WO2017099146A1 - Resin for printing ink, varnish for printing ink, printing ink, and process for producing resin for printing ink - Google Patents

Abstract

Provided is a novel resin for printing inks which retains the properties of rosin-modified phenolic resins for use in conventional offset printing inks and which is inexpensive. The resin is a rosin-modified resin obtained by reacting at least: (A) either crude and/or distilled tall oil or a mixture comprising crude and/or distilled tall oil and a rosin; and (B) a polyhydric alcohol.

Description

Printing ink resin, printing ink varnish, printing ink and method for producing printing ink resin

The present invention relates to a resin for printing ink, a varnish for printing ink, a printing ink and a method for producing a resin for printing ink. The printing ink resin obtained by the present invention is particularly useful as an offset printing ink resin. Moreover, it can be used suitably also for newspaper ink, letterpress printing ink, and gravure printing ink.

Conventionally, rosin-modified phenolic resins that can impart excellent printability to ink have been used as offset printing ink resins. Normally, offset printing ink is prepared by heating and mixing the rosin-modified phenolic resin, drying oil or semi-drying oil, solvent or fatty acid ester, and gelling agent as necessary, and uniforming the ink varnish. After the preparation, a pigment is further mixed, and a product is produced through a kneading process and a preparation process.

Specific printing inks include, for example, a resole resin having an average number of phenols of 6 to 10, a rosin and / or a condensation product of rosin and unsaturated carboxylic acid, and a reaction product of a polyhydric alcohol. A printing ink containing a varnish containing a rosin-modified phenol resin having a weight average molecular weight of 40,000 to 200,000 has been proposed (Patent Document 1).

However, since such rosin-modified phenolic resins use formaldehyde and alkylphenols as the main raw materials for the resole resins used, they have problems in terms of environment and work hygiene. Therefore, in recent years, development of a resin for offset printing ink that does not use formaldehyde and alkylphenol has been promoted (for example, Patent Document 2).

On the other hand, in recent years, the digitization of information has become common, and the demand for printed matter and printing ink has decreased. Under such circumstances, requirements for raw materials constituting printing inks are changing, and there is one price.

As a technique for solving the problem, for example, a varnish for printing ink obtained from rosins, fatty acids or fatty acid esters, resol type phenol resins, and polyhydric alcohols has been developed (for example, Patent Document 3).

JP 2002-322411 A JP 2000-159867 A JP 2005-154703 A

However, in the varnish for printing ink using the fatty acid etc. disclosed in Patent Document 3, it is difficult to achieve both the ink performance and the cost of the obtained ink.

Accordingly, an object of the present invention is to provide a novel printing ink resin that is inexpensive while maintaining the characteristics of a rosin-modified phenolic resin used in conventional offset printing inks.

In order to achieve the above object, the rosin-modified resin of the present invention comprises:
at least

(A) crude tall oil and / or distilled tall oil, or a mixture comprising crude tall oil and / or distilled tall oil and rosin;

(B) a polyhydric alcohol;
It is obtained by reacting.

It is possible to provide a new inexpensive printing ink resin while maintaining the characteristics of the rosin-modified phenolic resin used in conventional offset printing inks.

The rosin-modified resin of the present invention, which is a printing ink resin, will be described.

The “rosin-modified resin” in the present invention means at least (A) crude tall oil and / or distilled tall oil, or a mixture containing crude tall oil and / or distilled tall oil and rosin, and (B) a polyhydric alcohol. Is a rosin-modified resin obtained by reacting The “rosin-modified polyester resin” can be obtained by esterifying the component (A) using the component (B).

The rosin-modified resin in the present invention may be a rosin-modified resin obtained by adding (C) a resol type phenol resin and reacting in addition to the components (A) and (B). In this case, the obtained rosin-modified resin is “rosin-modified phenol resin”. (A) Component crude tall oil and / or distilled tall oil, or mixture of crude tall oil and / or distilled tall oil and rosin is modified with aldehyde and phenols (B) component resole type phenolic resin To do. The resulting resin is introduced with a cross-linked structure, and printing inks made using this resin have preferred characteristic values.

Hereinafter, each of “rosin-modified polyester resin” and “rosin-modified phenol resin” in the present invention will be described in detail.

(Rosin-modified polyester resin)
The term “rosin-modified polyester resin” means (A) crude tall oil and / or distilled tall oil, or a mixture containing crude tall oil and / or distilled tall oil and rosin, and (B) polyhydric alcohol. It means a resin obtained by esterification.

((Component A))

As the component (A), at least one of crude tall oil and distilled tall oil can be used. Moreover, you may use the mixture containing at least 1 type of crude tall oil and distilled tall oil, and a rosin as (A) component. Crude tall oil and distilled tall oil may be used alone or in combination.

Here, the crude tall oil is recovered as a by-product in a kraft method in which chemicals such as sodium hydroxide are added to wood chips and decomposed under high temperature and high pressure to take out pulp fibers. It can be obtained by neutralizing a black liquor obtained by concentrating a liquid containing a mixture of lignin and resin components and chemicals that has hardened pulp fibers with an acid such as sulfuric acid. That is, tall rosin is obtained by rectifying crude tall oil. Distilled tall oil is recovered as a by-product when rectifying crude tall oil and separating tall rosin and tall fatty acids.

The type of wood that is the raw material for crude tall oil is not particularly limited, but is preferably pine-derived crude tall oil. The type of pine is not particularly limited, and examples include horse ear pine, Tuda pine, and Eliotti pine.

When the component (A) is a mixture, the mixture can contain rosin. Examples of rosin include tall rosin, gum rosin, and wood rosin. Examples of rosin derivatives include polymerized rosin, acrylated rosin, hydrogenated rosin, and disproportionated rosin. These rosins may be used alone or in combination of two or more.

(A) The mixture of component (A) can contain rubber and petroleum resin as required. Regardless of the type, any publicly known materials can be used, and the softening point can be easily adjusted by using the resin, and a resin having a desired softening point can be obtained.

Examples of the rubber include natural rubber, isoprene rubber, butadiene rubber, natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, acrylonitrile butadiene rubber, chloroprene rubber, butyl rubber, and ethylene propylene rubber. These rubbers may be used alone or in combination of two or more.

Examples of petroleum resins include aliphatic polymers, aromatic polymers, alicyclic polymers, and the like. These petroleum resins may be used alone or in combination of two or more.

The total content of crude tall oil and distilled tall oil in the mixture of component (A) is usually 50% by weight or less, and preferably 30% by weight or less. Since crude tall oil and distilled tall oil contain fatty acids (hereinafter, fatty acids contained in tall oil may be simply referred to as “fatty acids”), resins obtained from them as raw materials have low softening points. It tends to be. If the total content of crude tall oil and distilled tall oil increases, the softening point of the resulting resin may be below 120 ° C., so the total content of crude tall oil and distilled tall oil is usually 50% by weight. Or less, preferably 30% by weight or less. In addition, since crude tall oil and distilled tall oil contain impurities, if the total content of crude tall oil and distilled tall oil increases, the reaction becomes complicated and the physical properties of the resulting rosin-modified resin must be adjusted. May be difficult.

As the crude tall oil and / or distilled tall oil in component (A), those obtained by polymerizing crude tall oil (polymerized crude tall oil) and those obtained by polymerizing distilled tall oil (polymerized distilled tall oil) are used. You may do it. Since the softening point of the resulting resin is improved by using a raw material obtained by polymerizing crude tall oil and / or distilled tall oil, the proportion of crude tall oil and distilled tall oil used as a raw material may be increased. it can. Polymerized crude tall oil and polymerized distilled tall oil are mainly obtained by polymerizing rosin and fatty acids contained in crude tall oil and distilled tall oil.

When polymerized crude tall oil and / or polymerized distilled tall oil is used, the total amount of polymerized crude tall oil and polymerized distilled tall oil is determined by the following formula: In general, it can be contained in an amount of 90% by weight or less, preferably 80% by weight or less, and more preferably 70% by weight or less, based on the total amount of the mixture. Even when polymerized crude tall oil or polymerized distilled tall oil is used, if these are excessively contained, the softening point may be lowered. Although there is no particular lower limit of the content of the polymerized crude tall oil and / or polymerized distilled tall oil, it is usually good up to 30% by weight based on the mixture to add unpolymerized crude tall oil or distilled tall oil. Resin characteristics can be obtained. Therefore, it is effective to use a polymerized crude tall oil or distilled tall oil when the crude tall oil or distilled tall oil is introduced in an amount exceeding 30% by weight with respect to the mixture. That is, the total amount of the polymerized crude tall oil and the polymerized distilled tall oil is 30% by weight or more and 90% by weight or less based on the total amount of the polymerized crude tall oil and / or the mixture containing the polymerized crude tall oil and rosin. It is preferable that In addition, when using for printing ink, the preferable softening point of resin is 100 degreeC or more normally, Preferably it is 120 degreeC or more and 200 degrees C or less. This is because when the softening point is 120 ° C. or higher, the dryness and offset property of the printed matter can be kept good. Further, considering the solubility in the ink solvent, it is appropriate that the softening point of the resin is 200 ° C. or less. Of course, even if the ratio of the polymerized crude tall oil and / or polymerized distilled tall oil to the mixture is 30% by weight or less, the polymerized crude tall oil or polymerized distilled tall oil is used. It is effective to do.

Polymerization of crude tall oil and distilled tall oil is usually carried out at 100 to 200 ° C., preferably 130 to 180 ° C. in an atmosphere of an inert gas such as nitrogen or argon. The polymerization time is usually 1 to 24 hours, although it depends on the crude tall oil used. The polymerization in the present specification is a change in which two or more monomer molecules are bonded to form a compound having an integral multiple of molecular weight, and includes a phenomenon of oligomerization such as dimerization and trimerization.

Polymerization of crude tall oil and distilled tall oil is preferably performed in the presence of a catalyst. Catalysts include formic acid, acetic acid, phosphoric acid, sulfuric acid, phenolsulfonic acid, paratoluenesulfonic acid, methanesulfonic acid, sulfosuccinic acid, 5-sulfosalicylic acid, 4-sulfophthalic acid, 5-sulfoisophthalic acid, and other carboxylated sulfones Pendants such as acids, arylsulfonic acids substituted with alkyl groups, solid acids having sulfonic acid groups, fluorosulfonic acids, trifluoromethanesulfonic acids, polystyrene sulfonic acids, polyvinyl sulfonic acids, or fluorinated polymers having sulfonic acid type functional groups Polymer hydrogen fluoride having sulfonic acid group, clay, zinc chloride, aluminum chloride, titanium tetrachloride, boron trifluoride and boron trifluoride phenol complex, boron trifluoride dimethyl ether complex or boron trifluoride diethyl ether complex, etc. No trifluoride Containing derivatives. The catalyst can be used alone or in combination of two or more.

Among the above-mentioned catalysts, a more preferable catalyst is an acid catalyst, more preferably a sulfonic acid derivative, still more preferably 4-sulfophthalic acid or trifluoromethanesulfonic acid. The catalyst is preferably used in an amount of 0.01 to 5% by weight based on the crude tall oil or distilled tall oil. In addition, in the case of polymerization after mixing crude tall oil and distilled tall oil, the amount of the catalyst used is within the range of 0.01 wt% to 5 wt% with respect to the total of the crude tall oil and distilled tall oil. It is preferable to use it. The catalyst may remain in the final product or may optionally be neutralized with an alkali such as potassium hydroxide or amine.

When a mixture of polymerized crude tall oil and / or distilled tall oil and rosin is used as the component (A), the polymerized crude tall oil and / or distilled tall oil is mixed with rosin at the predetermined ratio described above. Prepare a mixture. When preparing the mixture, mixing at an appropriate viscosity is easier to mix, so mixing is performed under heated conditions of 100 to 300 ° C, preferably 150 to 250 ° C.

In the polymerization of crude tall oil or distilled tall oil, the polymerization may be carried out after mixing crude tall oil and / or distilled tall oil and rosin. If the polymerization is carried out after mixing crude tall oil and / or distilled tall oil and rosin, it is preferable in terms of the process.

Examples of rosins that can be used as the component (A) include tall rosin, gum rosin, and wood rosin. In addition, rosin derivatives may be used, and specific examples include polymerized rosin, acrylated rosin, hydrogenated rosin, disproportionated rosin and the like. These rosins may be used alone or in combination of two or more. In addition, the rosin that can be used as the component (A) may be simply referred to as “rosins”.

Also, rubber and petroleum resin can be mixed into the mixture as necessary. By mixing rubber and petroleum resin, it is easy to adjust the softening point of the resulting resin, and a resin having a desired softening point is obtained. The types of rubbers and petroleum resins that can be mixed are not particularly limited, and any publicly known and publicly available materials can be used. Specific examples of the rubber include natural rubber, isoprene rubber, butadiene rubber, natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, acrylonitrile butadiene rubber, chloroprene rubber, butyl rubber, and ethylene propylene rubber. These rubbers may be used alone or in combination of two or more.

Specific examples of petroleum resins include aliphatic polymers, aromatic polymers, and alicyclic polymers. These petroleum resins may be used alone or in combination of two or more.

Prior to reacting with the component (B), the mixture as the component (A) is described as at least one of α, β-unsaturated carboxylic acid and its anhydride (hereinafter simply referred to as “α, β-unsaturated carboxylic acids”). May be modified). That is, component (A) and α, β-unsaturated carboxylic acid undergo an addition reaction (Alder ene reaction or Diels-Alder reaction), and α, β-unsaturated carboxylic acid, rosin and / or (in tall oil) Of adducts of fatty acids. Since this adduct has at least two carboxyl groups in the molecule, it forms an ester bond with the polyhydric alcohol as the component (B) to increase the molecular weight. As described above, a resin having a desired viscoelasticity can be obtained by increasing the molecular weight of the α, β-unsaturated carboxylic acid in advance.

Examples of the α, β-unsaturated carboxylic acids include a chain α, β-unsaturated monocarboxylic acid having 3 to 5 carbon atoms or an anhydride thereof, and a chain α having 3 to 5 carbon atoms. , Β-unsaturated dicarboxylic acid or its anhydride, aromatic α, β-unsaturated carboxylic acid and the like. Specific examples include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, crotonic acid, and cinnamic acid.

Moreover, a metal compound may be used as a crosslinking agent as necessary. Specifically, metal compounds such as hydroxides and oxides such as lithium, sodium, potassium, calcium, zinc, magnesium, aluminum, cobalt, copper, lead, and manganese may be used as the crosslinking agent. In this case, metal ions derived from the metal compound crosslink carboxyl groups (—COOH) present in the resin raw material, and increase the molecular weight of the resulting resin. More specifically, at least two molecules selected from the group consisting of fatty acids, rosin, α, β-unsaturated carboxylic acids, and the above adducts in the mixture are exchanged via metal ions derived from metal compounds. A crosslinked body having a crosslinked structure is formed.

In the rosin-modified resin according to this embodiment, unreacted rosins; unreacted fatty acids; α, β-unsaturated carboxylic acids; reaction products of rosins and α, β-unsaturated carboxylic acids; fatty acids and α, The compound selected from the group consisting of reactants of β-unsaturated carboxylic acids preferably includes a crosslinked product formed by crosslinking via a metal ion derived from a metal compound. Specific examples of the crosslinked body include crosslinked bodies as shown in the following (I) to (X).

(I) A crosslinked product formed by crosslinking an unreacted fatty acid and a reaction product of a rosin and an α, β-unsaturated carboxylic acid via a metal ion.

(II) A crosslinked product formed by crosslinking an unreacted fatty acid with a reaction product of a fatty acid and an α, β-unsaturated carboxylic acid via a metal ion.

(III) A crosslinked product formed by crosslinking an unreacted fatty acid and an unreacted rosin via a metal ion.

(IV) A crosslinked product formed by crosslinking an unreacted fatty acid and an α, β-unsaturated carboxylic acid via a metal ion.

(V) A crosslinked product formed by crosslinking an unreacted rosin and a reaction product of rosins and α, β-unsaturated carboxylic acids via metal ions.

(VI) A crosslinked product formed by crosslinking an unreacted rosin and a reaction product of a fatty acid and an α, β-unsaturated carboxylic acid via a metal ion.

(VII) A crosslinked product formed by crosslinking an unreacted rosin and an α, β-unsaturated carboxylic acid via a metal ion.

(VIII) A crosslinked product formed by crosslinking α, β-unsaturated carboxylic acids with a reaction product of rosin and α, β-unsaturated carboxylic acids via a metal ion.

(IX) A crosslinked product formed by crosslinking α, β-unsaturated carboxylic acids with a reaction product of fatty acids and α, β-unsaturated carboxylic acids via metal ions.

(X) A crosslinked product formed by crosslinking a reaction product of rosins and α, β-unsaturated carboxylic acids with a reaction product of fatty acids and α, β-unsaturated carboxylic acids via metal ions.

As described above, the molecular weight of the resulting resin can be increased by cross-linking carboxyl groups present in the resin raw material via metal ions derived from the metal compound. As a result, the drying property and misting resistance of the ink are improved. Moreover, by containing a specific metal compound, when preparing an ink, affinity with a pigment can be improved and dispersibility can be improved.

((B component))
The rosin-modified resin according to this embodiment can be obtained by esterifying the above-described component (A) with the polyhydric alcohol (polyol) that is the component (B). In this case, for example, if many carboxyl groups remain in the resin, the ink tends to be emulsified in printing with water. Examples of the carboxyl group present in the resin raw material include a rosin in the mixture, a carboxyl group derived from a fatty acid, a carboxyl group derived from an α, β-unsaturated carboxylic acid or an anhydride thereof.

The polyhydric alcohol is an alcohol having a plurality of hydroxides in one molecule, and the kind thereof is not particularly limited in the present invention. Specific examples of the polyhydric alcohol include, for example, ethylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, and 1,6-hexanediol as the dihydric alcohol. Examples of the trihydric alcohol include glycerin, trimethylolpropane, trimethylolethane, triethylolethane, 3-methylpentane-1,3,5-triol, and 1,2,4-butanetriol. Examples of the tetrahydric alcohol include pentaerythritol, diglycerin, sorbitan, and mannitan. Among these, it is preferable to use a trihydric or higher polyhydric alcohol from the viewpoint that the high molecular weight of the resin is easy and the viscoelasticity necessary for the ink is easily obtained. In addition, a polyhydric alcohol may be used independently and may be used in combination of 2 or more types.

The (B) component polyhydric alcohol is preferably reacted with the (A) component at a ratio of preferably 0.5 to 2 equivalents with respect to 1 equivalent of the carboxyl group present in the resin raw material. By reacting the (A) component with the polyhydric alcohol of the (B) component at the above ratio, a resin that imparts the desired viscoelasticity necessary for the ink is more easily obtained. Furthermore, the obtained resin has better solubility in a solvent used in the production of ink, and the ink is less likely to be emulsified even in printing with water.

(Method for producing rosin-modified polyester resin)

The esterification reaction between the component (A) and the component (B) is not particularly limited as long as the esterification reaction proceeds, but is usually performed in the range of 200 ° C to 350 ° C.

In the esterification reaction, a known and publicly used esterification catalyst may be used as necessary. Examples of the esterification catalyst include metal catalysts such as acid catalysts such as Bronsted acid and Lewis acid.

Further, if necessary, esterification may be carried out under a disproportionation catalyst. Examples of the disproportionation catalyst include organic sulfur compounds, such as 4,4′-bis (phenol) sulfide, 4,4′-bis (phenol) sulfoxide, and 4,4′-bis (phenol) sulfone. 4,4'-bis (phenol) thiolsulfinate, 4,4'-bis (phenol) thiolsulfonate, 2,2'-bis (p-cresol) sulfide, 2,2'-bis (p -Cresol) sulfoxide, 2,2'-bis (p-cresol) sulfone, 2,2'-bis (pt-butylphenol) sulfide, 2,2-bis (pt-butylphenol) sulfoxide, 2,2 '-Bis (pt-butylphenol) sulfone, 4,4'-bis (6-tert-butylmetacresol) sulfide, 4,4'-bis (6-tert-butyl) Tacresol) sulfoxide, 4,4'-bis (6-t-butylmetacresol) sulfide, 4,4'-bis (6-t-butylorthocresol) sulfoxide, 4,4'-bis (6-t- Butyl orthocresol) sulfone, 4,4'-bis (6-t-butyl orthocresol) sulfone, 4,4'-bis (resorcinol) sulfide, 4,4'-bis (resorcinol) sulfoxide, 4,4'- Bis (resorcinol) sulfone, 1,1'-bis (β-naphthol) sulfide, 1,1'-bis (β-naphthol) sulfoxide, 1,1'-bis (β-naphthol) sulfone, 4,4'- Bis (α-naphthol) sulfide, 4,4′-bis (α-naphthol) sulfoxide, 4,4′-bis (α-naphthol) sulfone, t Amyl phenol disulfide oligomers, nonylphenol disulfide oligomer, such as police Gandolfo sulfoxide obtained by reacting with thionyl chloride and p- cresol.

Among these organic sulfur compounds, it is preferable to use a compound in which a hydroxyl group bonded to a benzene ring is sterically hindered. Specifically, 4,4′-bis (6-tert-butylmetacresol) sulfide 4,4'-bis (phenol) sulfide, 2,2'-bis (p-cresol) sulfide, 2,2'-bis (pt-butylphenol) sulfide, 4,4'-bis (resorcinol) sulfide A sulfide compound selected from 4,4'-bis (α-naphthol) sulfide, t-amylphenol disulfide oligomers, and nonylphenol disulfide oligomers is preferred.

By performing the esterification reaction in the presence of the above organic sulfur compound, disproportionation of conjugated double bonds such as abietic acid of rosin in the mixture occurs, and structurally stable dehydroabietic acid and dihydroabietic acid are produced. Accumulated. As a result, a rosin-modified polyester resin excellent in oxidation stability with time is obtained, and the storage stability of the varnish containing the resin is improved.

Note that the esterification reaction is completed after confirming the acid value, softening point, viscosity, solubility, etc. of the obtained resin and reaching the predetermined value.

The rosin-modified polyester resin obtained by the esterification reaction can be suitably used for components such as printing ink. The rosin-modified ester polyester resin according to this embodiment preferably has a softening point of 120 ° C. or higher, more preferably about 130 to 200 ° C. The acid value is preferably about 10 to 40 KOHmg / g.

In particular, the rosin-modified polyester resin according to this embodiment can be suitably used as a component of a resin for offset printing ink, and in addition to the rosin-modified polyester resin, shellac, gilsonite, Other ink resins such as alkyd resins and rosin-modified phenol resins may be contained.

(Rosin modified phenolic resin)
Next, the “rosin-modified phenolic resin” according to this embodiment will be described. “Rosin-modified phenolic resin” means, as a raw material, (A) crude tall oil and / or distilled tall oil, or a mixture containing crude tall oil and / or distilled tall oil and rosin, and (B) polyhydric alcohol. (C) A resin obtained by reacting these using a resol type phenol resin.

((Component A))
The crude tall oil and / or distilled tall oil of component (A) according to this embodiment, or the mixture of crude tall oil and / or distilled tall oil and rosin is obtained from aldehyde, phenols, etc. It is modified with resole type phenolic resin. Therefore, the obtained resin has a preferable characteristic value with a crosslinked structure introduced therein.

The crude tall oil and / or distilled tall oil of component (A) contained in the rosin-modified phenolic resin, or a mixture of crude tall oil and / or distilled tall oil and rosin is the same type as the rosin-modified polyester. it can.

In the component (A), the total amount may be crude tall oil and / or distilled tall oil, but is preferably 50% by weight or less. Since crude tall oil and distilled tall oil contain fatty acids (hereinafter, fatty acids contained in tall oil may be simply referred to as “fatty acids”), resins obtained from them as raw materials have low softening points. It tends to be. If the total content of crude tall oil and distilled tall oil increases, the softening point of the resulting resin may be below 120 ° C., so the total content of crude tall oil and distilled tall oil is usually 50% by weight. It is as follows.

In the rosin-modified phenolic resin according to this embodiment, as in the rosin-modified polyester resin described above, as component (A), a polymerized crude tall oil and / or a polymerized distilled tall oil, or a polymerized crude toll Oils and / or mixtures of polymerized distilled tall oil and rosin may be used. In this case, considering the raw material cost, it is preferable to use the total amount of the polymerized crude tall oil and / or polymerized distilled tall oil as the component (A). However, in order to finely adjust the properties of the resin obtained, a mixture containing the above-mentioned rosins may be used as the component (A).

When the above mixture is used as the component (A), the content of the polymerized crude tall oil and / or polymerized distilled tall oil and the polymerized crude tall oil and / or polymerized distilled tall oil in the rosin mixture is From the viewpoint of raw material costs, it is preferably 70% by weight or more, more preferably 90% by weight or more, and still more preferably no rosin (100% by weight). On the other hand, in consideration of the properties of the obtained resin, the content of the polymerized crude tall oil and / or polymerized distilled tall oil is preferably 50% by weight or more and 90% by weight or less, more preferably 70% by weight. Above 90% by weight. Therefore, the content of the polymerized crude tall oil and / or polymerized distilled tall oil is preferably 50% by weight or more and 100% by weight or less from the viewpoint of achieving both the raw material costs and the properties of the obtained resin.

((B component))
The B component polyhydric alcohol that can be used in the rosin-modified phenolic resin according to this embodiment can be the same as the rosin-modified polyester resin described above.
The amount of polyols used in the production of the rosin-modified phenol resin is not particularly limited, but it is usually sufficient to add from 0.3 equivalents to an excess amount with respect to 1 equivalent of carboxyl group, more preferably 0.5. To 1.5 equivalents, more preferably 0.7 to 1.2 equivalents.

((C component))
As resol type phenol resin, phenols (P) and formaldehyde (F) are subjected to addition condensation in the presence of alkali catalysts such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, lithium hydroxide, triethylamine. Various known condensates obtained by the above are mentioned. In this case, of course, the condensate obtained by neutralizing and washing with water can be used if necessary. When the phenols (P) and formaldehyde (F) are reacted, the molar ratio of F / P (molar ratio) is usually 1 to 3. The phenols are preferably phenols having a C ₁ to C ₂₀ alkyl group, more preferably phenols having a C ₁ to C ₁₀ alkyl group. Specific examples thereof include carboxylic acid, cresols, amylphenol. Bisphenol-A, p-butylphenol, p-octylphenol, p-nonylphenol, p-dodecylphenol and the like.

The amount of the resol type phenol resin used relative to the component (A) is not particularly limited, but is usually 10 to 120% by weight, preferably 30 to 100% by weight. In addition, in this embodiment, when manufacturing a rosin modified phenol resin by making (A) component, (B) component, and (C) component react, it replaces with the resol type phenol resin which is (C) component, and resole type | mold. You may use phenols (P) and formaldehyde (F) of the stage which manufactures a phenol resin. That is, a rosin-modified phenol resin may be produced by reacting a mixture containing the rosin (A), the polyhydric alcohols (B), phenols and formaldehyde.

(Method for producing rosin-modified phenolic resin)
Examples of the method for producing the rosin-modified phenolic resin according to this embodiment include the following three methods (i) to (iii).

(I) A method in which crude tall oil and / or distilled tall oil, or a mixture containing crude tall oil and / or distilled tall oil and rosin, a resol type phenol resin, and a polyhydric alcohol are simultaneously charged and reacted. .

(Ii) Crude tall oil and / or distilled tall oil, or a mixture containing crude tall oil and / or distilled tall oil and rosin, and a resol type phenol resin are added and reacted with a polyol component and esterified. How to react.

(Iii) Esterification of crude tall oil and / or distilled tall oil, or a mixture containing crude tall oil and / or distilled tall oil and rosin and a polyol component, and then charged with a resol type phenol resin How to react.

The above-mentioned crosslinking reaction for increasing the molecular weight can be carried out at an appropriate stage in the production methods (i) to (iii).

After completion of the reaction, the acid value, softening point, viscosity, solubility, etc. of the obtained resin are confirmed, and the reaction is terminated as soon as a predetermined value is reached.

The obtained resin can be suitably used for components such as printing ink. The rosin-modified ester polyester resin and rosin-modified phenol resin of the present invention preferably have a softening point of 120 ° C. or higher, more preferably about 130 to 200 ° C. The acid value is preferably about 10 to 40 KOHmg / g.

(Resin for ink for offset printing)
The resin for offset printing ink according to the present embodiment includes, in addition to the rosin-modified polyester resin and / or rosin-modified phenol resin, shellac, gilsonite, alkyd resin, and rosin-modified phenol as long as the effects of the present invention are not impaired. You may contain other resin for inks, such as resin.

(Ink for offset printing)
Next, the offset printing ink containing the rosin-modified polyester resin or rosin-modified phenol resin according to the present invention will be described. The rosin-modified polyester resin or rosin-modified phenol resin according to the present invention can be used as a resin for printing ink, particularly as a resin for ink for offset printing. In order to prepare varnishes, resins for offset printing ink are generally used as drying oil or semi-drying oil (for example, linseed oil, tung oil, soybean oil, soybean white squeezed oil, etc.) and solvents (for example, aliphatic hydrocarbon solvents, etc.) ).

In preparing the varnish using the resin for offset printing ink according to the present invention, various gelling agents may be added in consideration of viscoelasticity as long as the effects of the present invention are not impaired. The gelling agent is not particularly limited, and examples thereof include aluminum compounds such as aluminum alcoholate and aluminum soap; metal soaps such as manganese, cobalt and zirconium; alkanolamine and the like. A gelling agent may be used independently and may be used in combination of 2 or more types.

In consideration of the storage stability of varnish and ink, various antioxidants may be added as long as the effects of the present invention are not impaired. The antioxidant is not particularly limited, and examples thereof include hydroquinone, tertiary butyl hydroquinone, dibutylhydroxytoluene, eugenol, pyrogallol, catechol, and guaralacol. An antioxidant may be used independently and may be used in combination of 2 or more types.

An offset printing ink is prepared by dispersing a pigment of a desired color (black pigment, indigo pigment, red pigment, yellow pigment, etc.) in the varnish obtained from the resin for offset printing ink according to the present embodiment. The obtained printing ink is suitable for offset inks such as sheet-fed ink and off-wheel ink, and can also be used for newspaper ink, letterpress ink and gravure ink.
In addition, when the rosin-modified polyester resin or rosin-modified phenol resin of the present invention is used as a binder for offset printing inks, etc., printing properties such as emulsification characteristics, gloss, drying properties, misting, etc. of printing inks containing these resins However, it is equal to or higher than that of conventionally known rosin-modified phenolic resins. Accordingly, the present invention can provide printing inks that meet recent market demands.

Next, the present invention will be described based on examples and comparative examples, but the present invention is not limited to the following examples. “Parts” and “%” are based on mass unless otherwise specified. Moreover, the numerical value of the Example shown below can be substituted for the numerical value (namely, upper limit value or lower limit value) described in embodiment. In addition, this invention is not restrained by the following Example, a synthesis example, and a preparation example, Of course, arbitrary deformation | transformation can be made within the range of the technical idea of this invention.

(Preparation of resol type phenol resin)
First, a method for synthesizing (C) a resole type phenol resin used when synthesizing a rosin-modified phenol resin according to the present embodiment will be described.
In a flask equipped with a stirrer, water separator, condenser and thermometer, 275 parts of xylene, 1633 parts of p-butylphenol and 86.5 parts of p-octylphenol were charged and dissolved at 70 ° C., and then 92% paraformaldehyde After adding 626.5 parts, it cooled to 60 degreeC and added 1.8 parts of lithium hydroxide monohydrate. Thereafter, the temperature was raised to 95 ° C. and an addition reaction was performed for 6 hours to obtain a resol type phenol resin having a solid content of 87.5%.
Example 1

(Preparation of rosin-modified polyester resin 1)
A flask equipped with a stirrer, a water separator, a condenser tube, and a thermometer was charged with 300 parts of crude tall oil and 700 parts of tall rosin and heated to 160 ° C. in a nitrogen atmosphere. 87.5 parts of maleic anhydride was added thereto, the temperature was raised to 200 ° C., 5.2 parts of calcium hydroxide, 3.1 parts of sodium hydroxide, and 2.7 parts of magnesium oxide were added, The reaction was performed for about 1 hour. Next, 195 parts of pentaerythritol was added, the temperature was raised to about 270 ° C., the reaction was carried out until the prescribed acid value, viscosity, and solubility were reached, and then the pressure was reduced at 0.08 MPa for 30 minutes and cooled to solid rosin. Modified polyester resin 1 was obtained. The acid value of the resin was 9.5 KOH mg / g, the softening point was 133 ° C., and the n-hexane tolerance was 1.9 g / g.
Example 2

(Preparation of rosin-modified polyester resin 2)
A flask equipped with a stirrer, a water separator, a condenser tube and a thermometer was charged with 300 parts of distilled tall oil and 700 parts of tall rosin and heated to 160 ° C. in a nitrogen atmosphere. 87.5 parts of maleic anhydride was added thereto, the temperature was raised to 200 ° C., 5.2 parts of calcium hydroxide, 3.1 parts of sodium hydroxide, and 2.7 parts of magnesium oxide were added, The reaction was performed for about 1 hour. Next, 195 parts of pentaerythritol was added, the temperature was raised to about 270 ° C., the reaction was carried out until the prescribed acid value, viscosity, and solubility were reached, and then the pressure was reduced at 0.08 MPa for 30 minutes and cooled to solid rosin. Modified polyester resin 2 was obtained. The acid value of the resin was 10.5 KOH mg / g, the softening point was 144 ° C., and the n-hexane tolerance was 1.2 g / g.
Example 3

(Preparation of rosin-modified polyester resin 3)
A flask equipped with a stirrer, a water separator, a condenser tube and a thermometer was charged with 252 parts of crude tall oil and 588 parts of tall rosin, and the temperature was raised to 160 ° C. in a nitrogen atmosphere. After 98 parts of maleic anhydride was added thereto, the temperature was raised to 200 ° C., 4.4 parts of calcium hydroxide, 2.7 parts of sodium hydroxide, and 2.3 parts of magnesium oxide were added. Reacted for hours. Next, 113 parts of pentaerythritol was added, the temperature was raised to about 270 ° C., the reaction was performed until the prescribed acid value, viscosity, and solubility were reached, and then the pressure was reduced at 0.08 MPa for 30 minutes and cooled to solid rosin. A modified polyester resin 7 was obtained. The acid value of the resin was 9.5 KOH mg / g, the softening point was 133 ° C., and the n-hexane tolerance was 1.9 g / g.
Example 4

(Preparation of rosin-modified phenolic resin 1)
A flask equipped with a stirrer, a water separator, a cooling pipe and a thermometer was charged with 543 parts of distilled tall oil and 500 parts of Petol 140 (manufactured by Tosoh Corporation), and the temperature was raised to 180 ° C. in a nitrogen atmosphere. Subsequently, it stirred for 30 minutes and was made to cool to 150 degreeC. The resol type phenol resin (617 parts) (solid part 540 parts) was charged therein, and the temperature was raised. At 200 ° C., 49.6 parts of glycenline was charged, and the temperature was raised to 255 ° C. After reacting until the temperature reached a predetermined acid value, viscosity, and solubility, the solution was reduced in pressure at 0.08 MPa for 30 minutes and cooled to obtain a solid rosin-modified phenolic resin 1. The acid value of the resin was 11.7 KOH mg / g, the softening point was 154 ° C., and the n-hexane tolerance was 1.9 g / g.
Example 5

(Preparation of rosin-modified phenolic resin 2)
A flask equipped with a stirrer, a water separator, a cooling pipe and a thermometer was charged with 543 parts of crude tall oil and 500 parts of Petcoal 140 (manufactured by Tosoh Corporation), and the temperature was raised to 180 ° C. in a nitrogen atmosphere. Subsequently, it stirred for 30 minutes and was made to cool to 150 degreeC. The resol type phenolic resin 617 parts (solid part 540 parts) was charged therein, and the temperature was raised. At 200 ° C., 2.6 parts of pentaerythritol and 47 parts of glycerin were added, and the temperature was raised to 255 ° C. After reacting until the temperature reached a predetermined acid value, viscosity, and solubility, the solution was reduced in pressure at 0.08 MPa for 30 minutes and cooled to obtain a solid rosin-modified phenolic resin 1. The acid value of the resin was 10.0 KOH mg / g, the softening point was 153 ° C., and the n-hexane tolerance was 2.3 g / g.
Example 6

(Preparation of rosin-modified phenolic resin 3)
A flask equipped with a stirrer, a water separator, a condenser tube and a thermometer was charged with 500 parts of crude tall oil and 500 parts of tall rosin and heated to 180 ° C. under a nitrogen atmosphere. Next, 3.8 parts of magnesium oxide and 2.5 parts of calcium hydroxide were added. After the addition, the mixture was stirred for 30 minutes and cooled to 150 ° C. The resol type phenolic resin 512 parts (solid part 448 parts) was charged here, the temperature increase was started, maleic anhydride 25 parts was added at 180 ° C., and at 200 ° C., pentaerythritol 112.5 parts, glycerin 12.5 The temperature was raised to 255 ° C. After reacting until the temperature reached a predetermined acid value, viscosity, and solubility, the solution was reduced in pressure at 0.08 MPa for 30 minutes and cooled to obtain a solid rosin-modified phenolic resin 1. The acid value of the resin was 23.8 KOH mg / g, the softening point was 138 ° C., and the n-hexane tolerance was 3.4 g / g.
Example 7

(Preparation of rosin-modified phenolic resin 4)
A flask equipped with a stirrer, a water separator, a condenser tube and a thermometer was charged with 500 parts of distilled tall oil and 500 parts of tall rosin and heated to 180 ° C. in a nitrogen atmosphere. Next, 3.8 parts of magnesium oxide and 2.5 parts of calcium hydroxide were added. After the addition, the mixture was stirred for 30 minutes and cooled to 150 ° C. 457 parts (400 parts of the solid part) of the resol type phenol resin were charged therein, the temperature was raised, 22.5 parts of maleic anhydride was added at 180 ° C., and further at 121 ° C., 121 parts of pentaerythritol and 5.7 glycenline. The temperature was raised to 255 ° C. After reacting until the temperature reached a predetermined acid value, viscosity, and solubility, the pressure was reduced at 0.08 MPa for 30 minutes, and the solid rosin-modified phenolic resin 2 was obtained. The acid value of the resin was 24.1 KOH mg / g, the softening point was 141 ° C., and the n-hexane tolerance was 2.3 g / g.
Example 8

(Preparation of rosin-modified phenolic resin 5)
A flask equipped with a stirrer, a water separator, a condenser tube and a thermometer was charged with 700 parts of crude tall oil and 300 parts of tall rosin and heated to 180 ° C. in a nitrogen atmosphere. Here, 3.7 parts of magnesium oxide as a crosslinking agent and 2.5 parts of calcium hydroxide were added and stirred for 30 minutes, and then cooled to 150 ° C., and 544 parts of the resol type phenol resin (solid part 476 parts) were charged. At 180 ° C., 30 parts of maleic anhydride was added as an anhydride of α, β-unsaturated dicarboxylic acid. At 200 ° C., 112.5 parts of pentaerythritol and 12.5 parts of glycerin were added. The temperature was raised to ° C. After reacting until the temperature reached a predetermined acid value, viscosity, and solubility, the solution was reduced in pressure at 0.08 MPa for 30 minutes and cooled to obtain a solid rosin-modified phenolic resin 7. The acid value of the resin was 20.0 KOH mg / g, the softening point was 132 ° C., and the n-hexane tolerance was 3.7 g / g.
Example 9

(Preparation of rosin-modified phenolic resin 6)
A flask equipped with a stirrer, a water separator, a condenser tube and a thermometer was charged with 500 parts of crude tall oil and 500 parts of tall rosin and heated to 180 ° C. in a nitrogen atmosphere. Here, 3.7 parts of magnesium oxide as a crosslinking agent and 2.5 parts of calcium hydroxide were added and stirred for 30 minutes, and then cooled to 150 ° C., and 493 parts of the resol type phenol resin (solid part 432 parts) were charged, At 180 ° C., 25 parts by weight of maleic anhydride was charged as an anhydride of α, β-unsaturated dicarboxylic acid, and at 200 ° C., 111 parts of pentaerythritol and 12.5 parts of glycerin were charged to 255 ° C. The temperature rose. After reacting until the temperature reached a predetermined acid value, viscosity, and solubility, the mixture was reduced in pressure at 0.08 MPa for 30 minutes and cooled to obtain solid rosin-modified phenolic resin 8. The acid value of the resin was 19.3 KOH mg / g, the softening point was 130 ° C., and the n-hexane tolerance was 3.4 g / g.
Example 10

(Preparation of rosin-modified polyester resin 4)
A flask equipped with a stirrer, a water separator, a condenser tube and a thermometer was charged with 546 parts of crude tall oil and heated to 160 ° C. in a nitrogen atmosphere. Next, 7.5 parts of 4-sulfophthalic acid (50% aqueous solution) was added and held at the same temperature for 4 hours, and 3.3 parts of oleylamine and 294 parts of tall rosin were added. After the addition, the mixture was stirred for 30 minutes, 98 parts of maleic anhydride was added, and the temperature was raised to 200 ° C., 4.4 parts of calcium hydroxide, 2.7 parts of sodium hydroxide, and 2.3 parts of magnesium oxide. Partly added and allowed to react for about 1 hour. Next, 113 parts of pentaerythritol was added, the temperature was raised to about 270 ° C., the reaction was performed until the prescribed acid value, viscosity, and solubility were reached, and then the pressure was reduced at 0.08 MPa for 30 minutes and cooled to solid rosin. Modified polyester resin 1 was obtained. The acid value of the resin was 36.4 KOH mg / g, the softening point was 134 ° C., and the n-hexane tolerance was 2.8 g / g.
Example 11

(Preparation of rosin-modified polyester resin 5)
650 parts of crude tall oil and 350 parts of tall rosin were charged into a flask equipped with a stirrer, a water separator, a condenser tube and a thermometer, and the temperature was raised to 160 ° C. in a nitrogen atmosphere. Next, 15 parts of 4-sulfophthalic acid (50% aqueous solution) was added, held at the same temperature for 4 hours, and 7.5 parts of oleylamine was added. After the addition, the mixture is stirred for 30 minutes, 109 parts of maleic anhydride is added, and the temperature is raised to 200 ° C., 3.9 parts of calcium oxide, 2.5 parts of sodium hydroxide, and 2.7 parts of magnesium oxide It was added and allowed to react for about 1 hour. Next, 114 parts of pentaerythritol was added, the temperature was raised to about 270 ° C., the reaction was continued until the prescribed acid value, viscosity, and solubility were reached, and then the pressure was reduced at 0.08 MPa for 30 minutes and cooled to solid rosin. Modified polyester resin 2 was obtained. The acid value of the resin was 37.8 KOH mg / g, the softening point was 135 ° C., and the n-hexane tolerance was 3.2 g / g.
Example 12

(Preparation of rosin-modified polyester resin 6)
A flask equipped with a stirrer, a water separator, a condenser tube and a thermometer was charged with 546 parts of distilled tall oil and heated to 160 ° C. in a nitrogen atmosphere. Next, 7.5 parts of 4-sulfophthalic acid (50% aqueous solution) was added and held at the same temperature for 4 hours, and 3.3 parts of oleylamine and 294 parts of tall rosin were added. After the addition, the mixture was stirred for 30 minutes, 97 parts of maleic anhydride was added, and the temperature was raised to 200 ° C., 4.4 parts of calcium hydroxide, 2.7 parts of sodium hydroxide, and 2.3 parts of magnesium oxide. Partly added and allowed to react for about 1 hour. Next, 100 parts of pentaerythritol and 12 parts of glycerin are added, the temperature is raised to about 270 ° C., and the reaction is carried out until a predetermined acid value, viscosity, and solubility are reached, and then the pressure is reduced and cooled at 0.08 MPa for 30 minutes. Thus, a solid rosin-modified polyester resin 3 was obtained. The acid value of the resin was 35.3 KOH mg / g, the softening point was 136 ° C., and the n-hexane tolerance was 2.3 g / g.
Example 13

(Preparation of rosin-modified polyester resin 7)
273 parts of crude tall oil and 273 parts of distilled tall oil were charged into a flask equipped with a stirrer, a water separator, a condenser and a thermometer, and the temperature was raised to 160 ° C. in a nitrogen atmosphere. Next, 7.5 parts of 4-sulfophthalic acid (50% aqueous solution) was added and held at the same temperature for 4 hours, and 3.3 parts of oleylamine and 294 parts of tall rosin were added. After the addition, the mixture was stirred for 30 minutes, 97 parts of maleic anhydride was added, and the temperature was raised to 200 ° C., 4.4 parts of calcium hydroxide, 2.7 parts of sodium hydroxide, and 2.3 parts of magnesium oxide. Partly added and allowed to react for about 1 hour. Next, 100 parts of pentaerythritol and 12 parts of glycerin are added, the temperature is raised to about 270 ° C., and the reaction is carried out until a predetermined acid value, viscosity, and solubility are reached, and then the pressure is reduced and cooled at 0.08 MPa for 30 minutes. Thus, a solid rosin-modified polyester resin 4 was obtained. The acid value of the resin was 37.0 KOH mg / g, the softening point was 134 ° C., and the n-hexane tolerance was 2.4 g / g.
Example 14

(Preparation of rosin-modified phenolic resin 7)
Into a flask equipped with a stirrer, a water separator, a cooling tube and a thermometer, 978 parts of crude tall oil was charged and heated to 160 ° C. in a nitrogen atmosphere. Next, 14.6 parts of 4-sulfophthalic acid (50% aqueous solution) was added, held at the same temperature for 4 hours, and 7.4 parts of oleylamine was added. After the addition, the mixture was stirred for 30 minutes and heated up to 180 ° C. Here, 9.9 parts of zinc oxide as a crosslinking agent was added and stirred for 30 minutes, and then cooled to 150 ° C. Next, 457 parts (400 parts of a solid part) of the resol type phenol resin were charged, and the temperature was raised. At 180 ° C., 22.5 parts of maleic anhydride was added as an anhydride of α, β-unsaturated dicarboxylic acid, Further, at 200 ° C., 119 parts of pentaerythritol and 7.7 parts of glycerin were charged, and the temperature was raised to 255 ° C. After reacting until the temperature reached a predetermined acid value, viscosity, and solubility, the solution was reduced in pressure at 0.08 MPa for 30 minutes and cooled to obtain a solid rosin-modified phenolic resin 1. The acid value of the resin was 17.5 KOH mg / g, the softening point was 134 ° C., and the n-hexane tolerance was 5.7 g / g.
Example 15

(Preparation of rosin-modified phenolic resin 8)
Into a flask equipped with a stirrer, a water separator, a condenser tube and a thermometer, 685 parts of crude tall oil was charged and heated to 160 ° C. in a nitrogen atmosphere. Next, 10.3 parts of 4-sulfophthalic acid (50% aqueous solution) was added, held at the same temperature for 4 hours, charged with 5.2 parts of oleylamine and 300 parts of tall rosin, and heated to 180 ° C. in a nitrogen atmosphere. I let you. Here, 3.8 parts of magnesium oxide as a crosslinking agent was added and stirred for 30 minutes, and then cooled to 150 ° C. Next, 544 parts of the resol-type phenol resin (476 parts of a solid part) were added, and the temperature was raised. At 180 ° C., 24 parts of maleic anhydride was added as an anhydride of α, β-unsaturated dicarboxylic acid, and further 200 At 0 ° C., 111 parts of pentaerythritol and 12.5 parts of glycerin were charged, and the temperature was raised to 255 ° C. After reacting until the temperature reached a predetermined acid value, viscosity, and solubility, the pressure was reduced at 0.08 MPa for 30 minutes, and the solid rosin-modified phenolic resin 2 was obtained. The acid value of the resin was 18.5 KOH mg / g, the softening point was 135 ° C., and the n-hexane tolerance was 3.0 g / g.
Example 16

(Preparation of rosin-modified phenolic resin 9)
In a flask equipped with a stirrer, a water separator, a condenser tube and a thermometer, 489 parts of crude tall oil was charged and heated to 160 ° C. in a nitrogen atmosphere. Next, 7.3 parts of 4-sulfophthalic acid (50% aqueous solution) was added, held at the same temperature for 4 hours, and 3.7 parts of oleylamine and 500 parts of tall rosin were added. After the addition, the mixture was stirred for 30 minutes and heated up to 180 ° C. Here, 3.7 parts of magnesium oxide and 2.5 parts of calcium hydroxide as a crosslinking agent were added and stirred for 30 minutes, and then cooled to 150 ° C. Next, 493 parts of the resol type phenolic resin (432 parts of solid part) were charged, and the temperature was raised. At 180 ° C., 25 parts of maleic anhydride was added as an anhydride of α, β-unsaturated dicarboxylic acid, and further 200 At 0 ° C., 111 parts of pentaerythritol and 12.5 parts of glycerin were charged, and the temperature was raised to 255 ° C. After reacting until the temperature reached a predetermined acid value, viscosity, and solubility, the pressure was reduced at 0.08 MPa for 30 minutes and cooled to obtain a solid rosin-modified phenolic resin 3. The acid value of the resin was 18.0 KOH mg / g, the softening point was 137 ° C., and the n-hexane tolerance was 3.2 g / g.
Example 17

(Preparation of rosin-modified phenolic resin 10)
A flask equipped with a stirrer, a water separator, a condenser tube and a thermometer was charged with 489 parts of distilled tall oil and heated to 160 ° C. in a nitrogen atmosphere. Next, 7.3 parts of 4-sulfophthalic acid (50% aqueous solution) was added, held at the same temperature for 4 hours, and 3.7 parts of oleylamine and 500 parts of tall rosin were added. After the addition, the mixture was stirred for 30 minutes and heated up to 180 ° C. Here, 3.7 parts of magnesium oxide as a crosslinking agent and 2.5 parts of calcium hydroxide were added and stirred for 30 minutes, and then cooled to 150 ° C., and 493 parts of the resol type phenol resin (solid part 432 parts) were charged, At 180 ° C., 23 parts of maleic anhydride was added as an anhydride of α, β-unsaturated dicarboxylic acid, and at 200 ° C., 111 parts of pentaerythritol and 12.5 parts of glycerin were added up to 255 ° C. The temperature rose. After reacting until the temperature reached a predetermined acid value, viscosity, and solubility, the solution was reduced in pressure at 0.08 MPa for 30 minutes and cooled to obtain a solid rosin-modified phenolic resin 4. The acid value of the resin was 19.0 KOH mg / g, the softening point was 141 ° C., and the n-hexane tolerance was 3.3 g / g.
Example 18

(Preparation of rosin-modified phenolic resin 11)
A flask equipped with a stirrer, a water separator, a condenser tube, and a thermometer was charged with 500 parts of crude tall oil and 500 parts of tall rosin and heated to 160 ° C. in a nitrogen atmosphere. Next, 15 parts of 4-sulfophthalic acid (50% aqueous solution) was added, held at the same temperature for 4 hours, and 7.5 parts of oleylamine was added. After the addition, the mixture was stirred for 30 minutes and heated up to 180 ° C. Here, 3.7 parts of magnesium oxide as a crosslinking agent and 2.5 parts of calcium hydroxide were added and stirred for 30 minutes, and then cooled to 150 ° C., and 493 parts of the resol type phenol resin (solid part 432 parts) were charged, At 180 ° C., 23 parts of maleic anhydride was added as an anhydride of α, β-unsaturated dicarboxylic acid, and at 200 ° C., 111 parts of pentaerythritol and 12.5 parts of glycerin were added at 255 ° C. The temperature was raised to. After reacting until the temperature reached a predetermined acid value, viscosity, and solubility, the pressure was reduced at 0.08 MPa for 30 minutes and cooled to obtain a solid rosin-modified phenolic resin 5. The acid value of the resin was 18.4 KOH mg / g, the softening point was 142 ° C., and the n-hexane tolerance was 3.2 g / g.
Comparative Example 1

(Preparation of rosin-modified polyester resin 8)
A flask equipped with a stirrer, a water separator, a condenser tube, and a thermometer was charged with 300 parts of tall oil fatty acid (Hartol FA-1 manufactured by Harima Chemicals Co., Ltd.) and 700 parts of tall rosin up to 160 ° C. under a nitrogen atmosphere. The temperature was raised. After 98 parts of maleic anhydride was added, the temperature was raised to 200 ° C., 5.2 parts of calcium oxide, 3.1 parts of sodium hydroxide, and 2.7 parts of magnesium oxide were added, and about 1 hour. Reacted. Next, 205 parts of pentaerythritol was added, the temperature was raised to about 270 ° C., the reaction was carried out until the prescribed acid value, viscosity, and solubility were reached, and the solid rosin was then cooled under reduced pressure at 0.08 MPa for 30 minutes. Modified polyester resin 3 was obtained. The acid value of the resin was 11.1 KOH mg / g, the softening point was 137 ° C., and the n-hexane tolerance was 2.9 / g or more.
Comparative Example 2

(Preparation of rosin-modified polyester resin 9)
A flask equipped with a stirrer, a water separator, a condenser tube, and a thermometer was charged with 150 parts of tall oil fatty acid (Hartol FA-1 manufactured by Harima Chemicals Co., Ltd.) and 850 parts of tall rosin up to 160 ° C. under a nitrogen atmosphere. The temperature was raised. 87.5 parts of maleic anhydride was added thereto, the temperature was raised to 200 ° C., 5.2 parts of calcium oxide, 3.1 parts of sodium hydroxide, and 2.7 parts of magnesium oxide were added. The reaction was carried out for 1 hour. Next, 195 parts of pentaerythritol was added, the temperature was raised to about 270 ° C., the reaction was carried out until the prescribed acid value, viscosity, and solubility were reached, and then the pressure was reduced at 0.08 MPa for 30 minutes and cooled to solid rosin. Modified polyester resin 4 was obtained. The acid value of the resin was 10.4 KOH mg / g, the softening point was 135 ° C., and the n-hexane tolerance was 2.0 g / g or more.
Comparative Example 3

(Preparation of rosin-modified phenolic resin 12)
A flask equipped with a stirrer, a water separator, a condenser tube, and a thermometer was charged with 500 parts of tall oil fatty acid (Hartol FA-1 manufactured by Harima Chemicals Co., Ltd.) and 500 parts of tall rosin and heated to 180 ° C. under a nitrogen atmosphere. The temperature was raised. Next, 3.8 parts of magnesium oxide and 2.5 parts of calcium hydroxide were added. After the addition, the mixture was stirred for 30 minutes and cooled to 150 ° C. This was charged with 537 parts of the resol type phenolic resin (solid part 470 parts), temperature increase was started, and 43.8 parts of maleic anhydride was added at 180 ° C., and further at 200 ° C., 112.5 parts of pentaerythritol and glycenline 12 .5 parts was charged and the temperature was raised to 255 ° C. After reacting until the temperature reached a predetermined acid value, viscosity, and solubility, the pressure was reduced at 0.08 MPa for 30 minutes and cooled to obtain a solid rosin-modified phenolic resin 3. The acid value of the resin was 24.2 KOH mg / g, the softening point was 128 ° C., and the n-hexane tolerance was 7.3 g / g.
Comparative Example 4

(Preparation of rosin-modified phenolic resin 13)
A flask equipped with a stirrer, a water separator, a condenser tube, and a thermometer was charged with 250 parts of tall oil fatty acid (Hartol FA-1 manufactured by Harima Kasei Co., Ltd.) and 750 parts of tall rosin and heated to 180 ° C. under a nitrogen atmosphere. The temperature was raised. Next, 3.8 parts of magnesium oxide and 2.5 parts of calcium hydroxide were added. After the addition, the mixture was stirred for 30 minutes and cooled to 150 ° C. Here, 493 parts of the resol type phenolic resin (432 parts of solid part) was charged, the temperature was raised, 30.8 parts of maleic anhydride was added at 180 ° C., and at 200 ° C., 111 parts of pentaerythritol and 12.3 of glycerin were added. The temperature was raised to 255 ° C. After reacting until the temperature reached a predetermined acid value, viscosity, and solubility, the solution was reduced in pressure at 0.08 MPa for 30 minutes and cooled to obtain a solid rosin-modified phenolic resin 4. The acid value of the resin was 22.0 KOH mg / g, the softening point was 133 ° C., and the n-hexane tolerance was 3.8 g / g.

Various characteristics were evaluated using the prepared resin for offset ink. The experimental conditions for each item are as follows.

[Judgment result of resinification]
In view of each characteristic value, the rosin-modified polyester resin was comprehensively judged.
○ (good): Resin can be used for ink.
X (impossible): Resin cannot be used for ink.
<Preparation of varnish for printing ink>
Each resin, soybean oil white squeezed oil and AF6 (manufactured by JX Nippon Oil & Energy Corporation, aroma-free solvent) obtained in Examples 1 to 18 and Comparative Examples 1 to 4 were used as resin: soybean oil white squeezed oil: It put into the flask by AF6 = 55: 30: 15, and stirred at 190 degreeC for 1 hour. Next, soybean oil white squeezed oil and AF6 were added so that the ratio of soybean oil white squeezed oil in the varnish was not less than 30%, and a rheometer (manufactured by Thermo Haake, HAAKE Rheo Stress 600), 25 ° C., 1.0 Hz. An ink varnish having a viscosity adjusted to about 100 Pa · s was obtained.
<Preparation of printing ink>
60 parts of each varnish obtained and 19 parts of neutral carbon black (Mitsubishi Chemical Co., Ltd., RCF # 52) were mixed. Subsequently, neutral carbon black was disperse | distributed to the varnish using the three roll mill (Inoue Seisakusho make, S-4 3/4 * 11). Next, AF6 and a dryer (manufactured by Toei Chemical Co., Ltd., cobalt naphthenate 6%) were added and adjusted so that the tack at 30 ° C. was about 5.0 to 6.0 to obtain an ink for evaluation. . The obtained resins of Examples 1 to 4 and Comparative Examples 1 to 4 and the inks for evaluation (using the resins of Examples 1 to 4 and Comparative Examples 1 to 4 respectively) were evaluated by the following methods. The evaluation results are shown in Tables 1 to 4 together with the determination of the resin results of the resins of Examples 1 to 18 and Comparative Examples 1 to 4.

[Acid value]
The measurement was performed according to JIS K5902.

[Softening point]
In accordance with JIS K5902 (ring and ball method), the measurement was performed using an automatic softening point measuring device (RSP-102, manufactured by Rouai Co., Ltd.).

[33% linseed oil viscosity]
Viscosity of linseed oil (manufactured by Nissin Oilio Group Co., Ltd.) and rosin-modified polyester resin in a ratio of 2: 1 by weight and dissolved by heating at 25 ° C. using a Gardner bubble viscometer Say.

[Hexane tolerance]
Linseed oil (Nisshin Oillio Group Co., Ltd.) and rosin-modified polyester resin were blended in a ratio of 2: 1 by weight, and normal hexane (Showa Chemical Co., Ltd.) was added to the mixture after heating and dissolving. The ratio of the amount of hexane required to do was measured.

[Tack value]
One cup of ink was placed on an incometer (manufactured by Toyo Seiki Co., Ltd.), and the tack value when rotated at 400 rpm for 1 minute was measured.

[Anti-misting]
10 levels of ink scattering on white paper placed on the front and bottom of the roll when 2 cups of ink are placed on the incomuter (Toyo Seiki Co., Ltd.) and rotated at 2000 rpm for 2 minutes. The observation was divided into two. The larger the value, the better the misting resistance.

[Set drying]
After 0.2 mL of ink was developed on art paper with a RI tester 4-split roll, the ink was pressurized over time, and the time until setting was completed was measured.

[Gloss value]
0.8 mL of ink was developed on art paper with an entire roll of RI tester (RI-2, manufactured by Ishikawajima Industrial Machinery Co., Ltd.). The art paper was placed at 23 ° C. and 50% R.D. H. And the reflectance of the ink film surface at 60 ° -60 ° was measured using a gloss meter (manufactured by Dazai Equipment Co., Ltd., Micro Trigloss). The larger the value, the better the gloss.

The resin constants in Tables 1 to 4 are the evaluation results of the resins of Examples 1 to 18 and Comparative Examples 1 to 4, and the ink evaluation results in Tables 1 to 4 are the results of Examples 1 to 18 and the comparisons. 4 is an evaluation result of inks containing each resin of Examples 1 to 4. As shown in Tables 1 to 4, the printing ink containing the resin for printing inks of the present invention using crude tall oil and / or distilled tall oil has higher drying and misting resistance than the case of using tall oil fatty acid. It was found that the printed matter can be given a good gloss while keeping the color. In addition, the printing ink containing the resin for printing ink of the present invention using the polymerized crude tall oil and / or the polymerized distilled tall oil maintains further drying and misting resistance than the case of using tall oil fatty acid. As a result, it was found that the printed matter can be given further excellent gloss. It has also been found that the use of the printing ink resin of the present invention can improve the performance of a plurality of inks in a trade-off relationship.

Claims (19)

1. At least (A) crude tall oil and / or distilled tall oil, or a mixture comprising crude tall oil and / or distilled tall oil and rosin;
   (B) a polyhydric alcohol;
   A rosin-modified resin obtained by reacting
2. (A) is a mixture containing crude tall oil and / or distilled tall oil and rosin, and the total content of crude tall oil and distilled tall oil in the mixture is more than 0% by weight and 50% by weight or less. The rosin-modified resin according to claim 1.
3. The rosin-modified resin according to claim 1, wherein (A) is a mixture containing a polymerized crude tall oil and / or a polymerized distilled tall oil and rosin.
4. The rosin-modified resin according to claim 3, wherein a total content of the polymerized crude tall oil and the polymerized distilled tall oil in the mixture is more than 30% by weight and 90% by weight or less.
5. The rosin-modified resin according to claim 3, wherein the polymerization of the polymerized crude tall oil and the polymerization of the polymerized distilled tall oil are performed in the presence of a catalyst.
6. The catalyst is formic acid, acetic acid, phosphoric acid, sulfuric acid, phenolsulfonic acid, paratoluenesulfonic acid, methanesulfonic acid, sulfosuccinic acid, 5-sulfosalicylic acid, 4-sulfophthalic acid, 5-sulfoisophthalic acid, and other carboxylated sulfones. Pendants such as acids, arylsulfonic acids substituted with alkyl groups, solid acids having sulfonic acid groups, fluorosulfonic acids, trifluoromethanesulfonic acids, polystyrene sulfonic acids, polyvinyl sulfonic acids, or fluorinated polymers having sulfonic acid type functional groups Polymer hydrogen fluoride having sulfonic acid group, clay, zinc chloride, aluminum chloride, titanium tetrachloride, boron trifluoride and boron trifluoride phenol complex, boron trifluoride dimethyl ether complex or boron trifluoride diethyl ether complex, etc. No borotrifluoride It is at least one selected from the group consisting of derivatives, rosin-modified resin according to claim 5.
7. At least (A) crude tall oil and / or distilled tall oil, or a mixture comprising crude tall oil and / or distilled tall oil and rosin;
   (B) a polyhydric alcohol;
   (C) a resol type phenol resin;
   The rosin-modified resin according to claim 1, which is obtained by reacting.
8. The rosin according to claim 7, wherein (A) is a polymerized crude tall oil and / or polymerized distilled tall oil, or a mixture comprising polymerized crude tall oil and / or polymerized distilled tall oil and rosin. Modified resin.
9. (A) is a mixture comprising polymerized crude tall oil and / or polymerized distilled tall oil and rosin, and the total content of the polymerized crude tall oil and polymerized distilled tall oil in the mixture is: The rosin-modified resin according to claim 8, which is 50% by weight or more and 100% by weight or less.
10. The rosin-modified resin according to claim 8, wherein the polymerization of the polymerized crude tall oil and the polymerization of the polymerized distilled tall oil are performed in the presence of a catalyst.
11. The catalyst is formic acid, acetic acid, phosphoric acid, sulfuric acid, phenolsulfonic acid, paratoluenesulfonic acid, methanesulfonic acid, sulfosuccinic acid, 5-sulfosalicylic acid, 4-sulfophthalic acid, 5-sulfoisophthalic acid, and other carboxylated sulfones. Pendants such as acids, arylsulfonic acids substituted with alkyl groups, solid acids having sulfonic acid groups, fluorosulfonic acids, trifluoromethanesulfonic acids, polystyrene sulfonic acids, polyvinyl sulfonic acids, or fluorinated polymers having sulfonic acid type functional groups Polymer hydrogen fluoride having sulfonic acid group, clay, zinc chloride, aluminum chloride, titanium tetrachloride, boron trifluoride and boron trifluoride phenol complex, boron trifluoride dimethyl ether complex or boron trifluoride diethyl ether complex, etc. No trifluoride It is at least one selected from the group consisting of derivatives, rosin-modified resin according to claim 9.
12. The rosin-modified phenolic resin according to claim 7, wherein (C) is a reaction product of a phenol having a C ₁ to C ₂₀ alkyl group.
13. The rosin-modified resin according to claim 1, wherein the crude tall oil and / or distilled tall oil is derived from pine.
14. The rosin-modified resin according to claim 1, wherein (B) is glycerin and / or pentaerythritol.
15. A varnish for printing ink, comprising the rosin-modified resin according to claim 1, a drying oil or semi-drying oil, and a solvent.
16. A printing ink comprising the rosin-modified resin according to claim 1, a drying oil or semi-drying oil, a solvent, a gelling agent, and a pigment.
17. A first step of polymerizing crude tall oil and / or distilled tall oil under a temperature condition of 100 to 200 ° C. under a catalyst;
    A second step of reacting at least a polymerized crude tall oil and / or polymerized distilled tall oil, or a mixture comprising crude tall oil and / or distilled tall oil and rosin, and a polyhydric alcohol;
    A process for producing a rosin-modified resin, comprising:
18. The method for producing a rosin-modified resin according to claim 17, wherein the second step includes a step of reacting a polymerized crude tall oil and / or a polymerized distilled tall oil, a resol type phenol resin, and a polyhydric alcohol. .
19. The rosin-modified resin according to claim 17, wherein the second step includes a step of reacting a mixture containing crude tall oil and / or distilled tall oil and rosin, a resol type phenol resin, and a polyhydric alcohol. Production method.