JP7040366B2 - Varnish composition for offset printing ink, offset printing ink - Google Patents

Description

The present invention relates to a varnish composition for offset printing inks and offset printing inks.

The varnish composition for offset printing ink is generally prepared by mixing a binder resin, vegetable oils, and if necessary, a petroleum-based solvent, and then adding and mixing a gelling agent to the varnish composition. (Patent Document 1). As the binder resin, a rosin-based resin such as a rosin-modified phenol resin is widely used, and such a varnish composition for offset printing ink has excellent drying property and misting resistance when used as an offset printing ink. In addition, abrasion resistance is also required.

As a technique for exhibiting abrasion resistance, an offset printing ink composition in which polyethylene wax is blended with a rosin ester resin or a rosin-modified phenol resin is known (Patent Document 2). However, such an additive has a problem that the gloss is lowered while the friction resistance is improved.

Japanese Unexamined Patent Publication No. 2001-139670 Japanese Unexamined Patent Publication No. 2016-204557

An object of the present invention is to provide a varnish composition for an offset printing ink that provides an offset printing ink that maintains gloss even if the abrasion resistance is improved and is also excellent in misting resistance.

As a result of diligent studies, the present inventors have found that a varnish composition for offset printing inks containing polycaprolactones in a binder resin unexpectedly improves abrasion resistance and maintains gloss, and has determined the present invention. It was completed. That is, the present invention relates to the following varnish composition for offset printing ink and offset printing ink.

1. 1. At least one resin (A) selected from the group consisting of rosin-modified phenolic resin, rosin-modified alkyd resin and rosin-modified petroleum resin, polycaprolactones (B), vegetable oils (C) and / or petroleum-based solvent ( A varnish composition for offset printing ink containing D).

2. 2. The varnish composition for offset printing ink according to item 1 above, further comprising a gelling agent (E).

3. 3. (B) The varnish composition for offset printing ink according to item 1 or 2 above, wherein the weight average molecular weight of the component is 500 to 10,000.

4. The varnish composition for offset printing ink according to any one of the above items 1 to 3, wherein the content of the component (B) is 1 to 12 parts by weight with respect to 100 parts by weight of the component (A).

5. An offset printing ink containing the varnish composition for the offset printing ink according to any one of the above items 1 to 4.

According to the varnish composition for offset printing ink of the present invention, since it contains polycaprolactones, gloss can be maintained even if the friction resistance of the offset printing ink is improved, and it has a feature of excellent misting resistance. ..

The varnish composition for offset printing ink of the present invention is at least one resin (A) (hereinafter referred to as (A) component) selected from the group consisting of a rosin-modified phenol resin, a rosin-modified alkyd resin and a rosin-modified petroleum resin. Polycaprolactones (B) (hereinafter referred to as (B) component), vegetable oils (C) (hereinafter referred to as (C) component) and / or petroleum solvent (D) (hereinafter referred to as (D) component). Is included. Hereinafter, the component (A) will be described in detail.

(Rosin-modified phenolic resin)
The rosin-modified phenolic resin includes rosins (a1) (hereinafter referred to as (a1) component), a phenol-formaldehyde condensate (a2) (hereinafter referred to as (a2) component), and a polyol (a3) (hereinafter referred to as (a3) component). It is a reaction product of).

The component (a1) is not particularly limited, and is, for example, natural rosin such as gum rosin, tall oil rosin, wood rosin; polymerized rosin derived from natural rosin; obtained by disproportionating or hydrogenating natural rosin or polymerized rosin. Stabilized rosins; examples include unsaturated acid-modified rosins obtained by reacting unsaturated carboxylic acids with natural rosins and polymerized rosins in a deal with Alder. These may be used alone or in combination of two or more. The unsaturated carboxylic acid is not particularly limited, and is, for example, an unsaturated dicarboxylic acid such as (anhydrous) maleic acid, fumaric acid and (anhydrous) itaconic acid, acrylic acid, methacrylic acid, crotonic acid and silicic acid. And the like, unsaturated monocarboxylic acids and the like. Further, the amount of unsaturated carboxylic acid used is not particularly limited, and is usually about 1 to 30 parts by weight with respect to 100 parts by weight of rosin as a raw material, and is preferably 1 to 10 from the viewpoint of generating insoluble matter. It is about a heavy part.

The component (a2) is not particularly limited, and various known resol-type phenol resins, novolak-type phenol resins, and the like can be used. As a resol type phenol resin, a phenol (P) and formaldehyde (F) are added / condensed in the presence of a basic catalyst within a range where the F / P (molar ratio) is usually about 1 to 3. Examples thereof include the condensed product. Examples of the novolak-type phenolic resin include condensates that have undergone an addition / condensation reaction in the presence of various acid catalysts within a range where the F / P is usually about 0.5 to 2. Further, each condensate may be neutralized and washed with water. Further, the production of each condensate can be carried out in the presence of water or an organic solvent (xylene or the like). Among them, the resol type phenol resin is preferable from the viewpoint of increasing the molecular weight of the rosin-modified phenol resin.

The phenols are not particularly limited, and examples thereof include coal acid, cresol, amylphenol, bisphenol A, pt-butylphenol, pn-octylphenol, pn-nonylphenol, pn-dodecylphenol and the like. ..

The formaldehyde is not particularly limited, and examples thereof include formalin and paraformaldehyde.

The basic catalyst is not particularly limited, and examples thereof include organic amines, sodium hydroxide, magnesium hydroxide, calcium hydroxide, calcium acetate, magnesium acetate, zinc acetate and the like. Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, oxalic acid, methanesulfonic acid, paratoluenesulfonic acid, dodecylbenzenesulfonic acid and the like. These may be used alone or in combination of two or more.

The component (a3) is not particularly limited as long as it is a compound having two or more hydroxyl groups in one molecule, and various known compounds can be used. For example, diols such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol; glycerin, trimethylolpropane, trimethylolethane. Triols such as; tetraols such as pentaerythritol, diglycerin, ditrimethylolpropane and ditrimethylolethane, and the like, which may be used alone or in combination of two or more. Of these, triol and / or tetraol are preferable because the physical properties (softening point, weight average molecular weight, etc.) of the rosin-modified phenol resin can be easily controlled.

The amount of the component (a1), the component (a2), and the component (a3) used is not particularly limited, and the rosin-modified phenolic resin has a high molecular weight, is soluble in an aliphatic hydrocarbon solvent, and has a misting resistance of offset printing ink. From the viewpoint of the above, the amounts of the components (a1) to (a3) used are set as follows, with the total amount used being 100% by weight.
-(A1) component: usually about 41 to 87% by weight, preferably about 46 to 73% by weight- (a2) component: usually about 9 to 50% by weight, preferably about 22 to 46% by weight- (a3) Ingredients: Usually about 3 to 9% by weight, preferably about 4 to 8% by weight.

The amounts of the component (a1) and the component (a3) used are not particularly limited, but from the viewpoint of misting resistance and gloss of the offset printing ink, the total hydroxyl group equivalent number (OH) of the component (a3) and the component (a1). The ratio (OH / COOH) to the total number of carboxyl group equivalents (COOH) is usually preferably about 0.5 to 1.5.

The acid value (JIS K5601) is also not particularly limited, but is usually about 5 to 30 mgKOH / g, preferably 10 to 25 mgKOH / g from the viewpoint of solubility of the rosin-modified phenol resin in an aliphatic hydrocarbon solvent.

The softening point (JIS K5601) is also not particularly limited, but is usually about 120 to 200 ° C., preferably 140 to 200 ° C. from the viewpoint of misting resistance and drying property of the offset printing ink.

Further, the weight average molecular weight (referred to as a polystyrene-equivalent value in gel permeation chromatography; the same applies hereinafter) is not particularly limited, but is 10,000 in terms of friction resistance, gloss, drying property, settability, etc. of the offset printing ink. It is about 400,000 to 400,000, preferably 20,000 to 400,000.

The rosin-modified phenolic resin in the present invention can be produced by reacting the component (a1), the component (a2) and the component (a3). The reaction order of each component is not particularly limited, and for example, a method of reacting all the components at the same time, a method of reacting the reaction product of the component (a1) and the component (a2) with the component (a3), and the component (a1). A method of reacting the component (a2) with the reaction product of the component (a3) and the component (a3) can be mentioned. The reaction temperature is usually about 100 to 300 ° C., and the reaction time is usually about 1 to 24 hours. Further, in the reaction, the acidic catalyst or the basic catalyst used in the production of the component (a2) can be used.

In the production of the rosin-modified phenol resin, the component (B) described later may be used as a reaction component.

(Rosin-modified alkyd resin)
The rosin alkyd resin is not particularly limited, and examples thereof include a resin obtained by reacting a hydroxyl group-containing resin obtained by reacting rosins and a polyol by a conventional method with a polybasic acid by a conventional method (specifically). Refer to Japanese Patent Application Laid-Open No. 2014-172962 for specific conditions and the like).

The polyol is not particularly limited, and examples thereof include those exemplified as the component (a3).

The polybasic acid is not particularly limited, and examples thereof include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic acid, trimellitic anhydride, succinic anhydride, succinic anhydride, maleic acid, and maleic anhydride. ..

In the production of the rosin-modified alkyd resin, the component (B) described later may be used as a reaction component.

(Rosin-modified petroleum resin)
The rosin-modified petroleum resin is not particularly limited, and for example, rosins, petroleum resins or polar group-containing petroleum resins, and polyols, and if necessary, aliphatic monoalcohols, aliphatic dialcohols, aliphatic monoamines, and Examples thereof include a resin obtained by reacting with at least one compound selected from an aliphatic monoepoxy (for specific conditions and the like, refer to Japanese Patent No. 4639448, Japanese Patent No. 5546091 and the like).

The petroleum resin is not particularly limited, and is, for example, a DCPD-based petroleum resin (as a raw material, for example, cyclopentadiene, dicyclopentadiene, etc.); a C5-based petroleum resin (as a raw material, for example, penten, cyclopentadiene, pentadiene, isoprene, etc.). C9-based petroleum resin (as raw materials, for example, methylbutene, inden, methylindene, vinyltoluene, styrene, α-methylstyrene, β-methylstyrene, etc.); Copolymerized petroleum resin; Copolymerized petroleum resin composed of raw material of C5 series petroleum resin and raw material of the C9 series petroleum resin; Copolymerized petroleum resin composed of raw material of DCPD series petroleum resin and raw material of C9 series petroleum resin; DCPD series petroleum resin Examples thereof include a raw material of C5 series petroleum resin, a copolymerized petroleum resin composed of a raw material of the C9 series petroleum resin, and the like.

The polar group-containing petroleum resin refers to a petroleum resin in which a carboxyl group, a hydroxyl group, or the like is introduced. When a carboxyl group is introduced, the petroleum resin is reacted with a polybasic acid, and when a hydroxyl group is introduced, it is reacted with a compound having a double bond and a hydroxyl group in the molecule such as allyl alcohol. Examples of the polybasic acid include those described in the above paragraph.

The polyol is not particularly limited, and examples thereof include those exemplified as the component (a3).

The aliphatic monoalcohol is not particularly limited, and examples thereof include decyl alcohol, icosanol, triacontanol, and tetracontanol.

The aliphatic dialcohol is not particularly limited, and examples thereof include 1,2-octadecanediol, decanediol, icosandiol, triacontanediol, and tetracontanediol.

The aliphatic monoamine is not particularly limited, and examples thereof include decylamine, icosylamine, triactylamine, tetracontylamine, beef tallow alkylamine, and soybean alkylamine.

The aliphatic monoepoxy is not particularly limited, and for example, 1,2-epoxyhexane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxydodecane, 1,2-epoxytetradecane, 1 , 2-Epoxy hexadecane, 1,2-Epoxy octadecane, ethylhexyl glycidyl ether and the like.

In the production of the rosin-modified petroleum resin, the component (B) described later may be used as a reaction component.

The component (B) is a component added so that the friction resistance of the offset printing ink can be improved and the gloss can be maintained without deterioration.

The component (B) is not particularly limited, and examples thereof include a ring-opening polymer of ε-caprolactone (polycaprolactone), polycaprolactone polyol, and (meth) acryloyl group-containing polycaprolactone.

The polycaprolactone polyol is not particularly limited, and examples thereof include polycaprolactone diol, polycaprolactone triol, and polycaprolactone tetraol. Examples of commercially available products include "Plaxel 205", "Plaxel 205AL", "Plaxel 208", "Plaxel 210", "Plaxel 220" (hereinafter, polycaprolactone diol), "Plaxel 303" manufactured by Daicel Corporation. Examples thereof include "Plaxel 305", "Plaxel 308", "Plaxel 312", "Plaxel 320" (hereinafter, polycaprolactone triol), "Plaxel 410" (hereinafter, polycaprolactone tetraol) and the like.

The (meth) acryloyl group-containing polycaprolactone is not particularly limited, and examples thereof include polycaprolactone (meth) acrylate and ω-carboxypolycaprolactone (meth) acrylate.

These components (B) may be used alone or in combination of two or more. Of these, polycaprolactone polyol is preferable, and polycaprolactone diol and / or polycaprolactone triol is more preferable from the viewpoint of maintaining the gloss of the offset printing ink.

The weight average molecular weight of the component (B) is not particularly limited, but is usually about 500 to 10,000. If the weight average molecular weight is less than 500, the emulsifying property of the offset printing ink becomes too high, and if it exceeds 10,000, the gloss of the offset printing ink tends to decrease. From the same point of view, it is preferably about 1,000 to 10,000.

The content of the component (B) is not particularly limited, but is usually about 1 to 12 parts by weight with respect to 100 parts by weight (solid) of the component (A) from the viewpoint of maintaining the gloss of the offset printing ink. From the same point of view, it is preferably about 1 to 10 parts by weight.

The component (C) is not particularly limited, and is, for example, vegetable oils such as flaxseed oil, tung oil, safflower oil, dehydrated castor oil, and soybean oil; flaxseed oil fatty acid methyl, soybean oil fatty acid methyl, flaxseed oil fatty acid ethyl, and soybean oil. Examples thereof include monoesters of vegetable oils such as fatty acid ethyl, linseed oil fatty acid propyl, soybean oil fatty acid propyl, linseed oil fatty acid butyl and soybean oil fatty acid butyl, and these may be used alone or in combination of two or more. Among them, vegetable oil having an unsaturated bond in the molecule is preferable, and soybean oil and / or linseed oil is more preferable, from the viewpoint of drying property of the offset printing ink.

The content of the component (C) is not particularly limited, but is usually about 10 to 200 parts by weight with respect to 100 parts by weight (solid) of the component (A) from the viewpoint of drying property of the offset printing ink. From the same point of view, it is preferably about 10 to 150 parts by weight.

The component (D) is not particularly limited, but is, for example, No. 0 solvent, No. 4 solvent, No. 5 solvent, No. 6 solvent, No. 7 solvent, AF solvent No. 4, which are petroleum solvents manufactured by JXTG Energy Co., Ltd. , AF solvent No. 5, AF solvent No. 6, AF solvent No. 7, and the like, and these may be used alone or in combination of two or more.

The content of the component (D) is not particularly limited, but the varnish composition for offset printing ink has an appropriate viscosity, and 100 weight of the component (A) is maintained from the viewpoint of maintaining a balance between misting resistance and gloss of the offset printing ink. It is usually about 10 to 200 parts by weight with respect to a part (solid). From the same point of view, it is preferably about 10 to 150 parts by weight.

Further, the varnish composition for offset printing ink of the present invention may contain a gelling agent (E) (hereinafter, referred to as a component (E)), if necessary.

The component (E) is not particularly limited, and is, for example, aluminum octylate, aluminum stearate, aluminum triisopropoxide, aluminum tributoxide, aluminum dipropoxide monoacetyl acetate, aluminum dibutoxide monoacetyl acetate, and aluminum triacetyl. Examples thereof include aluminum-based chelating agents such as acetate, which may be used alone or in combination of two or more.

The varnish composition for offset printing ink of the present invention is obtained by mixing and stirring each of the above components. The temperature at the time of stirring is not particularly limited, but is preferably about 100 to 240 ° C. A known additive such as an antioxidant can be added to the varnish composition for offset printing ink.

The offset printing ink of the present invention uses the varnish for offset printing ink of the present invention, and is blended with pigments (yellow, red, indigo, black) and various known additives, and is used for roll mills, ball mills, and attritors. , It is obtained by kneading and preparing so that the ink constant becomes appropriate using a known ink manufacturing apparatus such as a sand mill. Examples of the additive include a surfactant, a wax, and the like for improving the ink fluidity and the ink surface film.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, "part" and "%" are both based on weight.

(Acid value)
Measured according to JIS K5601.

(Softening point)
Measured according to JIS K5601.

(Weight average molecular weight)
It is a polystyrene-equivalent value measured under a tetrahydrofuran solvent by gel permeation chromatography (GPC). The GPC device is HLC-8220 (manufactured by Tosoh Corporation), and the column is TSK-GEL column (manufactured by Tosoh Corporation). ) Is shown by the measured value obtained.

(Viscosity of flaxseed oil in varnish composition for printing ink)
The 33% flax oil viscosity (Pa · s) is 25 ° C. using a cone and plate viscometer manufactured by Nippon Leology Equipment Co., Ltd. for a mixture of resin and flax oil heated at a weight ratio of 1: 2. It is a value (Pa · s) measured in.

Production Example 1-1 (Production of octylphenol / formaldehyde condensate)
1000 parts of pn-octylphenol, 396 parts of 92% paraformaldehyde, 584 parts of xylene and 500 parts of water were charged in a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer, and the temperature was raised to 50 ° C. with stirring. .. Next, 89 parts of a 45% sodium hydroxide solution was charged in the same reaction vessel, the temperature of the reaction system was gradually raised to 90 ° C. while cooling, the temperature was kept warm for 2 hours, and sulfuric acid was further added dropwise to bring the pH to around 6. It was adjusted. Then, the aqueous layer containing formaldehyde and the like was removed, washed again with water, and then the contents were cooled to obtain a 70 wt% xylene solution of an octylphenol / formaldehyde condensate.

Production Example 1-2
1000 parts of nonylphenol, 444 parts of 92% paraformaldehyde, 604 parts of xylene and 500 parts of water were charged in a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer, and the temperature was raised to 50 ° C. with stirring. Next, 89 parts of a 45% sodium hydroxide solution was charged in the same reaction vessel, the temperature of the reaction system was gradually raised to 90 ° C. while cooling, the temperature was kept warm for 2 hours, and sulfuric acid was further added dropwise to bring the pH to around 6. It was adjusted. Then, the aqueous layer containing formaldehyde and the like was removed, washed again with water, and then the contents were cooled to obtain a 70 wt% xylene solution of a nonylphenol / formaldehyde condensate.

Production Example 2-1 (Production of rosin-modified phenolic resin (A-1))
950 parts of gumrosin was placed in a reaction vessel equipped with a stirrer, a reflux condenser with a water divider, and a thermometer, and the temperature was raised to 180 ° C. and melted while stirring under a nitrogen atmosphere. The reaction system was then heated to 240 ° C. Subsequently, 714 parts (solid content 500 parts) of the octylphenol / formaldehyde condensate solution of Production Example 1-1 was added dropwise into the system over 6 hours. After completion of the dropping, 84 parts of glycerin and 1.0 part of p-toluenesulfonic acid were added, and the mixture was reacted in a temperature range of 240 to 280 ° C. until the acid value reached 25 mgKOH / g. After completion of the reaction, the viscosity of 33 wt% flaxseed oil was adjusted to 14 Pa · s, and the pressure was reduced at 0.02 MPa for 10 minutes to obtain a rosin-modified phenolic resin (A-1) (acid value: 19.1 mgKOH / g, A softening point: 181.0 ° C. and a weight average molecular weight: 126,000) were obtained.

Production Example 2-2 (Production of rosin-modified phenolic resin (A-2))
It was synthesized in the same manner as in Production Example 2-1 except that the solution of the octylphenol / formaldehyde condensate was changed to the solution of the nonylphenol / formaldehyde condensate of Production Example 1-2, and the rosin-modified phenol resin (A-2) (acid value). : 20.0 mgKOH / g, softening point: 174.0 ° C., weight average molecular weight: 150,000) was obtained.

Production Example 2-3 (Production of rosin-modified phenolic resin (A-3))
950 parts of gum rosin was charged in the same reaction vessel as in Production Example 2-1 and heated to 180 ° C. while stirring under a nitrogen atmosphere to melt. The reaction system was then heated to 240 ° C. Subsequently, 714 parts (solid content 500 parts) of the octylphenol / formaldehyde condensate solution of Production Example 1-1 was added dropwise into the system over 6 hours. After completion of the dropping, 84 parts of glycerin, 33 parts of polycaprolactone and 1.0 part of p-toluenesulfonic acid were added, and the reaction was carried out within a temperature range of 240 to 280 ° C. until the acid value reached 25 mgKOH / g. After completion of the reaction, the viscosity of 33 wt% flaxseed oil was adjusted to 14 Pa · s, and the pressure was reduced at 0.02 MPa for 10 minutes to obtain a rosin-modified phenolic resin (A-3) (acid value: 19.1 mgKOH / g, A softening point: 178.0 ° C., weight average molecular weight: 120,000) was obtained.

Production Example 2-4 (Production of rosin-modified alkyd resin (A-4))
1,000 parts of gum rosin was charged in the same reaction vessel as in Production Example 2-1 and heated to 180 ° C. while stirring under a nitrogen atmosphere to melt it. Next, 267 parts of fumaric acid was charged, the temperature of the reaction system was raised to 230 ° C. with stirring, and the mixture was kept warm for 1 hour and then cooled to obtain fumaric acid-modified rosin (acid value: 340 mgKOH / g). Next, 675 parts of the polymerized rosin, 86 parts of the fumaric acid-modified rosin, and 57 parts of isophthalic acid were charged in a reaction vessel equipped with the same instrument, and the temperature was raised to 180 ° C. while stirring under a nitrogen atmosphere to melt the mixture. I let you. Then, 55 parts of pentaerythritol and 55 parts of glycerin were added, the temperature of the reaction system was raised to 260 ° C. with stirring, and the reaction was carried out until the acid value became 30 mgKOH / g or less, and then 1 part of paratoluenesulfonic acid. Was further charged, and further reacted until the acid value became 20 mgKOH / g or less. Then, the viscosity of 33% by weight flaxseed oil was adjusted to 8.0 Pa · s, and the pressure was reduced to 0.02 MPa for 10 minutes and cooled to make a rosin-modified alkyd resin (A-4) (acid value 18.8 mgKOH / g,). A softening point of 155.0 ° C. and a weight average molecular weight of 98,000) were obtained.

Production Example 2-5 (Production of rosin-modified petroleum resin (A-5))
Put 1,000 parts of DCPD-based petroleum resin (trade name: Quinton 1325, manufactured by Nippon Zeon Co., Ltd.) in the same reaction vessel as in Production Example 2-1 and stir the reaction system to 180 ° C. in a nitrogen atmosphere. The temperature was raised to melt it. Next, 70 parts of maleic anhydride was charged, the temperature of the reaction system was raised to 230 ° C. with stirring, and the reaction system was kept warm for 3 hours, and then cooled to contain a carboxyl group-containing petroleum resin (acid value 75 mgKOH / g, weight average molecular weight 4,000). Got
Next, 450 parts of the polymerized rosin, 120 parts of the fumaric acid-modified rosin obtained in Production Example 3, and 298 parts of the above-mentioned carboxyl group-containing petroleum resin were charged in a reaction vessel equipped with the same apparatus, and stirred under a nitrogen atmosphere. While raising the temperature to 180 ° C., the mixture was melted. Then, 29 parts of pentaerythritol and 31 parts of glycerin were added, the temperature of the reaction system was raised to 260 ° C. while stirring under a nitrogen atmosphere, and the reaction was carried out until the acid value became 30 mgKOH / g or less, and then paratoluenesulfon. One part of the acid was charged and further reacted until the acid value became 20 mgKOH / g or less. Then, the viscosity of 33% by weight flaxseed oil was adjusted to 8.0 Pa · s, reduced pressure at 0.02 MPa for 10 minutes, and cooled to rosin-modified petroleum resin (A-5) (acid value 15.3 mgKOH / g, A softening point of 160.0 ° C. and a weight average molecular weight of 58,000) were obtained.

Example 1 (Preparation of varnish composition for offset printing ink)
45 parts of rosin-modified phenolic resin as component (A), 1 part of polycaprolactone (trade name "Plaxel H1P", manufactured by Daicel Co., Ltd.) with a weight average molecular weight of 10,000 as component (B), and large as component (C). 15 parts of soybean oil (trade name "soybean white squeezed oil", manufactured by Nisshin Oillio Co., Ltd.), and AF solvent No. 7 (manufactured by JXTG Energy Co., Ltd., boiling point range: 259 to 282 ° C, aromatic) as component (D) Hydrocarbon content: 0%) 39.5 parts were mixed and dissolved at 200 ° C. for 30 minutes. Next, after cooling this to 80 ° C., 0.5 part of aluminum dipropoxide monoacetyl acetate (trade name: "Kerope EP-2", manufactured by Hope Pharmaceutical Co., Ltd.) (hereinafter referred to as gelling agent) is added. , The varnish composition for offset printing ink was obtained by heating to 200 ° C. and causing a gelation reaction for 1 hour.

Examples 2 to 14, Comparative Examples 1 to 6
Varnish compositions for offset printing inks were obtained with the compositions shown in Table 1.

<Preparation of offset printing ink and ink performance test>
Using each offset printing ink varnish composition (hereinafter, also referred to as varnish composition), the meat is kneaded with a three-roll mill at the following blending ratios, and the tack value is 7.5 ± 0.5, and the flow value of the spread meter. The ink was appropriately prepared so that the (diameter value) was 40.0 ± 1.0, and used as the offset printing ink according to the present invention. For the varnish compositions of Example 14 and Comparative Example 5, the component (D-2) was used instead of the component (D-1) below.
Phthalocyanine blue (indigo pigment) 15 parts Varnish composition 70-75 parts (D-1) Ingredients 10-15 parts

(Gloss)
After spreading 0.4 ml of offset printing ink on art paper with an RI tester (manufactured by Ishikawajima Sangyo Kikai Co., Ltd.), the temperature was 23 ° C. and 50% R. H. The humidity was adjusted for 24 hours, and the reflectance at 60 ° -60 ° was measured with a gloss meter. The larger the value, the better the gloss.

(Abrasion resistance)
The color-developed material prepared for the gloss measurement was tested using a Sutherland type love tester (manufactured by Tester Sangyo Co., Ltd.) under the conditions of 2 pounds and 20 times. The friction resistance was relatively evaluated based on the result of Comparative Example 1.
(Evaluation criteria)
5: Very good compared to Comparative Example 1 4: Good compared to Comparative Example 1 3: Slightly better than Comparative Example 1 2: Equivalent to Comparative Example 1: Poor compared to Comparative Example 1

(Misching resistance)
Spread 2.6 ml of offset printing ink on an incometer (manufactured by Toyo Seiki Seisakusho Co., Ltd.), rotate it at a roll temperature of 30 ° C. at 400 rpm for 1 minute, and then rotate it at 1800 rpm for 2 minutes, and place it on white paper placed directly under the roll. The degree of ink scattering was observed and evaluated on a scale of 1 to 5. The larger the value, the better the misting resistance.
(Evaluation criteria)
5: The degree of ink scattering on white paper is low 4: The degree of ink scattering on white paper is slightly low 3: The degree of ink scattering on white paper is slightly high 2: The degree of ink scattering on white paper is high 1: Very high degree of ink scattering on white paper

The symbols of each component in Table 1 indicate the following compounds.
<Ingredient (A)>
(A-1) Rosin-modified phenolic resin of Production Example 2-1 (A-2) Rosin-modified phenolic resin of Production Example 2-2 (A-3) Rosin-modified phenolic resin of Production Example 2-3 (A-4) Rosin-modified phenol formaldehyde of Production Example 2-4 (A-5) Rosin-modified petroleum resin of Production Example 2-5 <(B) component>
(B-1) Polycaprolactone (trade name "Plaxel H1P", manufactured by Daicel Corporation, weight average molecular weight: 10,000)
(B-2) Polycaprolactone diol (trade name "Plaxel 205", manufactured by Daicel Corporation, weight average molecular weight: 530)
(B-3) Polycaprolactone triol (trade name "Plaxel 305", manufactured by Daicel Corporation, weight average molecular weight: 550)
(B-4) Polycaprolactone diol (trade name "Plaxel 240", manufactured by Daicel Corporation, weight average molecular weight: 4,000)
<Ingredient (C)>
(C-1) Soybean oil (trade name "Soybean white squeezed oil", manufactured by Nisshin Oillio Co., Ltd.)
(C-2) Flaxseed oil (trade name "NB flaxseed oil", manufactured by Nisshin Oillio Co., Ltd.)
<(D) component>
(D-1) AF Solvent No. 7 (manufactured by JXTG Energy Co., Ltd., boiling point: 259 to 282 ° C., aromatic hydrocarbon content: 0%)
(D-2) AF Solvent No. 4 (manufactured by JXTG Energy Co., Ltd., boiling point: 240 to 265 ° C., aromatic hydrocarbon content: 0%)
<(F) component>
(F-1) Polyethylene wax (trade name "paraffin", manufactured by Wako Pure Chemical Industries, Ltd.)

Claims (5)

At least one resin (A) selected from the group consisting of rosin-modified phenolic resin, rosin-modified alkyd resin and rosin-modified petroleum resin, polycaprolactones (B), vegetable oils (C) and / or petroleum-based solvent ( A varnish composition for offset printing ink containing D). The varnish composition for offset printing ink according to claim 1, further comprising a gelling agent (E). (B) The varnish composition for offset printing ink according to claim 1 or 2, wherein the weight average molecular weight of the component is 500 to 10,000. The varnish composition for offset printing ink according to any one of claims 1 to 3, wherein the content of the component (B) is 1 to 12 parts by weight with respect to 100 parts by weight of the component (A). An offset printing ink containing the varnish composition for the offset printing ink according to any one of claims 1 to 4.