitably at the time of a grinding | pulverization.

  As the pigment, various known inorganic pigments or organic pigments can be used. Examples of inorganic pigments include chrome lead, zinc yellow, bitumen, barium sulfate, cadmium red, titanium oxide, zinc white, bengara, alumina white, calcium carbonate, ultramarine, carbon black, graphite, and aluminum powder. Organic pigments include soluble azo pigments [C (β-naphthol) pigments, 2B pigments, 6B (β-oxynaphthoic) pigments, etc.], insoluble azo pigments (β-naphthol pigments, β-oxynaphthoic acid anilides). Pigments, monoazo yellow pigments, disazo yellow pigments, pyrazolone pigments, etc.), phthalocyanine pigments (copper phthalocyanine (α blue, β blue, ε blue) pigments, halogenated copper phthalocyanine pigments, metal-free phthalocyanine pigments), etc. Can be illustrated.

[About printing ink composition]
The printing ink composition according to the present invention is obtained by kneading the coated pigment and various known printing ink varnishes with various known dispersing / stirring equipment (ball mill, attritor, sand mill, three-roll mill, etc.), Can be obtained.

  The method for producing the printing ink varnish is not particularly limited. For example, it can be prepared by various known means using various binder resins, various ink solvents, and various gelling agents.

As the binder resin, in addition to known binder resins such as alkyd resins, petroleum resins, and rosin esters, rosin-based polyester resins according to the present invention can also be used.

In addition to the organic solvent, various known vegetable oils, fatty acid esters, and the like can be used as the ink solvent. Examples of the vegetable oil include linseed oil, tung oil, polymerized oils thereof, safflower oil, dehydrated castor oil, soybean oil, and the like. Among these, from the viewpoint of the drying property of the printing ink film, vegetable oil having an unsaturated bond is preferable, and soybean oil is preferable in consideration of the influence on the environment.

Moreover, as this gelling agent, various well-known things can be used without limitation. Specifically, aluminum-based chelating agents such as aluminum octylate, aluminum stearate, aluminum triisopropoxide, aluminum dipropoxide monoacetyl acetate can be used.

  In addition, you may use various well-known surfactant, wax, an additive, etc. as needed for the printing ink composition which concerns on this invention.

  Since the printing ink composition contains the coating pigment, it is excellent in various performances such as sharpness, colorability, dispersibility, and water resistance of the coating. The printing ink composition can be used for various ink applications, such as newspaper printing ink compositions, letterpress printing ink compositions, gravure printing ink compositions, and particularly offset printing inks. In particular, when used as an offset printing ink composition, there is an advantage that over-emulsification with dampening water hardly occurs.

Hereinafter, the present invention will be described more specifically with reference to production examples and examples, but the present invention is not limited thereto. Hereinafter, “parts” means parts by weight.

(Production of α, β-unsaturated carboxylic acid-modified rosin (a))
A reaction vessel equipped with a stirrer, a reflux condenser with a water separator and a thermometer was charged with 1,000 parts of gum rosin and heated to 180 ° C. while stirring the reaction system in a nitrogen atmosphere to melt it. Next, 267 parts of fumaric acid was charged in the same reaction vessel, and the reaction system was heated to 230 ° C. with stirring and kept warm for 1 hour. Thereafter, the reaction vessel was cooled to obtain solid fumaric acid-modified rosin (acid value 342.0, softening point 148 ° C.).

(Production of polar group-containing petroleum resin (e))
In the same reaction vessel, 1,000 parts of DCPD petroleum resin (trade name Quinton 1325, manufactured by Nippon Zeon Co., Ltd.) was charged, and the temperature was raised to 180 ° C. while stirring the reaction system in a nitrogen atmosphere. Melted. Next, 70 parts of maleic anhydride was charged into the same reaction vessel, and the reaction system was heated to 230 ° C. with stirring and kept warm for 3 hours. Thereafter, the reaction vessel was cooled to obtain a solid carboxyl group-containing petroleum resin resin (theoretical equivalent 65, weight average molecular weight 1,500). The weight average molecular weight of the petroleum resin is a polystyrene equivalent value measured in a THF solvent by gel permeation chromatography (GPC). As a GPC apparatus, HLC-8020 (manufactured by Tosoh Corporation) is used, and as a column, TSK. -A GEL column (manufactured by Tosoh Corporation) was used. (The same applies hereinafter.)

(Production of phenol-formaldehyde condensate)
In the same reaction vessel, 1,000 parts of nonylphenol, 270 parts of paraformaldehyde and 1,000 parts of water were charged, and the temperature was raised to 50 ° C. with stirring. Next, 100 parts of sodium hydroxide was charged into the same reaction vessel, the reaction system was gradually heated to 90 ° C. while cooling, and then kept warm for 2.5 hours, and sulfuric acid was added dropwise to adjust the pH to around 6. . Thereafter, 150 parts of xylene was added, the aqueous layer part containing formaldehyde and the like was removed, and the contents were further cooled to obtain a 70% xylene solution of resol-type nonylphenol.

Production Example 1
(Production of rosin-based polyester resin 1)
In a reaction vessel similar to Production Example 1, 588 parts of polymerized rosin (trade name: Silvatac 140, manufactured by Silvachem, acid value 140), 266 parts of solid fumaric acid-modified rosin of Production Example 1, and alkenyl anhydride succinate having 18 carbon atoms 52 parts of acid was charged, and the reaction system was heated to 180 ° C. while stirring in a nitrogen atmosphere to melt them. Next, 47 parts of pentaerythritol and 47 parts of glycerin were added to the reaction vessel, and the reaction system was kept warm at 260 ° C. with stirring. When the acid value of the resin became 30 or less, 1 part of paratoluenesulfonic acid was charged. The esterification reaction was continued until the acid value became 20 or less. After completion of the reaction, the reaction system was adjusted so that the 33 wt% linseed oil viscosity was 8.0 Pa · s, further reduced in pressure at 0.02 MPa for 10 minutes, and then cooled to obtain solid rosin polyester resin 1. Obtained. The acid value of the rosin-based polyester resin 1 was 15.8, the softening point was 173 ° C., and the weight average molecular weight was 130,000.

Reference production example 1
(Production of rosin-based polyester resin 2)
In the same reaction vessel as in Production Example 1, 353 parts of polymerized rosin (trade name: Silvatac 140, manufactured by Silvachem, acid value: 140), 101 parts of fumaric acid-modified rosin obtained in Production Example 1, obtained in Production Example 2 426 parts of polar group-containing petroleum resin were charged, and the reaction system was heated to 180 ° C. with stirring in a nitrogen atmosphere to melt them. Next, 22 parts of pentaerythritol, 22 parts of glycerin and 76 parts of 1,2-octadecanediol were added to the reaction vessel, and the reaction system was kept warm at 260 ° C. with stirring, so that the acid value of the resin became 30 or less. Then, 1 part of p-toluenesulfonic acid was charged and the esterification reaction was carried out until the acid value became 20 or less. After completion of the reaction, the reaction system was adjusted so that the 33 wt% linseed oil viscosity was 8.0 Pa · s, further reduced in pressure at 0.02 MPa for 10 minutes, and then cooled to obtain a solid rosin polyester resin 2. Obtained. The acid value of the rosin-based polyester resin 2 was 14.2, the softening point was 168 ° C., and the weight average molecular weight was 103,000.

Production Example 2
(Production of rosin-based polyester resin 3)
In a reaction vessel similar to Production Example 1, 676 parts of polymerized rosin (trade name: Silvatac 140, manufactured by Silvachem, acid value: 140), 68 parts of alkenyl succinic anhydride having 18 carbon atoms, and 135 parts of isophthalic acid were charged and reacted. While stirring the system in a nitrogen atmosphere, the temperature was raised to 180 ° C. to melt them. Next, 121 parts of pentaerythritol was added to the reaction vessel, and the reaction system was kept warm at 260 ° C. with stirring. When the acid value of the resin became 50 or less, 1 part of paratoluenesulfonic acid was added. The esterification reaction was continued until it became 20 or less. After completion of the reaction, the 33 wt% linseed oil viscosity of the reaction system was adjusted to 8.0 Pa · s, and the pressure was reduced at 0.02 MPa for 10 minutes to cool down to obtain a rosin polyester resin 3. The rosin polyester resin 3 had an acid value of 14.0, a softening point of 172 ° C., and a weight average molecular weight of 131,000.

Reference production example 2
(Manufacture of rosin-based polyester resin 4)
In a reaction vessel similar to Production Example 1, 311 parts of polymerized rosin (trade name: Silvatac 140, manufactured by Silvachem, acid value: 140), 51 parts of fumaric acid-modified rosin of Production Example 1, and polar group content of Production Example 2 478 parts of resin was charged and the reaction system was heated to 180 ° C. while stirring in a nitrogen atmosphere to melt them. Next, 31 parts of pentaerythritol and 31 parts of glycerin were added to the reaction vessel, and the reaction system was kept at 180 ° C. for 1 hour with stirring. When the acid value of the resin became 50 or less, 1 part of paratoluenesulfonic acid was added. Was esterified until the acid value was 20 or less. Thereafter, 85 parts of soybean oil fatty acid (trade name “TOENOL # 1125”, manufactured by Toei Chemical Co., Ltd., acid value 198) was added to the reaction vessel, and the reaction system was kept at 260 ° C. for 1 hour. Thereafter, when the acid value of the resin became 30 or less, 12 parts of isophthalic acid and 1 part of paratoluenesulfonic acid were charged into the reaction vessel, and the esterification reaction was carried out at the same temperature until the acid value became 20 or less. After the completion of the reaction, the 33 wt% linseed oil viscosity of the reaction system was adjusted to 8.0 Pa · s, and the pressure was reduced at 0.02 MPa for 10 minutes, followed by cooling to obtain rosin-based polyester resin 4. The acid value of the rosin-based polyester resin 4 was 13.8, the softening point was 178 ° C., and the weight average molecular weight was 158,000.

Comparative production example 1
(Production of rosin-modified phenolic resin)
In a reaction vessel similar to Production Example 1, 552 parts of gum rosin was charged, and the mixture was heated to 230 ° C. and stirred while stirring in a nitrogen atmosphere. Next, 52 parts of pentaerythritol and 2 parts of zinc oxide were added, the temperature was raised to 260 ° C. with stirring, and the reaction was continued until the acid value became 20 or less. After further cooling to 230 ° C., 394 parts of the resol-type nonylphenol 70% xylene solution (solid content: 276 parts) was dropped into the system over a period of 4 hours within a temperature range of 230 to 260 ° C. After completion of the dropping, the 33% by weight linseed oil viscosity was adjusted to 8.0 Pa · s, and after reducing the pressure at 0.02 MPa for 10 minutes, the contents were cooled to obtain a rosin-modified phenolic resin (hereinafter referred to as “resin A”). It was. The acid value was 16.8, the softening point was 168 ° C., and the weight average molecular weight was 92,000.

Reference example 1
Gum rosin calcium salt (trade name: Lime Resin No. 1, manufactured by Arakawa Chemical Industries, Ltd.) was used as it was as a pigment coating agent. (Hereinafter referred to as Resin B)

Reference example 2
(Manufacture of rosin polyester resin for binder resin)
A reaction vessel similar to Production Example 1 was charged with 238 parts of an α-olefin having a carbon number of 16 to 18 (trade name “Dialene 168”, manufactured by Mitsubishi Chemical Corporation), and the reaction system was stirred at 155 under a nitrogen atmosphere. The temperature was raised to ˜160 ° C. and melted. Next, 98 parts of maleic anhydride and 13.5 parts of di-t-butyl peroxide (trade name “Perbutyl D”, manufactured by NOF Corporation) were continuously added to the reaction vessel over 1 hour. While stirring, the reaction system was kept at 155 to 160 ° C. for 1 hour, and 271 parts of stearyl alcohol was further added and reacted at 220 ° C. for 4 hours to produce a resin (weight average molecular weight: 4,300). Next, 94 parts of the resin, 359 parts of polymerized rosin (trade name: Silvatac 140, manufactured by Silvachem, acid value: 140), 57 parts of the fumaric acid-modified rosin were added to the same reaction vessel as in Production Example 1. And 433 parts of the carboxyl group-containing petroleum resin resin were charged and heated to 180 ° C. with stirring in a nitrogen atmosphere to melt them. Subsequently, 29 parts of pentaerythritol and 29 parts of glycerin were added to the reaction vessel, and the temperature was raised to 260 ° C. with stirring, and the esterification reaction was performed until the acid value became 20 or less. After completion of the reaction, the 33% by weight linseed oil viscosity was adjusted to 8.0 Pa · s, and the pressure was reduced at 0.02 MPa for 10 minutes, followed by cooling to obtain a solid binder resin. The binder resin had an acid value of 15.5, a softening point of 165 ° C., and a weight average molecular weight of 150,000.

Examples and comparative examples (self-heating evaluation)
The rosin polyester resins 1 to 4 and the self-heating value (mJ) of the resin B were measured using a scanning differential calorimeter (EXSTAR6000 DSC6200) manufactured by Seiko Instruments Inc. Specifically, 10 mg of each resin was placed in the apparatus, and the measurement was performed under the conditions of a temperature rising rate of 10 ° C./min, a temperature range of room temperature to 200 ° C., and a measurement atmosphere. As a result, none of the rosin-based polyester resins 1 to 4 and the resin B showed a peak indicating the generation of heat. (That is, the ratio [mJ / mg] was substantially 0 in all cases.)
On the other hand, the ratio [mJ / mg] of the resin A was 37.

(Manufacture of coated pigments)
7 parts by weight of rosin-based polyester resin 1 and 70 parts by weight of crude phthalocyanine blue (indigo pigment) were added to the attritor, and dry pulverization was performed at 160 ° C. for 1 hour in a nitrogen stream. The resulting pigment is referred to as coated pigment 1. Similarly, coated pigments 2 to 4 were obtained for rosin polyester resins 2 to 4, and coated pigment A and coated pigment B were obtained for resins A and B.

(Adjustment of printing ink composition)
45.0 parts of binder resin obtained in Reference Example 2, 10 parts of soybean oil, 45.0 parts of AF solvent 7 were charged in a container, and mixed and dissolved at 180 ° C. for 30 minutes to obtain a varnish. . Subsequently, the varnish was cooled to 60 ° C., and further 1.0 part of aluminum chelate (trade name: ALCH, manufactured by Kawaken Fine Chemical Co., Ltd.) was added, and the system was stirred and mixed. Thereafter, the product was kept at 190 ° C. for 1 hour to obtain a gel varnish.

Next, using the gel varnish, the coated pigment and other raw materials were kneaded with a three roll mill so as to have the blending ratio shown in Table 1, and the tack value was 6.5 ± 0.5 and the flow value was 41. Printing ink 1 adjusted to be 0 ± 1.0 was obtained. Moreover, the printing inks 2-4, the printing ink A, and the printing ink B were obtained similarly about the coating pigments 2-4, the coating pigment A, and the coating pigment B.

(Printing ink emulsification test)
3.9 ml of printing ink A is developed on a dynamic emulsification tester (manufactured by Nippon Rheology Equipment Co., Ltd.), and then pure water is supplied at a rate of 5 ml / min (roll temperature 30 ° C., roll rotation speed 200 rpm). ), The amount of water in the printing ink was measured using an infrared moisture meter. As a result, the emulsification rate of printing ink 1 was 40%, printing ink 2 was 38%, printing ink 3 was 37%, and printing ink 4 was 36%. On the other hand, the printing ink A was 39% and the printing ink B was 68% (overemulsification).

Claims (3)

α, β-unsaturated carboxylic acid-modified rosin and / or polymerized rosin (a) 10 to 90% by weight, glycerin and / or pentaerythritol (b) 1 to 30% by weight, C10 to C40 alkyl (anhydrous) Acid and / or alkenyl (anhydrous) succinic acid having 10 to 40 carbon atoms (c) 3 to 40% by weight, and if necessary, aromatic polybasic acid (d) and / or polar group-containing petroleum resin (e) Ratio of calorific value (mJ) and solid content weight (mg) corresponding to the calorific peak area obtained by reaction in the presence of air using a scanning differential calorimetry device obtained by reacting the raw material containing [mJ / Mg] is 15 or less, a pigment coating agent containing a rosin-based polyester resin. A coated pigment obtained by dry pulverizing a pigment in the presence of the pigment coating agent according to claim 1 . A printing ink composition containing the coated pigment of claim 2 .