Ink composition, ink

Abstract

To provide a composition for ink that exhibits high gloss and excellent flowability when made into ink.SOLUTION: This invention relates to: a composition for ink that contains a reaction product (A) composed of a rosin-based resin (a1), a formaldehyde (a2) and a phenol (a3), and at least one resin (B) selected from the group consisting of a rosin-modified phenolic resin, a rosin-modified alkyd resin and a petroleum resin; and an ink containing the composition for ink.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an ink composition and an ink. [Background technology]

[0002] An ink composition is a solution of an ink resin, vegetable oil, and, if necessary, a gelling agent, in various ink solvents. Conventionally, rosin-modified phenolic resins have been widely used as ink resins (see Patent Documents 1 and 2, etc.).

[0003] In addition, when preparing the ink, a pigment is blended into the composition, but if the pigment is not sufficiently dispersed, the ink will have poor fluidity and the gloss will decrease when printed. On the other hand, in order to sufficiently disperse the pigment, mechanical dispersion for a long period of time can be used, but this leads to a decrease in productivity. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 1-036668 [Patent Document 2] Japanese Patent Application Publication No. 1-170676 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide an ink composition which exhibits high gloss and excellent flowability when made into ink. [Means for solving the problem]

[0006] The present inventors have conducted extensive research and found that the above problems can be solved by incorporating a reaction product of a rosin resin and a phenolic resin as a resin component of the ink, thereby completing the present invention. That is, the present invention relates to the following ink composition and ink.

[0007] 1. An ink composition comprising: a reaction product (A) of a rosin-based resin (a1), formaldehyde (a2) and a phenol (a3); and one or more resins (B) selected from the group consisting of rosin-modified phenolic resins, rosin-modified alkyd resins and petroleum resins.

[0008] 2. The ink composition according to item 1 above, wherein the component (a1) is an unmodified rosin and / or an unsaturated carboxylic acid-modified rosin.

[0009] 3. The ink composition according to item 1 or 2 above, wherein the component (a3) ​​is one or more members selected from the group consisting of butylphenol, octylphenol and nonylphenol.

[0010] 4. The ink composition according to any one of items 1 to 3 above, wherein the weight average molecular weight of component (A) is 1,000 to 5,000.

[0011] 5. The ink composition according to any one of items 1 to 4 above, wherein the content of component (A) is 1 to 25 parts by weight per 100 parts by weight of the total of components (A) and (B).

[0012] 6. The ink composition according to any one of items 1 to 5 above, further comprising a vegetable oil and / or a petroleum-based solvent.

[0013] 7. The ink composition according to any one of items 1 to 6 above, further comprising a gelling agent.

[0014] 8. An ink comprising the ink composition according to any one of items 1 to 7 above. Effect of the Invention

[0015] The ink composition according to the present invention has high gloss and excellent flowability when made into an ink, and is particularly suitable for use as an offset printing ink. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] The ink composition of the present invention contains a reaction product (A) (hereinafter referred to as component (A)) consisting of a rosin-based resin (a1) (hereinafter referred to as component (a1)), formaldehyde (a2) (hereinafter referred to as component (a2)), and a phenol (a3) ​​(hereinafter referred to as component (a3)), as well as one or more resins (B) (hereinafter referred to as component (B)) selected from the group consisting of rosin-modified phenolic resins, rosin-modified alkyd resins, and petroleum resins.

[0017] The component (A) is a component that exhibits high gloss and excellent fluidity by increasing the dispersibility of the pigment. Each component will be described below.

[0018] The component (a1) is not particularly limited, and examples thereof include unmodified rosins such as gum rosin, tall oil rosin, and wood rosin; polymerized rosins derived from unmodified rosin; disproportionates or hydrogenates of unmodified rosin or polymerized rosin; and unsaturated carboxylic acid-modified rosins obtained by subjecting unmodified rosin or polymerized rosin to a Diels-Alder reaction with an unsaturated carboxylic acid. These may be used alone or in combination of two or more. The "unmodified rosin" includes abietane-type resin acids such as abietic acid, neoabietic acid, and levopimaric acid; and pimaric-type resin acids such as palustric acid and pimaric acid, but may also include dihydroagatic acid, communic acid, and the like.

[0019] The unsaturated carboxylic acid is not particularly limited, and examples thereof include unsaturated dicarboxylic acids such as maleic acid (anhydride), fumaric acid, and itaconic acid (anhydride), and unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid. The amount of the unsaturated carboxylic acid used is also not particularly limited, and is usually about 1 to 30 parts by weight, and preferably about 1 to 10 parts by weight, per 100 parts by weight of unmodified rosin or polymerized rosin.

[0020] The component (a2) is not particularly limited, and examples thereof include formalin and paraformaldehyde.

[0021] The amount of the component (a2) used is not particularly limited, but is usually 3 to 40 parts by weight, and preferably 5 to 30 parts by weight, per 100 parts by weight of the component (a1) calculated as solid content.

[0022] The component (a3) ​​is a phenol, such as carbolic acid (phenol) or alkylphenol. The alkylphenol means a phenol having an alkyl group at at least one of the ortho-position (o-), meta-position (m-) or para-position (p-) relative to the phenol hydroxyl group. The alkyl group of the alkylphenol may be an n-alkyl group, an isoalkyl group, an s-alkyl group or a t-alkyl group having a straight chain structure or a branched structure.

[0023] Examples of alkylphenols include methylphenol (cresol), butylphenol, pentylcresol, octylphenol, nonylphenol, decylphenol, dodecylphenol, tetradecylphenol, and hexyldecylphenol. These may be used alone or in combination of two or more. Among them, alkylphenols having an alkyl group with 4 to 12 carbon atoms are preferred, and butylphenol, octylphenol, and nonylphenol are more preferred, from the viewpoints of solubility in petroleum-based solvents, and excellent drying properties and emulsification resistance of the ink.

[0024] The amount of the component (a3) ​​used is not particularly limited, but is usually 15 to 90 parts by weight, and preferably 20 to 70 parts by weight, per 100 parts by weight of the component (a1) calculated as solid content.

[0025] The ratio of the (a2) component to the (a3) ​​component used is not particularly limited, but the molar ratio [(a2) / (a3)] of each is usually about 1 to 3. Hereinafter, the (a2) / (a3) ratio is also referred to as the F / P ratio.

[0026] In addition, instead of the components (a2) and (a3) ​​of the present invention, a resol type phenolic resin which is a condensate of the components (a2) and (a3) ​​may be used. Examples of the resol type phenolic resin include condensates obtained by addition-condensation reaction in the presence of a basic catalyst. In addition, a novolac type phenolic resin which is a condensate obtained by addition-condensation reaction of the components (a2) and (a3) ​​in the presence of an acidic catalyst may be appropriately used in combination with the resol type phenolic resin.

[0027] The basic catalyst is not particularly limited, and examples thereof include organic amines such as triethylamine, metal oxides such as magnesium oxide and zinc oxide, metal hydroxides such as sodium hydroxide, magnesium hydroxide and calcium hydroxide, and metal acetates such as calcium acetate, magnesium acetate and zinc acetate. Examples of the acidic catalyst include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as oxalic acid, methanesulfonic acid, paratoluenesulfonic acid and dodecylbenzenesulfonic acid. These may be used alone or in combination of two or more.

[0028] The condensation products may be neutralized and washed before use. The condensation products may be produced in the presence of an organic solvent such as toluene or xylene, or water. The reaction conditions are not particularly limited, but for example, the components (a2) and (a3) ​​may be charged and reacted at a temperature of about 20 to 110° C. for about 1 to 10 hours.

[0029] The component (A) of the present invention is obtained by reacting the components (a1) to (a3). Examples of the production method include charging the components (a1) to (a3) ​​all at once and reacting them in the presence of a catalyst, or mixing the component (a1) with a condensate of the components (a2) and (a3) ​​and reacting them by heat.

[0030] The catalyst is not particularly limited, and examples thereof include the above-mentioned basic catalysts, etc. The amount of the catalyst used is also not particularly limited, and is preferably 0.05 to 5 parts by weight, and more preferably 0.05 to 3 parts by weight, per 100 parts by weight of the component (a1).

[0031] The reaction conditions are not particularly limited, but are preferably carried out at a temperature of about 150 to 300° C. for a time of about 1 to 10 hours.

[0032] The physical properties of the obtained component (A) are not particularly limited, but for example, the weight average molecular weight (referring to a polystyrene equivalent value in gel permeation chromatography; the same applies hereinafter) is preferably 1,000 to 5,000, and more preferably 2,000 to 4,000. When the weight average molecular weight of component (A) is within this range, in addition to high gloss and excellent fluidity of the ink, excellent drying properties and emulsification resistance of the ink are ensured.

[0033] In addition, other physical properties are not particularly limited, but for example, the acid value (JIS K5601) is usually about 80 to 140 mgKOH / g in terms of solubility in petroleum-based solvents.

[0034] The softening point (JIS K5601) is not particularly limited, but is usually about 100 to 180°C.

[0035] The content of component (A) in the ink composition of the present invention is preferably 1 to 25 parts by weight, and more preferably 10 to 20 parts by weight, based on 100 parts by weight of the total of components (A) and (B), in terms of solid content weight. When the content of component (A) is within this range, the ink is ensured to have high gloss and excellent fluidity, as well as excellent drying properties and emulsification resistance.

[0036] The component (B) is one or more resins selected from the group consisting of rosin-modified phenolic resins, rosin-modified alkyd resins, and petroleum resins. Each of the resins will be described below.

[0037] (rosin modified phenolic resin) The rosin-modified phenolic resin is a reaction product of a rosin-based resin, a phenol, formaldehyde, and a polyol.

[0038] As the rosin resin, phenols, and formaldehyde, those exemplified as specific examples of the components (a1) to (a3) ​​above can be used. It is preferable to use a resol-type phenolic resin in which phenols and formaldehyde are pre-condensed, since it is easy to increase the molecular weight of the rosin-modified phenolic resin. The reaction conditions are as described in the previous paragraph.

[0039] A polyol is a compound having two or more hydroxyl groups in one molecule. The polyol is not particularly limited, and examples thereof include diols such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and 3-methyl-1,5-pentanediol; triols such as glycerin, trimethylolpropane, and trimethylolethane; and tetraols such as pentaerythritol, diglycerin, ditrimethylolpropane, and ditrimethylolethane, which may be used alone or in combination of two or more. Among them, triols and / or tetraols are preferred because they are easy to control the physical properties (softening point, weight average molecular weight, etc.) of the rosin-modified phenolic resin.

[0040] The amounts of rosin resin, formaldehyde, phenols and polyols used are not particularly limited, and are set as follows, with the total amount of these components taken as 100% by weight, from the viewpoints of high molecular weight, solubility in petroleum-based solvents, and misting resistance of the ink. Note that the amounts of formaldehyde and alkylphenols are stated in terms of the content of their condensates. Rosin-based resin: usually about 41 to 87% by weight, preferably about 46 to 73% by weight Phenols / formaldehyde (condensation product): usually about 9 to 50% by weight, preferably about 22 to 46% by weight Polyol: usually about 3 to 9% by weight, preferably about 4 to 8% by weight

[0041] The amounts of the rosin resin and polyol used are not particularly limited, but from the standpoint of the misting resistance and gloss of the ink, it is usually preferable that the ratio (OH / COOH) of the total hydroxyl group equivalent number of the polyol (OH) to the total carboxyl group equivalent number of the rosin resin (COOH) be about 0.5 to 1.5.

[0042] The method for producing the rosin-modified phenolic resin is not particularly limited, and examples thereof include the following methods. (1) A method in which rosin resin, phenols / formaldehyde (condensation product), and polyol are charged together and reacted. (2) A method of reacting a polyol with a reaction product of a rosin resin and a phenol / formaldehyde (condensation product). (3) A method of reacting a reaction product of a rosin resin and a polyol with a phenol / formaldehyde (condensate) The reaction temperature is usually about 100 to 300° C., and the reaction time is usually about 1 to 24 hours. In the reaction, the acidic catalyst or basic catalyst used in the production of the phenol / formaldehyde (condensation product) can be used.

[0043] The physical properties of the obtained rosin-modified phenolic resin are not particularly limited, but for example, the weight average molecular weight is about 10,000 to 400,000, and preferably 20,000 to 400,000, from the viewpoints of high ink gloss, excellent abrasion resistance and drying properties.

[0044] In addition, the acid value (JIS K5601) is not particularly limited, but from the viewpoint of solubility in petroleum-based solvents, it is usually about 5 to 30 mgKOH / g, and preferably 10 to 25 mgKOH / g.

[0045] In addition, the softening point (JIS K5601) is not particularly limited, but is usually about 120 to 200°C, preferably 140 to 200°C, from the viewpoint of the misting resistance and drying property of the ink.

[0046] (rosin modified alkyd resin) The rosin-modified alkyd resin is not particularly limited, and examples thereof include a resin obtained by reacting a hydroxyl group-containing resin obtained by reacting a rosin-based resin with a polyol in a conventional manner with a polybasic acid in a conventional manner (for specific conditions, etc., see JP 2019-48971 A).

[0047] The polyol is not particularly limited, and examples thereof include those exemplified in the previous paragraph.

[0048] The polybasic acid is not particularly limited, and examples thereof include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic acid, trimellitic anhydride, succinic acid, succinic anhydride, maleic acid, and maleic anhydride.

[0049] (Petroleum resin) The petroleum resin is not particularly limited, and examples thereof include DCPD-based petroleum resins (raw materials include, for example, cyclopentadiene, dicyclopentadiene, etc.); C5-based petroleum resins (raw materials include, for example, pentene, cyclopentene, pentadiene, isoprene, etc.); C9-based petroleum resins (raw materials include, for example, methylbutene, indene, methylindene, vinyltoluene, styrene, α-methylstyrene, β-methylstyrene, etc.); copolymerized petroleum resins made from raw materials for DCPD-based petroleum resins and raw materials for C5-based petroleum resins; copolymerized petroleum resins made from raw materials for C5-based petroleum resins and raw materials for the C9-based petroleum resins; copolymerized petroleum resins made from raw materials for DCPD-based petroleum resins and raw materials for C9-based petroleum resins; copolymerized petroleum resins made from raw materials for DCPD-based petroleum resins, raw materials for C5-based petroleum resins, and raw materials for the C9-based petroleum resins.

[0050] The petroleum resin may be one in which a polar group such as a carboxyl group or a hydroxyl group has been introduced (hereinafter referred to as a polar group-containing petroleum resin). When a carboxyl group is introduced as the polar group, the petroleum resin is reacted with a polybasic acid, and when a hydroxyl group is introduced, the petroleum resin 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 previous paragraph.

[0051] Furthermore, as the petroleum resin, a rosin-based resin, the petroleum resin or the polar group-containing petroleum resin, and a polyol may be used, and if necessary, a rosin-modified petroleum resin obtained by reacting at least one compound selected from an aliphatic monoalcohol, an aliphatic dialcohol, an aliphatic monoamine, and an aliphatic monoepoxy may be used (for specific conditions, etc., see JP 2019-48971 A).

[0052] The polyol is not particularly limited, and examples thereof include those exemplified in the previous paragraph.

[0053] The aliphatic monoalcohol is not particularly limited, and examples thereof include decyl alcohol, icosanol, triacontanol, and tetracontanol.

[0054] The aliphatic dialcohol is not particularly limited, and examples thereof include 1,2-octadecanediol, decanediol, icosanediol, triacontanediol, and tetracontanediol.

[0055] The aliphatic monoamine is not particularly limited, and examples thereof include decylamine, icosylamine, triacontylamine, tetracontylamine, beef tallow alkylamine, and soybean alkylamine.

[0056] The aliphatic monoepoxy is not particularly limited, and examples thereof include 1,2-epoxyhexane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxydodecane, 1,2-epoxytetradecane, 1,2-epoxyhexadecane, 1,2-epoxyoctadecane, and ethylhexyl glycidyl ether.

[0057] The content of component (B) in the ink composition of the present invention is preferably 75 to 99 parts by weight, and more preferably 80 to 90 parts by weight, based on 100 parts by weight of the total of components (A) and (B), in terms of solid content weight. When the content of component (B) is within this range, the ink is ensured to have high gloss and excellent fluidity, as well as excellent drying properties and emulsification resistance.

[0058] The ink composition of the present invention may further contain vegetable oils and / or petroleum-based solvents.

[0059] Examples of vegetable oils include vegetable oils such as linseed oil, tung oil, safflower oil, dehydrated castor oil, and soybean oil; vegetable oil monoesters such as linseed oil fatty acid methyl, soybean oil fatty acid methyl, linseed oil fatty acid ethyl, soybean oil fatty acid ethyl, linseed oil fatty acid n-propyl, soybean oil fatty acid n-propyl, linseed oil fatty acid n-butyl, and soybean oil fatty acid n-butyl. These may be used alone or in combination of two or more. Among them, from the viewpoint of drying property of ink, vegetable oils having unsaturated bonds in the molecule are preferred, and soybean oil and / or linseed oil are more preferred.

[0060] The content of the vegetable oil is not particularly limited, but from the viewpoint of drying property of the ink, it is usually about 10 to 200 parts by weight, and preferably about 10 to 150 parts by weight, per 100 parts by weight (solid) of the combined weight of components (A) and (B).

[0061] The petroleum-based solvent is not particularly limited, and examples thereof include petroleum-based solvents from JXTG Nippon Oil & Energy Corporation such as No. 0 Solvent, No. 4 Solvent, No. 5 Solvent, No. 6 Solvent, No. 7 Solvent, AF Solvent No. 4, AF Solvent No. 5, AF Solvent No. 6, and AF Solvent No. 7, which may be used alone or in combination of two or more.

[0062] The content of the petroleum-based solvent is not particularly limited, but from the viewpoint of providing an appropriate viscosity for the ink composition and maintaining a balance between the misting resistance and gloss of the ink, it is usually about 10 to 200 parts by weight, and preferably about 10 to 150 parts by weight, per 100 parts by weight (solid) of the combined weight of component (A) and component (B).

[0063] The ink composition of the present invention may further contain a gelling agent.

[0064] The gelling agent is not particularly limited, and examples thereof include aluminum-based gelling agents such as aluminum octylate, aluminum stearate, aluminum triisopropoxide, aluminum tributoxide, aluminum dipropoxide monoacetylacetate, aluminum dibutoxide monoacetylacetate, and aluminum triacetylacetate, which may be used alone or in combination of two or more kinds.

[0065] The ink composition of the present invention is not particularly limited, and can be obtained by mixing component (A), component (B), vegetable oil and / or petroleum-based solvent, and, if necessary, a gelling agent with stirring, and reacting the mixture at a temperature of usually about 100 to 240° C. During the reaction, additives such as antioxidants may be added.

[0066] The method of blending the components is not particularly limited, and may include mixing all of the components at once, or dissolving the components (A) and (B) in a petroleum-based solvent, mixing the resulting mixture, and then blending the vegetable oil, the petroleum-based solvent, and, if necessary, a gelling agent.

[0067] The ink of the present invention contains the ink composition of the present invention. Specifically, the ink composition, pigments (yellow, red, indigo, black, etc.), and, if necessary, the above-mentioned vegetable oils, petroleum-based solvents, and additives such as surfactants and waxes are milled using an ink manufacturing device such as a roll mill, ball mill, attritor, sand mill, etc., to prepare appropriate ink constants. EXAMPLES

[0068] The present invention will be described in more detail below with reference to examples, but is not limited thereto. Unless otherwise specified, all "parts" and "%" are by weight.

[0069] (Acid value) Measurements were performed in accordance with JIS K5601.

[0070] (softening point) Measurements were performed in accordance with JIS K5601.

[0071] (Weight average molecular weight) The values ​​are polystyrene-equivalent values ​​measured by gel permeation chromatography (GPC) in a tetrahydrofuran solvent, and are shown as measured values ​​obtained using an HLC-8320 (manufactured by Tosoh Corporation) as the GPC device and a TSK-GEL column (manufactured by Tosoh Corporation) as the column.

[0072] (Linseed oil viscosity) The viscosity of 33% linseed oil (Pa s) was measured at 25°C using a cone-and-plate viscometer (HAAKE) for a heated mixture of resin and linseed oil in a weight ratio of 1:2.

[0073] Production Example 1-1 (Production of octylphenol-formaldehyde condensate) In a reaction vessel equipped with a stirrer, reflux condenser and thermometer, 1000 parts of pn-octylphenol, 290 parts of 92% paraformaldehyde, 553 parts of xylene and 500 parts of water were charged and heated to 50°C while stirring. Next, 89 parts of 45% sodium hydroxide solution was charged in the same reaction vessel, and the reaction system was gradually heated to 90°C while cooling, and then kept at that temperature for 2 hours, and sulfuric acid was added dropwise to adjust the pH to around 6. After that, the aqueous layer containing formaldehyde and other substances was removed, and the contents were washed again and cooled to obtain a xylene solution of octylphenol-formaldehyde condensate (condensate concentration: 70%).

[0074] Production Example 1-2 (Production of nonylphenol-formaldehyde condensation product) In a reaction vessel similar to that of Production Example 1-1, 1000 parts of nonylphenol, 237 parts of 92% paraformaldehyde, 530 parts of xylene, and 500 parts of water were charged, and the temperature was raised to 50°C while stirring. Next, 89 parts of 45% sodium hydroxide solution was charged in the same reaction vessel, and the reaction system was gradually heated to 90°C while cooling, and then kept at that temperature for 2 hours, and sulfuric acid was further added dropwise to adjust the pH to about 6. Thereafter, the aqueous layer containing formaldehyde, etc. was removed, and the contents were washed again with water and cooled to obtain a xylene solution of nonylphenol-formaldehyde condensate (condensate concentration: 70%).

[0075] Production Example 1-3 (Production of fumaric acid modified rosin) A reaction vessel equipped with a stirrer, a reflux condenser with a water divider, and a thermometer was charged with 1,000 parts of gum rosin, and the reaction system was heated to 180°C while stirring under a nitrogen atmosphere to melt it. Next, 267 parts of fumaric acid was charged into the reaction vessel, and the reaction system was heated to 230°C while stirring and kept at that temperature for 1 hour. After that, the reaction vessel was cooled to obtain 1,240 parts of solid fumaric acid-modified rosin (acid value 342 mgKOH / g, softening point 148°C).

[0076] Production Example 1-4 (Production of carboxyl group-containing petroleum resin) In a reaction vessel similar to that in Production Example 1-3, 1,000 parts of DCPD-based petroleum resin (product name: "Quinton 1325", manufactured by Zeon Corporation) were charged, and the reaction system was heated to 180°C while stirring under a nitrogen atmosphere to melt. Next, 70 parts of maleic anhydride were charged, and the reaction system was heated to 230°C while stirring and kept at that temperature for 3 hours, and then cooled to obtain 1010 parts of a carboxyl group-containing petroleum resin (acid value: 75 mgKOH / g, weight average molecular weight: 4,000).

[0077] Production Example 2-1 (Production of component (A-1)) 950 parts of Chinese gum rosin were charged into a reaction vessel similar to that used in Production Example 1-3, and the temperature was raised to 220°C while stirring under a nitrogen atmosphere to melt the mixture, and 1071 parts (solid content 750 parts) of the octylphenol-formaldehyde condensate solution from Production Example 1-1 were added dropwise to the system over a period of 5 hours. 30 minutes after the completion of the addition, the pressure was reduced to 0.02 MPa for 10 minutes, and reaction product (A-1) (acid value: 100 mg KOH / g, softening point: 149°C, weight average molecular weight: 2,000) was obtained.

[0078] Production Example 2-2 (Production of component (A-2)) The same procedure as in Production Example 2-1 was repeated except that the amount of octylphenol-formaldehyde condensate was changed to 429 parts by weight (solid content: 300 parts), and a reaction product (A-2) (acid value: 132 mg KOH / g, softening point: 137°C, weight average molecular weight: 800) was obtained.

[0079] Production Example 2-3 (Production of component (A-3)) The same procedure as in Production Example 2-1 was repeated except that the amount of octylphenol-formaldehyde condensate was changed to 571 parts by weight (solid content: 400 parts), and a reaction product (A-3) (acid value: 121 mg KOH / g, softening point: 140°C, weight average molecular weight: 1,200) was obtained.

[0080] Production Example 2-4 (Production of component (A-4)) The same procedure as in Production Example 2-1 was repeated except that the weight part of the octylphenol-formaldehyde condensate was changed to 1,500 parts (solid content 1,050 parts), and a reaction product (A-4) (acid value: 90 mg KOH / g, softening point: 164°C, weight average molecular weight: 3,800) was obtained.

[0081] Production Example 2-5 (Production of component (A-5)) The same procedure as in Production Example 2-1 was carried out except that 857 parts (solid content 600 parts) of the nonylphenol-formaldehyde condensate of Production Example 1-2 was used instead of the solution of the octylphenol-formaldehyde condensate, to obtain a reaction product (A-5) (acid value: 113 mg KOH / g, softening point: 140°C, weight average molecular weight: 1,700).

[0082] Production Example 2-6 (Production of component (A-6)) The same procedure as in Production Example 2-5 was carried out except that 1,285 parts of nonylphenol-formaldehyde condensate (solid content 900 parts) was used, and a reaction product (A-6) (acid value: 95 mg KOH / g, softening point: 150°C, weight average molecular weight: 2,600) was obtained.

[0083] Production Example 2-7 (Production of component (A-7)) In a reaction vessel similar to that of Production Example 1-3, 1,000 parts of Chinese gum rosin were charged, and the temperature was raised to 180°C while stirring under a nitrogen atmosphere to melt it. Next, 20 parts of maleic anhydride were charged, and the reaction system was heated to 220°C while stirring and kept at that temperature for 1 hour, after which 571 parts (400 parts solids) of the octylphenol-formaldehyde condensate solution of Production Example 1-1 were dropped into the system over 4 hours. 30 minutes after the dropwise addition, the pressure was reduced to 0.02 MPa for 10 minutes to obtain the reaction product (A-7) (acid value: 125 mg KOH / g, softening point: 140°C, weight average molecular weight: 1,500).

[0084] Production Example 3-1 (Production of component (B-1)) 1,000 parts of Chinese gum rosin were charged into a reaction vessel equipped with a stirrer, a reflux condenser with a water divider, and a thermometer, and the mixture was heated to 180°C under a nitrogen atmosphere while stirring to melt it. The reaction system was then heated to 240°C. 1,071 parts (solid content 750 parts) of the octylphenol-formaldehyde condensate solution of Production Example 1-1 were then added dropwise to the system over a period of 5 hours. After the dropwise addition was completed, 96 parts of glycerin and 1.0 part of paratoluenesulfonic acid were added, and the mixture was allowed to react within a temperature range of 240-280°C until the acid value reached 20 mgKOH / g. After the reaction was completed, the viscosity of the 33 wt% linseed oil was adjusted to 10 Pa·s, and the pressure was reduced to 0.02 MPa for 10 minutes to obtain rosin-modified phenolic resin (B-1) (acid value: 20.0 mg KOH / g, softening point: 175.0°C, weight average molecular weight: 110,000).

[0085] Production Example 3-2 (Production of rosin-modified alkyd resin (B-2)) In a reaction vessel similar to that of Production Example 3-1, 1,000 parts of Chinese gum rosin were charged, and the mixture was heated to 180°C with stirring under a nitrogen atmosphere to melt. Next, 267 parts of fumaric acid were charged, and the reaction system was heated to 230°C with stirring and kept at that temperature for 1 hour, and then cooled to obtain a fumaric acid modified rosin (acid value: 340 mgKOH / g). Next, 675 parts of polymerized rosin, 86 parts of the fumaric acid-modified rosin, and 57 parts of isophthalic acid were charged into a reaction vessel equipped with the same equipment, and the mixture was heated to 180°C while stirring under a nitrogen atmosphere to melt. Then, 55 parts of pentaerythritol and 55 parts of glycerin were added, and the reaction system was heated to 260°C while stirring to react until the acid value was 30 mgKOH / g or less, and then 1 part of paratoluenesulfonic acid was charged and reacted until the acid value was 20 mgKOH / g or less. Then, the viscosity of 33 wt% linseed oil was adjusted to 8.0 Pa·s, and the pressure was reduced to 0.02 MPa for 10 minutes, and the mixture was cooled to obtain a rosin-modified alkyd resin (B-2) (acid value: 18.8 mgKOH / g, softening point: 155.0°C, weight average molecular weight: 98,000).

[0086] Production Example 3-3 (Production of Rosin Modified Petroleum Resin (B-3)) In a reaction vessel similar to that of Production Example 3-1, 450 parts of polymerized rosin, 120 parts of fumaric acid-modified rosin obtained in Production Example 1-3, and 298 parts of carboxyl group-containing petroleum resin obtained in Production Example 1-4 were charged, and the mixture was heated to 180°C while stirring under a nitrogen atmosphere to melt. Then, 29 parts of pentaerythritol and 31 parts of glycerin were added, and the mixture was heated to 260°C while stirring under a nitrogen atmosphere to react until the acid value was 30mgKOH / g or less. Next, 1 part of paratoluenesulfonic acid was charged, and the mixture was further reacted until the acid value was 20mgKOH / g or less. Then, the viscosity of 33% by weight linseed oil was adjusted to 8.0 Pa·s, and the mixture was decompressed at 0.02 MPa for 10 minutes and cooled to obtain rosin-modified petroleum resin (B-3) (acid value: 15.3mgKOH / g, softening point: 160.0°C, weight average molecular weight: 58,000).

[0087] Example 1 0.8 parts of component (A-1), 40.2 parts of component (B-1), 10 parts of soybean oil (trade name: "Soybean White Oil", manufactured by Nisshin Oillio Co., Ltd.), and 40 parts of AF Solvent No. 7 (manufactured by JXTG Energy Corporation) were mixed and dissolved at 180°C for 30 minutes. After cooling to 160°C, 0.85 parts of aluminum dipropoxide monoacetyl acetate (trade name: "Kerope EP-2", manufactured by Hope Pharmaceutical Co., Ltd.) (hereinafter referred to as gelling agent) was added, and the mixture was heated to 190°C and subjected to a gelling reaction for 1 hour to obtain an ink composition.

[0088] Examples 2 to 12, Comparative Examples 1 to 4 The ink compositions were obtained in the same manner as in Example 1, except that the types and contents of the (A) and (B) components were as shown in Table 1. Note that the ink composition of Comparative Example 4 was not subjected to evaluation because it could not be milled.

[0089] <Ink preparation and ink performance test> The ink composition was milled in the following proportions using a three-roll mill and appropriately adjusted so that the tack value was 7.5±0.5 and the spreadmeter flow value (diameter value) was 40±1.0. The tack value was measured using an incomer at a temperature of 30°C and a roll rotation speed of 400 rpm, and the flow value was measured at a temperature of 25°C. LIONOL RED 6B (red pigment) 15 parts Ink composition 65-85 parts AF Solvent No. 7 0-20 parts

[0090] (Glossy) 0.4 ml of each ink was spread on art paper using an RI tester (Ishikawajima Industrial Machinery Co., Ltd.), and then conditioned at 23°C and 50% RH for 24 hours, and the reflectance at 60°-60° was measured using a gloss meter. In this evaluation, Examples 1 to 10 were compared with Comparative Example 1, Example 11 with Comparative Example 2, and Example 12 with Comparative Example 3, and it was determined that the gloss was superior when the numerical value of the Example was larger. The results are shown in Table 1 (same below).

[0091] (Liquidity) In a room adjusted to a temperature of 25°C, 1.3 ml of each ink was placed on the top edge of a glass plate at an angle of 60° to the horizontal, and the distance it flowed in 30 minutes (unit: mm) was measured. The higher the value, the better the flowability.

[0092] [Table 1]

Claims

1. The composition comprises a reaction product (A) consisting of a rosin-based resin (a1), formaldehyde (a2) and a phenol (a3), and one or more resins (B) selected from the group consisting of a rosin-modified phenolic resin, a rosin-modified alkyd resin and a petroleum resin, The component (a1) is unmodified rosin and / or unsaturated carboxylic acid-modified rosin, The component (a3) ​​is at least one selected from the group consisting of butylphenol, octylphenol, and nonylphenol, An ink composition, wherein the weight average molecular weight of component (A) is 1,000 to 5,000.

2. 2. The ink composition according to claim 1, wherein the content of component (A) is 1 to 25 parts by weight per 100 parts by weight of the total of components (A) and (B).

3. The ink composition according to claim 1 or 2, further comprising a vegetable oil and / or a petroleum-based solvent.

4. The ink composition according to any one of claims 1 to 3, further comprising a gelling agent.

5. An ink comprising the ink composition according to any one of claims 1 to 4.

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