JP2023086113A - Composition for ink, and gravure ink - Google Patents

Abstract

To provide a composition for ink which has excellent adhesion to not only a high polar plastic film but also a low polar plastic film, and gravure ink containing the composition.SOLUTION: There are provided a composition for ink which contains a rosin phenol resin (A) that is a product of a reactive component containing rosins (a1) and phenols (a2), and one or more resins (B) selected from the group consisting of a polyurethane-based resin, a cellulose-based resin, a rubber-based resin, a polyamide-based resin, an acrylic resin and a vinyl acetate-based resin; and gravure ink containing the composition for ink.SELECTED DRAWING: None

Description

The present invention relates to an ink composition and gravure ink.

Various binder resins are used in the production of inks. (Patent Document 1).
However, such resins have excellent adhesion to high-polarity plastic films such as polyester films (PET) and nylon films (NY), while they have excellent adhesion to low-polarity plastic films such as polypropylene (PP). was difficult to exhibit sufficient adhesion.

JP 2012-193250 A

An object of the present invention is to provide an ink composition having excellent adhesion not only to highly polar plastic films but also to low polar plastic films, and a gravure ink containing the composition.

In addition to solving the above problems, the present inventors have also focused on using a rosin-based resin, which is a biomass material, from the viewpoint of reducing the environmental load. was completed. That is, the present invention relates to the following ink composition and gravure ink.

1. Rosin phenolic resin (A), which is a product of reaction components containing rosins (a1) and phenols (a2), as well as polyurethane-based resins, cellulose-based resins, rubber-based resins, polyamide-based resins, acrylic-based resins and acetic acid An ink composition containing one or more resins (B) selected from the group consisting of vinyl resins.

2. 2. The ink composition according to the preceding item 1, wherein the component (a2) is phenol and/or alkylphenol.

3. 3. The ink composition according to item 1 or 2, wherein the reactive component further contains an aliphatic polyol and/or an alicyclic polyol (a3).

4. 3. The ink composition according to item 1 or 2, wherein the content ratio of component (A) to component (B) is (A)/(B)=1/99 to 60/40 in terms of weight of non-volatile matter.

5. 3. The ink composition according to item 1 or 2, further comprising a pigment and an organic solvent.

6. A gravure ink comprising the ink composition according to 1 or 2 above.

According to the ink composition of the present invention, when used as an ink, it has excellent adhesion not only to high-polarity plastic films but also to low-polarity plastic films. The ink is particularly suitable for gravure ink.

The ink composition of the present invention comprises a rosin that is a product of reaction components containing rosins (a1) (hereinafter referred to as component (a1)) and phenols (a2) (hereinafter referred to as component (a2)). Phenolic resin (A) (hereinafter referred to as component (A)), and one selected from the group consisting of polyurethane-based resins, cellulose-based resins, rubber-based resins, polyamide-based resins, acrylic-based resins, and vinyl acetate-based resins It contains the above resin (B) (hereinafter referred to as component (B)).

Component (A) is a component that exhibits excellent adhesion to plastic films, and is a product of the reaction components including the components (a1) and (a2).

The component (a1) is a rosin, including natural rosin and modified rosin. These may be used alone or in combination of two or more.

Natural rosin is a mixture of resin acids collected from plants of the Pinaceae family, and is classified into gum rosin, tall oil rosin, and wood rosin according to the production method. The resin acid mainly includes abietic acid, and also includes neoabietic acid, parastric acid, dehydroabietic acid, levopimaric acid, pimaric acid, isopimaric acid, sandaracopimaric acid, and the like. In addition, natural rosin containing dihydroagatic acid, comic acid, etc. can also be used. These may be used alone or in combination of two or more.

As the natural rosin, a product obtained by purifying the rosin (hereinafter also referred to as a purified rosin) can also be used.

Purified rosin is obtained by purifying natural rosin by a purification method such as vacuum distillation, extraction, or recrystallization. Further, the purification conditions are not particularly limited.

In the case of vacuum distillation, the temperature is about 200-300° C. and the degree of vacuum is 60-3000 Pa.

In the extraction method, natural rosin is made into an alkaline aqueous solution, unsaponifiable substances not dissolved in the aqueous solution are extracted with various organic solvents, and the remaining aqueous layer is neutralized.

In the case of the recrystallization method, the component (a1) is dissolved in an organic solvent as a good solvent, the organic solvent is distilled off to obtain a concentrated solution, and an organic solvent as a poor solvent is added.

Examples of good solvents include aromatic hydrocarbons such as benzene, toluene and xylene; organic halogens such as chloroform; ketones such as acetone and methyl ethyl ketone; alcohols such as methanol, ethanol and isopropyl alcohol; etc. These may be used alone or in combination of two or more.

Examples of the poor solvent include aliphatic hydrocarbons such as n-hexane, n-heptane and isooctane; alicyclic hydrocarbons such as cyclohexane and decalin; These may be used alone or in combination of two or more.

Modified rosin refers to those obtained by modifying the above-mentioned natural rosin by various reactions. Modified rosins include, for example, hydrogenated natural rosin (hydrogenated rosin), disproportionated natural rosin (disproportionated rosin), polymerized natural rosin (polymerized rosin), α,β-unsaturated natural rosin carboxylic acid adducts (α,β-unsaturated carboxylic acid-modified rosins) or esters thereof (hydrogenated rosin esters, disproportionated rosin esters, polymerized rosin esters, α,β-unsaturated carboxylic acid-modified rosin esters), Esterified products of natural rosin and alcohol (rosin ester) and the like can be mentioned. These modified rosins may also be used after being purified after being modified. Furthermore, the modified rosin may contain unreacted natural rosin. These may be used alone or in combination of two or more.

Hydrogenated rosin is obtained by hydrogenating natural rosin, and can be obtained, for example, by heating natural rosin at 100 to 300° C. under a hydrogen atmosphere of 2 to 20 MPa in the presence of a hydrogenation catalyst. As for the reaction conditions, the pressure is preferably 5 to 20 MPa, and the reaction temperature is preferably 150 to 300°C.

Examples of the hydrogenation catalyst include supported catalysts such as palladium carbon, rhodium carbon, ruthenium carbon and platinum carbon; metal powders of nickel and platinum. The amount of hydrogenation catalyst used is usually 0.01 to 5 parts by weight, preferably 0.01 to 2 parts by weight, per 100 parts by weight of natural rosin.

Disproportionated rosin is obtained by disproportionating natural rosin, and is obtained, for example, by subjecting natural rosin to heat reaction in the presence of a disproportionation catalyst. As the reaction conditions, the temperature is 100 to 300°C, preferably 150 to 290°C.

Examples of the disproportionation catalyst include supported catalysts such as palladium carbon, rhodium carbon and platinum carbon; metal powders such as nickel and platinum; iodides such as iodine and iron iodide. The amount of disproportionation catalyst to be used is usually 0.01 to 5 parts by weight, preferably 0.01 to 1 part by weight, per 100 parts by weight of natural rosin.

Polymerized rosin can be obtained, for example, by heating natural rosin in an organic solvent containing a catalyst such as sulfuric acid, hydrogen fluoride, aluminum chloride or titanium tetrachloride at 40 to 160° C. for 1 to 5 hours. Examples of organic solvents include toluene and xylene.

The α,β-unsaturated carboxylic acid-modified rosin refers to natural rosin to which α,β-unsaturated carboxylic acid is added.

Examples of α,β-unsaturated carboxylic acids include α,β-unsaturated dicarboxylic acids such as maleic acid, maleic anhydride and fumaric acid; α,β-unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid; and these may be used alone or in combination of two or more. The amount of α,β-unsaturated carboxylic acid to be used is usually about 1 to 30 parts by weight per 100 parts by weight of natural rosin.

The above-mentioned α,β-unsaturated carboxylic acid-modified rosin can be obtained, for example, by collectively mixing the natural rosin and the α,β-unsaturated carboxylic acid in a reaction vessel, heating and melting the reaction temperature to 190 to 230° C. It can be obtained by a method such as a Diels-Alder reaction for up to 3 hours.

A rosin ester is an esterified product of natural rosin and alcohol.

Examples of the alcohol include aliphatic monools such as stearyl alcohol and isostearyl alcohol;
ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol (1,2-propanediol), 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1 ,4-butanediol, 2,3-butanediol, 2-methyl-1,2-propanediol, 1,5-pentanediol, 2-methyl-2,3-butanediol, 1,6-hexanediol, 1 ,2-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2,3-dimethyl-2,3-butanediol, 2-ethyl-hexanediol, 1,2-octanediol , 1,2-decanediol, 2,2,4-trimethylpentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol;
Aliphatic triols such as glycerin, butanetriol, butanetriol, trimethylolethane, triethylolethane, trimethylolpropane;
Aliphatic tetraols such as diglycerin, erythritol, threitol, pentaerythritol;
Aliphatic pentaols such as arabinitol and xylitol;
Aliphatic hexaols such as sorbitol, mannitol, iditol, dipentaerythritol;
Aliphatic octanols such as tripentaerythritol and the like are included. These may be used alone or in combination of two or more.

A rosin ester can be obtained, for example, by subjecting a natural rosin and an alcohol to an esterification reaction, usually at a temperature of 200-350° C. for 6-20 hours. Moreover, the reaction can be carried out under normal pressure, under reduced pressure, or under increased pressure. As for the ratio of the amount of natural rosin and alcohol used, the equivalent ratio [OH _(eq) /COOH _(eq) ] of the former carboxyl group and the latter hydroxy group is usually about 0.2 to 1.5. , preferably about 0.4 to 1.2. Moreover, in the reaction, an esterification catalyst such as p-toluenesulfonic acid or various antioxidants may be used. Moreover, the above reaction may be carried out under a nitrogen stream.

Among these components (a1), natural rosin is preferred because it readily reacts with component (a2).

Component (a2) includes, for example, phenol, naphthol, alkylphenol, and arylphenol.

Examples of alkylphenols include cresol, n-butylphenol, isobutylphenol, t-butylphenol, n-pentylphenol, cyclohexylphenol, octylphenol, n-nonylphenol and the like. The alkylphenol means one having an alkyl group at least one of the ortho-position (o-), meta-position (m-), and para-position (p-) with respect to the phenolic hydroxyl group. Any one having a linear structure or branched structure of n-alkyl group, isoalkyl group, s-alkyl group, or t-alkyl group can be used. These may be used alone or in combination of two or more.

Among these components (a2), phenol and alkylphenol are preferred, and phenol is more preferred, because they readily react well with component (a1).

Component (a2) is preferably used in an amount of 50 to 200 parts by weight in terms of non-volatile content per 100 parts by weight of component (a1).

In addition, in order to obtain an ink composition that exhibits even better adhesion to plastic films, the reaction component includes an aliphatic polyol and/or an alicyclic polyol (a3) (hereinafter referred to as component (a3)). ) may be further included.

Examples of aliphatic polyols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol (1,2-propanediol), 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,2-propanediol, 1,5-pentanediol, 2-methyl-2,3-butanediol, 1,6-hexanediol, 1,2-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2,3-dimethyl-2,3-butanediol, 2-ethyl-hexane Diol, 1,2-octanediol, 1,2-decanediol, 2,2,4-trimethylpentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3 - aliphatic diols such as propanediol;
Alicyclic triols such as glycerin, butanetriol, trimethylolethane, triethylolethane, trimethylolpropane;
Aliphatic tetraols such as diglycerin, erythritol, threitol, pentaerythritol;
Aliphatic pentaols such as arabinitol and xylitol;
Aliphatic hexaols such as sorbitol, mannitol, iditol, dipentaerythritol;
Aliphatic octanols such as tripentaerythritol and the like are included. These may be used alone or in combination of two or more.

Examples of alicyclic polyols include 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,1-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1 ,4-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,2-cyclooctanediol, 1,5-cyclooctanediol, 5-norbornene-2,2-dimethanol, 5-norbornene-2,3-diol Methanol, norbornane-2,3-dimethanol, norbornane-2,5-dimethanol, 2,6-decahydronaphthalenedimethanol, 1,3-adamantanediol, 1,4-adamantanediol, 2,4-adamantanediol , tricyclodecanedimethanol;
Fats such as 1,2,3-cyclopentanetriol, 1,2,4-cyclopentanetriol, 1,2,3-cyclohexanetriol, 1,3,5-cyclohexanetriol and 1,2,3-cyclooctanetriol cyclic triols;
1,2,3,4-cyclopentanetetraol, 1,2,3,4-cyclohexanetetraol, 1,2,3,5-cyclohexanetetraol, 1,2,4,5-cyclohexanetetraol, 1 , 2,3,4-cyclooctane tetraol and 1,2,5,6-cyclooctane tetraol. These may be used alone or in combination of two or more.

Among these components (a3), aliphatic polyols are preferred, and aliphatic diols and aliphatic triols, from the viewpoint of suppressing gelation during the reaction and obtaining component (A) having a desired softening point and weight average molecular weight. , aliphatic tetraols are more preferred, and ethylene glycol, glycerin, trimethylolethane and trimethylolpropane are more preferred.

The amount of component (a3) used is generally 1.5 in terms of the ratio (OH/COOH) of the total number of hydroxyl group equivalents (OH) of component (a3) to the total number of carboxyl group equivalents (COOH) of the rosin resin. Below, it is preferably 0.5 to 1.2.

In addition, the component (A) may contain additives. Additives include, for example, dehydrating agents, crystal nucleating agents, plasticizers, fluidity improvers, weathering agents, antioxidants, ultraviolet absorbers, heat stabilizers, light stabilizers, and the like. These may be used singly or in combination of two or more. Moreover, the additive can be appropriately added before, during, or after the production of the component (A).

The content of the additive is preferably 10% by weight or less, more preferably 1% by weight or less, relative to 100% by weight of component (A).

The component (A) of the present invention is obtained by reacting components (a1) and (a2), optionally component (a3), and the above additives. The order of addition and method of addition are not particularly limited.

(A) As a manufacturing method of a component, the following are mentioned, for example.
(1) The adduct obtained by reacting components (a1) and (a2) at a temperature of about 130 to 200° C. for 4 to 10 hours in the presence of an acid catalyst, if necessary, is further treated at a temperature of 180 to 350° C. (2) If necessary, in the presence of an acid catalyst, components (a1) and (a2) are reacted at a temperature of about 130 to 200° C. for 4 to 10 hours. Add the component (a3) to the adduct and further react at a temperature of about 180 to 350° C. for about 2 to 8 hours (3) To the reaction product obtained by performing the production method described in (1), Add the a3) component and further react at a temperature of about 180 to 350° C. for about 2 to 8 hours.

In the production method described above, the reaction after obtaining the adducts of the components (a1) and (a2) may be carried out under reduced pressure. The reduced pressure condition is preferably about 0.1 to 10 kPa.

Examples of acid catalysts include inorganic acids such as sulfuric acid, hydrogen chloride and boron trifluoride; organic acids such as oxalic acid, p-toluenesulfonic acid, methanesulfonic acid and dodecylbenzenesulfonic acid; These may be used alone or in combination of two or more. The amount of acid catalyst used is preferably 0.01 to 1 part by weight per 100 parts by weight of component (a1).

Also, a base may be added after the reaction of components (a1) and (a2). Examples of bases include metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and calcium hydroxide; metal acetates such as sodium acetate, potassium acetate, magnesium acetate, calcium acetate, and zinc acetate; potassium carbonate; , sodium carbonate, potassium carbonate, and calcium carbonate; and amines such as triethylamine and triphenylamine. These may be used alone or in combination of two or more. The amount of base used is preferably 0.01 to 1 part by weight per 100 parts by weight of component (a1).

The physical properties of the obtained component (A) include, for example, the hydroxyl value of component (A), which dissolves in an organic solvent when preparing an ink composition, and has excellent adhesion to plastic films. , preferably 20 mgKOH/g or more, more preferably 60 to 250 mgKOH/g. The hydroxyl value here is a value measured by a method based on JIS K0070.

Moreover, solid, a solution, an emulsion, etc. are mentioned as a form of (A) component. Examples of the emulsifier, production method, and the like used in producing the emulsion include those described in JP-A-2009-242683.

The content of component (A) is preferably 0.1 to 5% by weight, preferably 0.1 to 3% by weight, based on 100% by weight of all components of the ink composition, from the viewpoint of excellent adhesion to plastic films. % is more preferred. The term "all components of the ink composition" means all components such as component (A), component (B) described below, pigments, organic solvents and additives. When the form of component (B) is a solution (solute + solvent), the solvent is also included in the component (the same shall apply hereinafter).

Component (B) is one or more resins selected from the group consisting of polyurethane-based resins, cellulose-based resins, rubber-based resins, polyamide-based resins, acrylic-based resins, and vinyl acetate-based resins. These may be used alone or in combination of two or more, and commercially available products may also be used.

Examples of polyurethane-based resins include reaction products of polyols and polyisocyanates, and reaction products of terminal isocyanate prepolymers obtained from the reaction and chain extenders. These may be used alone or in combination of two or more.

Specific reaction components, reaction conditions and the like include, for example, those described in JP-A-2012-153883, JP-A-2004-059894, JP-A-2010-053340, and the like.

Cellulose resins include, for example, nitrocellulose, cellulose acetate propionate, cellulose acetate butyrate, hydroxyalkylcellulose, carboxyalkylcellulose and the like. Examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group and n-hexyl group. These may be used alone or in combination of two or more.

Examples of rubber-based resins include chlorinated rubber and cyclized rubber. These may be used alone or in combination of two or more.

A polyamide-based resin is a polycondensate of polycarboxylic acid and polyamine. A thermoplastic polyamide resin soluble in an organic solvent, which will be described later, is particularly preferred.

Examples of polycarboxylic acids include adipic acid, sebacic acid, azelaic acid, phthalic anhydride, isophthalic acid, suberic acid, glutaric acid, fumaric acid, pimelic acid, oxalic acid, malonic acid, succinic acid, maleic acid, and terephthalic acid. , 1,4-cyclohexyldicarboxylic acid, trimellitic acid, dimer acid, hydrogenated dimer acid, polymerized fatty acid and the like. These may be used alone or in combination of two or more.

Here, the polymerized fatty acid is obtained by a cyclization reaction or the like of a fatty acid having an ethylenic double bond. includes. The fatty acid constituting the dimer acid or polymerized fatty acid includes those derived from natural oils such as soybean oil, palm oil, and rice bran oil, and those obtained from oleic acid, linolenic acid, and linoleic acid are preferable. .

Examples of polyamines include aliphatic polyamines such as ethylenediamine, propylenediamine, hexamethylenediamine, methylaminopropylamine, diethylenetriamine and triethylenetetramine; alicyclic polyamines such as cyclohexylenediamine and isophoronediamine; Polyamines include aromatic polyamines such as phenylenediamine and diaminodiphenylmethane. These may be used alone or in combination of two or more.

The ratio of the polycarboxylic acid to the polyamine used is (carboxylic acid group)/(amino group)=0.8 to 1.2 in terms of equivalent ratio of carboxylic acid group to amino group. As for the reaction conditions, it is preferable to carry out the reaction at 180 to 230° C. in the presence of an inert gas. Moreover, it is preferable to have fractionation equipment for the dehydration reaction. Moreover, you may perform the said reaction under reduced pressure.

Examples of acrylic resins include those obtained by polymerizing a monomer having an ethylenic double bond in the presence of a polymerization initiator. Examples of monomers having an ethylenic double bond include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, n-hexyl (meth) acrylate, n - alkyl (meth)acrylates such as octyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate; dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, di-n-propylaminoethyl (meth)acrylate; Alkylaminoalkyl (meth)acrylates such as acrylates, dimethylamino n-propyl (meth)acrylate, diethylamino n-propyl (meth)acrylate, di-n-propylamino n-propyl (meth)acrylate; styrene, α-methylstyrene, etc. styrenes; hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; ) Unsaturated carboxylic acids such as acrylic acid, maleic acid, fumaric acid and itaconic acid. These may be used alone or in combination of two or more.

Vinyl acetate resins include, for example, vinyl acetate copolymers, vinyl chloride-vinyl acetate copolymers, ethylene-vinyl acetate copolymers, and the like. These may be used alone or in combination of two or more.

The form of component (B) includes solid, solution, emulsion and the like.

The content ratio of component (A) and component (B) is, in terms of non-volatile content weight, (A)/(B )=1/99 to 60/40, more preferably 2/98 to 50/50.

The ink composition of the present invention may further contain a pigment.

Examples of pigments include organic pigments and inorganic pigments. These may be used alone or in combination of two or more.

Organic pigments include azo, diazo, phthalocyanine, anthraquinone, perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, thioindigo, quinophthalone, azomethineazo, dict Examples include pyrrolopyrrole-based, isoindoline-based, carbon black (for example, furnace black, thermal lamp black, acetylene black, channel black, etc.).

Examples of inorganic pigments include magnesium oxide, titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, red iron oxide, alumina, and mica (mica). Titanium oxide whose surface is coated with silica or alumina can also be used.

The pigment content is preferably 2 to 40% by weight, more preferably 5 to 35% by weight, based on 100% by weight of all components of the ink composition.

Moreover, the ink composition of the present invention may further contain an organic solvent.

Examples of organic solvents include esters such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, and isobutyl acetate; alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, and n-butanol. ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene Glycol ethers such as glycol mono-n-propyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and diethylene glycol diethyl ether; aromatic hydrocarbons such as toluene and xylene; These may be used alone or in combination of two or more.

The ink composition of the present invention may further contain additives other than components (A), (B), pigments and organic solvents.

Examples of additives include pigment dispersants, surfactants, waxes, antistatic agents, and plasticizers. These may be used alone or in combination of two or more.

The gravure ink of the present invention contains an ink composition.

The ink composition and the gravure ink are prepared by kneading the components (A) and (B) and, if necessary, pigments, organic solvents and additives using a high-speed mixer, roll mill, ball mill, attritor, sand mill or the like. and prepared to have appropriate ink constants. The order of addition of the ingredients, kneading time, etc. may also be adjusted as appropriate.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to them. All "parts" and "%" are by weight unless otherwise specified.

(acid value)
The acid value of component (A) was measured according to JIS K5601.

(hydroxyl value)
The hydroxyl value of component (A) was measured according to JIS K0070.

Production example 1
After charging 100.0 parts of gum rosin and 150.0 parts of phenol into a reactor equipped with a stirrer, a condenser, a thermometer, and a nitrogen inlet tube/steam inlet tube, the temperature was raised to 100° C., and 96% sulfuric acid was added to 2.0 parts. One part was charged and reacted for 4 hours under a nitrogen gas stream. After adding 3.0 parts of slaked lime, the temperature was raised to 280° C. under a reduced pressure of 10 kPa, and the reaction was carried out at the same temperature for 1 hour. Then return to normal pressure,
16.4 parts of trimethylolpropane was added and reacted at 200 to 280° C. to obtain rosin phenol (A-1) having an acid value of 12.4 mgKOH/g and a hydroxyl value of 99 mgKOH/g.

Production example 2
After charging 100.0 parts of gum rosin and 150.0 parts of phenol in the same reaction vessel as in Production Example 1, the temperature was raised to 100° C., 2.1 parts of 96% sulfuric acid was charged, and the mixture was reacted for 4 hours under nitrogen gas flow. rice field. After adding 3.0 parts of slaked lime, the temperature was raised to 280° C. under a reduced pressure of 10 kPa, and the reaction was carried out at the same temperature for 1 hour. Thereafter, the pressure was returned to normal pressure, 8.8 parts of glycerin was added, and the mixture was reacted in the range of 200 to 280°C to obtain rosin phenol (A-2) having an acid value of 26.5 mgKOH/g and a hydroxyl value of 83 mgKOH/g. rice field.

Production example 3
After charging 100.0 parts of gum rosin and 150.0 parts of phenol in the same reaction vessel as in Production Example 1, the temperature was raised to 100° C., 2.1 parts of 96% sulfuric acid was charged, and the mixture was reacted for 4 hours under nitrogen gas flow. rice field. After adding 3.0 parts of slaked lime, the temperature was raised to 280° C. under a reduced pressure of 10 kPa, and the reaction was carried out at the same temperature for 1 hour. Then, the pressure was returned to normal pressure, 5.4 parts of glycerin was added, and the mixture was reacted in the range of 200 to 280°C to obtain rosin phenol (A-3) having an acid value of 31.9 mgKOH/g and a hydroxyl value of 48 mgKOH/g. rice field.

Production example 4
After charging 100.0 parts of gum rosin and 150.0 parts of phenol in the same reaction vessel as in Production Example 1, the temperature was raised to 100° C., 2.1 parts of 96% sulfuric acid was charged, and the mixture was reacted for 4 hours under nitrogen gas flow. rice field. After adding 3.0 parts of slaked lime, the temperature was raised to 280° C. under a reduced pressure of 10 kPa, and the reaction was carried out at the same temperature for 1 hour. After that, the pressure is returned to normal pressure, 11.4 parts of ethylene glycol is added, and the reaction is carried out in the range of 200 to 280° C. to obtain rosin phenol (A-4) having an acid value of 16.0 mgKOH/g and a hydroxyl value of 74 mgKOH/g. Obtained.

Production example 5
After charging 100.0 parts of gum rosin and 150.0 parts of phenol in the same reaction vessel as in Production Example 1, the temperature was raised to 100° C., 2.1 parts of 96% sulfuric acid was charged, and the mixture was reacted for 4 hours under nitrogen gas flow. rice field. After adding 3.0 parts of slaked lime, the temperature was raised to 280° C. under a reduced pressure of 10 kPa, and the reaction was carried out at the same temperature for 1 hour. Then, the pressure is returned to normal pressure, 5.8 parts of pentaerythritol is added, and the mixture is reacted in the range of 200 to 280° C. to obtain rosin phenol (A-5) having an acid value of 20.2 mgKOH/g and a hydroxyl value of 52 mgKOH/g. Obtained.

Production example 6
After charging 100.0 parts of gum rosin and 150.0 parts of phenol in the same apparatus as in Production Example 1, the temperature was raised to 100° C., 2.1 parts of 96% sulfuric acid was charged, and the mixture was reacted for 4 hours under nitrogen gas flow. . After adding 3.0 parts of slaked lime, the temperature was raised to 280° C. under reduced pressure of 10 kPa, and reacted at the same temperature for 4 hours to obtain rosin phenol (A-6) having an acid value of 50 mgKOH/g and a hydroxyl value of 23 mgKOH/g. Obtained.

Example 1
80.0 parts of glass beads in a 225 ml mayonnaise bottle, 3.6 parts of component (A-1) (non-volatile content), polyurethane resin (trade name: "TSP-3477", concentration of non-volatile content: 30) as component (B) %, manufactured by Arakawa Chemical Industries, Ltd.) 5.4 parts (non-volatile matter), 30 parts of titanium oxide as a pigment, 48.4 parts of a mixed solution of isopropyl alcohol:ethyl acetate = 1:2 (weight ratio) as an organic solvent The parts were charged and kneaded in a paint shaker for 60 minutes to obtain an ink composition.

Examples 2-13, Comparative Examples 1-3
Ink compositions were obtained in the same manner as in Example 1 except that the types and amounts of the components (A) and (B) shown in Table 1 were changed. The ink composition of Comparative Example 3 was not sufficiently dispersed, so the following items were not evaluated.

The ink compositions of Examples and Comparative Examples were used as gravure inks as they were, and the following evaluations were carried out.

<Adhesion>
Using a bar coater, the ink composition of each example and comparative example was applied onto an oriented polypropylene film (OPP film), dried for 10 seconds with a dryer, and then coated with the ink after 1 hour and 24 hours. Cellotape (registered trademark) was pressed onto the surface and the condition of the remaining ink was observed when the tape was peeled off.
(Evaluation criteria)
5. 4. The peeled area of the dry film was less than 5%. 3. The peeling area of the dry film was 5% or more and less than 20%. 2. The peeling area of the dry film was 20% or more and less than 50%. 1. The peeling area of the dry film was 50% or more and less than 80%. The peeling area of the dry film was 80% or more

The symbols in Table 1 mean the following components.
A-1: Rosin phenol resin of Production Example 1 A-2: Rosin phenol resin of Production Example 2 A-3: Rosin phenol resin of Production Example 3 A-4: Rosin phenol resin of Production Example 4 A -5: Rosin phenol resin of Production Example 5 A-6: Rosin phenol resin of Production Example 6 B-1: Polyurethane resin (trade name: "TSP-3477", manufactured by Arakawa Chemical Industries, Ltd.)
・ B-2: Vinyl chloride-vinyl acetate copolymer (trade name: “Solbin A”, manufactured by Nissin Chemical Industry Co., Ltd.)

Claims (6)

Rosin phenolic resin (A), which is a product of reaction components containing rosins (a1) and phenols (a2), as well as polyurethane-based resins, cellulose-based resins, rubber-based resins, polyamide-based resins, acrylic-based resins and acetic acid An ink composition containing one or more resins (B) selected from the group consisting of vinyl resins. 2. The ink composition according to claim 1, wherein component (a2) is phenol and/or alkylphenol. The ink composition according to claim 1 or 2, wherein the reactive component further contains an aliphatic polyol and/or an alicyclic polyol (a3). 3. The ink composition according to claim 1, wherein the content ratio of component (A) to component (B) is (A)/(B)=1/99 to 60/40 in terms of nonvolatile weight. 3. The ink composition according to claim 1, further comprising a pigment and an organic solvent. A gravure ink comprising the ink composition according to claim 1 or 2.