JP2008138131A - Printing ink resin composition, method for producing printing ink resin composition, printing ink binder and printing ink - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel printing ink resin composition which uses no alkylphenol-formaldehyde condensate and has various properties equal to the conventionally known rosin modified phenolic resin, and furthermore gives a printing ink excellent in flowability. <P>SOLUTION: The printing ink resin composition comprises a polar group-containing terpene resin (a), a rosin (b), and a polyol (c) as reaction components. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a resin composition for printing ink, a method for producing a resin composition for printing ink, a binder for printing ink, and a printing ink. Specifically, a resin composition for printing ink that does not contain a substance such as formaldehyde, a method for producing the resin composition, a binder for printing ink whose main component is the resin composition for printing ink, and a binder for printing ink as a main component. The present invention relates to printing inks such as offset printing inks, newspaper inks, letterpress printing inks and gravure printing inks.

Since rosin-modified phenolic resins mainly composed of rosins, alkylphenol-formaldehyde condensates, polyols, etc. have a high softening point, high viscosity, high gelling ability, and excellent solubility in ink solvents. Conventionally, it has been awarded as a resin composition for printing ink, particularly as a resin composition for offset printing ink (see, for example, Patent Document 1). However, since rosin-modified phenolic resin produces wastewater containing formaldehyde during the production of alkylphenol-formaldehyde condensate, which is the main raw material, environmental problems such as air pollution due to volatile organic compounds (VOC), and safety and health of the work environment In some cases, it is not preferable.

Therefore, the present applicant does not use an alkylphenol form-aldehyde condensate as a raw material, and has various physical properties (high softening point, high viscosity, high gelling ability, high solubility, etc.) comparable to rosin-modified phenol resin. (See, for example, Patent Document 2). However, because the resin does not have a sufficient structure (polar group such as carboxyl group and hydroxyl group) that contributes to wettability with the pigment, there is a further improvement in printing ink applications where fluidity is required. It was necessary.

JP-A-11-286528 Japanese Patent No. 3446728

The present invention does not use an alkylphenol-formaldehyde condensate, and has various physical properties (high softening point, high viscosity, high gelling ability, high solubility, etc.) comparable to conventionally known rosin-modified phenol resins, Moreover, it contains a novel printing ink resin composition that gives printing ink with excellent fluidity, a method for producing the same, a printing ink binder comprising the printing ink resin composition, and the printing ink binder An object of the present invention is to provide a printing ink.

  As a result of intensive studies, the present inventor has found that the above problems can be solved by a rosin-based polyester resin containing a polar group-containing terpene resin as a resin component, and has completed the present invention.

That is, the present invention relates to a resin composition for printing inks comprising, as reaction components, polar group-containing terpene resins (a), rosins (b), and polyols (c); and polar group-containing petroleum resins (d). A process for producing the printing ink resin composition; a printing ink binder comprising the printing ink resin composition, a vegetable oil, a gelling agent, and, if necessary, a solvent; the printing ink The present invention relates to a printing ink containing a binder.

The resin composition for printing inks according to the present invention has various physical properties (high softening point, high viscosity, high gelling ability, high solubility, etc.) comparable to conventionally known rosin-modified phenol resins, A printing ink excellent in fluidity can be provided. Such a resin composition for printing ink of the present invention is used as a resin for offset printing inks such as offset sheet-fed ink (sheet-fed ink), offset rotary ink (off-wheel ink), newspaper ink, etc. It can also be suitably used as a resin for printing ink and gravure printing ink.

  As described above, the resin composition for printing ink according to the present invention includes polar group-containing terpene resins (a) (hereinafter referred to as component (a)), rosins (b) (hereinafter referred to as component (b)). And a polyester resin having a polyol (c) (hereinafter referred to as component (c)) as a reaction component.

As said (a) component, various well-known things can be especially used without a restriction | limiting. Specific examples include polar group-containing terpene resins obtained by reacting various known terpene resins with the α, β-unsaturated carboxylic acids. Further, the terpene resins are not particularly limited, and known ones can be used. Specifically, for example, terpene compounds such as α-pinene, β-pinene, limonene, camphene, and the like that are cationically polymerized by various known methods can be used. Commercially available products may be used (for example, YS resin (trade name, manufactured by Yasuhara Chemical Co., Ltd.)). Further, the α, β-unsaturated carboxylic acids are not particularly limited, and known ones can be used. Specifically, for example, α, β-unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid and itaconic acid, and α, β-unsaturated materials such as acrylic acid, methacrylic acid, crotonic acid and cinnamic acid. Saturated monocarboxylic acid etc. are mentioned, These can be used individually by 1 type or in combination of 2 or more types.

In addition, although the manufacturing method of this (a) component is not specifically limited, For example, the method of carrying out radical copolymerization reaction of this terpene resin and this (alpha), (beta)-unsaturated carboxylic acid in presence of a well-known radical reaction initiator. And a method in which both are ene-reacted. Further, the physical properties of the component (a) are not particularly limited, but it is easy to adjust the softening point and molecular weight of the resin composition for printing ink according to the present invention to a desired range, and the fluidity of the printing ink according to the present invention. Therefore, it is preferable that the theoretical acid value is usually about 2 to 200 mgKOH / g and the weight average molecular weight is usually about 1,000 to 10,000. Here, the theoretical acid value is the value (eq / g) of the total carboxyl equivalent (eq) of the raw material relative to the total weight (g) of the raw material having a carboxyl group used in the resin composition for printing ink. The value converted into an acid value (mgKOH / g) is said (hereinafter the same).

As said (b) component, various well-known things can be especially used without a restriction | limiting. Specifically, for example, natural rosin such as gum rosin, tall oil rosin, wood rosin; polymerized rosin derived from natural rosin; natural rosin or stabilized rosin obtained by disproportionating or hydrogenating polymerized rosin; Examples include unsaturated acid-modified rosins obtained by addition reaction of the above α, β-unsaturated carboxylic acids to polymerized rosin, and these can be used alone or in combination of two or more. In the unsaturated acid-modified rosin, the amount of α, β-unsaturated carboxylic acid used is not particularly limited, but it may be usually about 1 to 30 parts by weight with respect to 100 parts by weight of the raw rosin. As the component (b), the polymerized rosin and / or unsaturated acid-modified rosin is particularly preferable because the resin composition for printing ink according to the present invention is likely to have a high molecular weight and a high softening point. Is preferably contained in an amount of 10% by weight or more based on the total amount of component (b).

As said (c) component, various well-known things can be especially used without a restriction | limiting. Specific examples include dipentaerythritol, pentaerythritol, diglycerin, glycerin, ditrimethylolpropane, trimethylolpropane, ditrimethylolethane, trimethylolethane, and the like. These may be used alone or in combination of two. A combination of the above can be used. In addition, as (c) component, since it is easy to control the softening point, molecular weight, etc. of the resin composition for printing inks according to the present invention, a trihydric alcohol (glycerin) having 4 or less carbon atoms in the longest carbon chain of the molecule. , Trimethylolpurpan, trimethylolethane, etc.) and tetrahydric alcohols (pentaerythritol, diglycerin, ditrimethylolpropane, ditrimethylolethane, etc.) having 4 or less carbon atoms in the longest carbon chain of the molecule are preferred.

  In the present invention, for the purpose of adjusting the molecular weight of the resin composition for a printing ink according to the present invention to a desired range or increasing the water resistance of the printing ink according to the present invention, the component (a) to ( In addition to the component c), polar group-containing petroleum resins (d) (hereinafter referred to as the component (d)) can be used as a reaction component of the polyester resin. (D) It does not specifically limit as a component, Various well-known things can be used. Specifically, for example, a petroleum resin having a double bond in the molecule and a polar group such as a carboxyl group and / or a hydroxyl group can be used.

As the petroleum resin having a double bond in the molecule, for example, a DCPD petroleum resin obtained from a DCPD raw material such as cyclopentadiene or dicyclopentadiene; obtained from a C5 raw material such as pentene, cyclopentene, pentadiene or isoprene. C5 petroleum resin; C9 petroleum resin obtained from C9 raw materials such as methylbutene, indene, methylindene, vinyltoluene, styrene, α-methylstyrene, β-methylstyrene; copolymer consisting of DCPD raw material and C5 raw material Petroleum resin; Copolymerized petroleum resin composed of DCPD-based material and C9-based material; Copolymerized petroleum resin composed of C5-based material and C9-based material; Copolymerized petroleum resin composed of DCPD-based material, C5-based material and C9-based material can give. These resins are usually produced in the presence of various catalysts (for example, Friedel-Crafts type catalyst in the case of cationic polymerization) or without any catalyst. Among these, a petroleum resin containing a DCPD-based raw material as a component is preferable because a polar group can be easily imparted and it can be easily adjusted to a desired softening point. Specifically, the above-mentioned DCPD petroleum resin, copolymerized petroleum resin composed of DCPD based material and C5 based material, copolymerized petroleum resin composed of DCPD based material and C9 based material, DCPD based material, C5 based material and C9 based material A copolymer petroleum resin consisting of

Among the components (d), those obtained by introducing a carboxyl group into the petroleum resin having a double bond in the molecule can be produced by various known methods. Specifically, for example, a petroleum resin having a double bond in the molecule and the α, β-unsaturated carboxylic acid are subjected to radical copolymerization reaction in the presence of various known radical reaction initiators, The method of carrying out an ene reaction is mentioned.

Moreover, what introduce | transduced the hydroxyl group into the petroleum resin which has a double bond in the molecule | numerator among (d) component can be manufactured by various well-known methods. Specifically, for example, a method of thermally polymerizing a petroleum resin having a double bond in the molecule and an α, β-unsaturated alcohol can be mentioned. Examples of the α, β-unsaturated alcohols include allyl alcohol, crotyl alcohol, 2-butyn-1-ol, 3-butyn-2-ol, 3-butyn-1-ol, and 5-norbornene. -2-Methanol, cinnamyl alcohol, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and the like can be mentioned, and these can be used alone or in combination of two or more.

Moreover, what introduce | transduced the carboxyl group and the hydroxyl group into the petroleum resin which has a double bond in the said molecule | numerator among (d) component can be manufactured by various well-known methods. Specifically, for example, the α, β-unsaturated carboxylic acid is further ene-added to a hydroxyl group-containing petroleum resin obtained by introducing a hydroxyl group into the petroleum resin having a double bond in the molecule as the component (d), A method of radical copolymerization of both in the presence of a radical reaction initiator may be mentioned. In each reaction, it is preferable that the α, β-unsaturated carboxylic acid is further reacted with the hydroxyl group-containing petroleum resin at a ratio of a carboxyl group equivalent to the hydroxyl group equivalent.

The component (d) can be used alone or in combination of two or more. In addition, as the component (d), those having two or more polar groups in the molecule are preferably used for the purpose of increasing the molecular weight and increasing the softening point of the printing ink resin composition. In particular, a petroleum resin having a carboxyl group and a hydroxyl group introduced is preferred because the resin composition for printing ink can easily have a high molecular weight and a high softening point.

In addition, the physical properties of the component (d) are not particularly limited, but the theoretical acid value is usually about 2 to 200 mgKOH / g, and the weight of the resin composition for printing ink is easily adjusted to a desired range. It is preferable that the average molecular weight is usually about 3,000 to 30,000.

  In the present invention, the component (a) to the component (c) (or the component (a) to the component (d)) are provided for the purpose of imparting solubility in the ink solvent to the printing ink resin composition. In addition, fatty acids (e1) (hereinafter referred to as component (e1)), aliphatic polybasic acids (e2) (hereinafter referred to as component (e2)), aliphatic monoalcohols (e3) (hereinafter referred to as components) (E3) component), aliphatic dialcohols (e4) (hereinafter referred to as component (e4)), aliphatic monoamines (e5) (hereinafter referred to as component (e5)), aliphatic monoepoxies (e6) (Hereinafter referred to as component (e6)), and a resin obtained by partially reacting a hydrophobic compound with a polymer obtained by reacting an α, β-unsaturated carboxylic acid with a hydrophobic polymerizable unsaturated compound (E7) (hereinafter referred to as (e7) component) More least one selected (e) (hereinafter, (e) that the component) can be a reactive component.

As said (e1) component, various well-known things can be especially used without a restriction | limiting, Especially the thing about 10-40 total carbons can be used preferably. Specifically, for example, fatty acids which may be linear, branched or cyclic (capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, Serotic acid, montanic acid, melissic acid, caproleic acid, Linderic acid, fizeteric acid, palmitoleic acid, oleic acid, gondoic acid, cetreic acid, ceracolenoic acid, ximenoic acid, lumenic acid, linoleic acid, eleostearic acid, linolenic acid, Linear fatty acids such as arachidonic acid, sardic acid, nisinic acid, stearolic acid and monomeric acids; branched fatty acids such as isoacids and tuberculostearic acid; cyclic fatty acids such as malvalic acid and shawl mugric acid], alkenyl Succinic acid (anhydride) and alkyl succinic acid (anhydride) [octenylsuccinic acid Acid, octenyl succinic anhydride, decenyl succinic acid, decenyl succinic anhydride, dodecenyl succinic acid, dodecenyl succinic anhydride, tetradecenyl succinic acid, tetradecenyl succinic anhydride, hexadecenyl succinic acid, hexadecenyl succinic anhydride, octadece Nylsuccinic acid, octadecenyl succinic anhydride, eicosenyl succinic acid, eicosenyl succinic anhydride, methylundecenyl succinic acid, methylundecenyl succinic anhydride, allylcyclopentenyl succinic acid, allylcyclopentenyl succinic anhydride, octyl succinic acid Acid, octyl succinic anhydride, decyl succinic acid, decyl succinic anhydride, dodecyl succinic acid, dodecyl succinic anhydride, tetradecyl succinic acid, tetradecyl succinic anhydride, hexadecyl succinic acid, hexadecyl succinic anhydride, octade Succinic anhydride, octadecyl succinic anhydride, methyl undecyl succinic acid, methyl undecyl succinic anhydride, allylcyclopentyl succinic acid, allyl cyclopentyl succinic anhydride, and the like. These may be used alone or in combination of two or more. Can be used in combination.

As said (e2) component, various well-known things can be especially used without a restriction | limiting, Especially the thing about 10-40 total carbons can be used preferably. Specifically, for example, unsaturated carboxylic acid-added higher fatty acids [unsaturated carboxylic acids (sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, docosanedioic acid, tetracosanedioic acid). Acid, hexacosane diacid, octacosane diacid, triacontane diacid; acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, etc.) and semi-drying oil or drying oil (Compounds obtained by addition reaction with higher fatty acids obtained from tung oil, linseed oil, sunflower oil, soybean oil, dehydrated castor oil, etc.)], unsaturated carboxylic acid-added olefin compounds [internal olefin oligomers (straight chain) Α-olefin oligomer, which may be in the form of a ring, a branched chain or a ring, or an oligomer such as ethylene or propylene Obtained by addition reaction (ene addition, etc.) with α, β-unsaturated dicarboxylic acids (maleic acid, maleic anhydride, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, etc.). And dimer acids (unsaturated fatty acids (beef tallow oleic acid, tall oil fatty acid, soybean oil fatty acid, etc.) were dimerized in the presence of a catalyst (montmorillonite clay, etc.). Dimer acid, etc.], α, ω-dicarboxylic acids, and the like. These may be used alone or in combination of two or more. The dimer acids can be obtained as a commercial product containing a dimer acid having 36 carbon atoms and a trimer acid having 54 carbon atoms as a by-product.

As said (e3) component, various well-known things can be especially used without a restriction | limiting, Especially the thing about 10-40 total carbons can be used preferably. Specifically, for example, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, eicosanol, docosanol, tetracosanol, hexacosanol, octacosanol, triacontanol, oleyl alcohol, isotridecyl alcohol, isostearyl alcohol Alcohol, geraniol, rosin alcohol, bisabolol, lanolin alcohol, etc. are mentioned, These can be used individually by 1 type or in combination of 2 or more types.

As said (e4) component, various well-known things can be especially used without a restriction | limiting, Especially the thing about 10-40 total carbons can be used preferably. Specifically, for example, decane diol, dodecane diol, tetradecane diol, hexadecane diol, octadecane diol, decene diol, dodecene diol, tetradecene diol, hexadecene diol, octadecene diol, lanolin alcohol, and the above dimer acids are hydrogenated. These can be used singly or in combination of two or more. The component (e4) and the component (c) partially overlap, but both components are distinguished.

As said (e5) component, various well-known things can be especially used without a restriction | limiting, Especially the thing about 10-40 total carbons can be used preferably. Specifically, for example, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, octadecenylamine, beef tallow alkylamine, soybean alkylamine, dioctadecylamine, dioctadecenylamine, etc. These can be used alone or in combination of two or more.

  As said (e6) component, various well-known things can be especially used without a restriction | limiting, Especially the thing about 10-40 total carbons can be used preferably. Specifically, for example, 1,2-epoxyhexane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxydodecane, 1,2-epoxytetradecane, 1,2-epoxyhexadecane, , 2-epoxyoctadecane, ethylhexyl glycidyl ether, and the like, which can be used alone or in combination of two or more.

The component (e7), that is, a polymer obtained by reacting an α, β-unsaturated carboxylic acid with a hydrophobic polymerizable unsaturated compound (hereinafter abbreviated as a polymer) and a hydrophobic compound are partially reacted. Will be described.

  As the “α, β-unsaturated carboxylic acids”, those similar to those used in the production of the component (a) can be used.

Specific examples of the “hydrophobic polymerizable unsaturated compound” include (a) an aliphatic unsaturated hydrocarbon monomer having about 2 to 50 carbon atoms [ethylene, propylene, 1-n-butene, di- Propylene, diisobutylene, tripropylene, tributylene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docosene, 1-tetracocene, Α-olefins such as 1-hexacocene, 1-octacocene, 1-triacontene, 1-dotriacontene, 1-tetratriatainene, 1-hexatriacontene, 1-octatriaten, 1-tetracontane, butadiene, etc. , Unsaturated polyolefin, etc.], (a) an alicyclic unsaturated hydrocarbon monomer having about 5 to 50 carbon atoms [ Chloropentene, cyclohexene, allylcyclopentane, vinylcyclohexane, etc.], (c) aromatic hydrocarbon monomers having about 8 to 50 carbon atoms (styrene, α-methylstyrene, etc.), (e) rosins [molecules as component (b) Rosin having carbon-carbon unsaturated bond in the inside], (e) Unsaturated oil (semi-drying oil or dry oil such as tung oil, linseed oil, safflower oil, soybean oil, dehydrated castor oil), (f) Examples include higher unsaturated fatty acids derived from the unsaturated oil, and these can be used alone or in combination of two or more.

The polymer can be obtained by copolymerizing the α, β-unsaturated carboxylic acid and the hydrophobic polymerizable unsaturated compound by various known methods. Specific examples of the copolymerization reaction method include a radical polymerization reaction method, a thermal polymerization reaction method, an ionic polymerization reaction method, etc. Among these, the color tone of the obtained polymer does not deteriorate, and the molecular weight is desired. The radical polymerization reaction method is preferred for reasons such as the above range and ease.

In the radical polymerization reaction method, various known radical polymerization initiators can be used. Specifically, for example, an azo initiator [2,2′-azobisisobutyronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis (N, N ′] -Dimethyleneisobutylamidine), etc.], peroxide initiators (di-t-butyl peroxide, benzoyl peroxide, dicumyl peroxide, potassium persulfate, ammonium persulfate, hydrogen peroxide, etc.). These can be used alone or in combination of two or more. The amount of the radical polymerization initiator used is usually within a range of about 0.01 to 10% by weight with respect to the total weight of the α, β-unsaturated carboxylic acids and the hydrophobic polymerizable unsaturated compound. Good.

Further, the temperature of the radical polymerization reaction is not particularly limited, and for example, an optimal temperature may be appropriately set according to the type of the radical initiator, and can be normally set appropriately from a range of about 100 to 200 ° C.

In the radical polymerization reaction method, various solvents can be used. Specifically, for example, aromatic hydrocarbons (toluene, xylene, etc.), alicyclic hydrocarbons (methylcyclohexane, ethylcyclohexane, etc.), aliphatic esters (ethyl acetate, butyl acetate, amyl acetate, cellosolve acetate) , Propylene glycol monomethyl ether, etc.], and these can be used alone or in combination of two or more. The solvent is a polymer that is inactive with both the α, β-unsaturated carboxylic acids and the hydrophobic polymerizable unsaturated compound that are raw materials, and that does not significantly inhibit the radical polymerization reaction and is obtained. It is preferable that the solvent be soluble in the solvent.

The method of partially reacting the polymer with the hydrophobic compound is not particularly limited. For example, in the presence or absence of various known acidic or basic catalysts, both are performed at about 100 to 300 ° C. at 1 to The method of making it react for about 20 hours is mentioned. In addition, since it is easy to adjust the weight average molecular weight of (e7) component, it is preferable to make both react so that about 20 to 80% of the carboxyl group which the said polymer has may be consumed. Examples of the acidic or basic catalyst include mineral acids (hydrochloric acid, sulfuric acid, etc.), sulfonic acids (methanesulfonic acid, paratoluenesulfonic acid, dodecylbenzenesulfonic acid, etc.), metal oxides (zinc oxide, magnesium oxide, calcium oxide). Etc.], metal hydroxides [magnesium hydroxide, calcium hydroxide, etc.], acetates [calcium acetate, magnesium acetate, zinc acetate, etc.], and these may be used alone or in combination of two or more. Can be used.

The physical properties of the component (e7) thus obtained are not particularly limited. For example, the weight average molecular weight is preferably about 4,000 to 35,000. If it is less than 4,000, it tends to be difficult to make the resin for printing ink according to the present invention have a desired molecular weight, and if it exceeds 35,000, the component (e7) and the above ( When reacting the component a) to the component (c) (or the component (a) to the component (d)), it tends to be difficult to control the reaction.

When the components (a) to (e) are used, the ratio (OH / COOH) of the total hydroxyl group equivalent number (OH) to the total carboxyl group equivalent number (COOH) in the printing ink resin composition according to the present invention is In general, it is preferably in the range of about 0.5 to 1.5. By setting it as the said numerical range, the resin composition for printing inks concerning this invention can be made into a desired molecular weight, and an appropriate emulsification characteristic can be provided to printing ink. When calculating the OH / COOH, when the aliphatic monoamines are used as the component (e), the secondary amine is regarded as a monovalent alcohol, and the primary amine is regarded as a divalent alcohol. The total equivalent number of amino groups of the aliphatic monoamines is defined as OH. In addition, when the aliphatic monoepoxy is used as the component (e), it is regarded as a divalent alcohol.

In addition, in the resin composition for printing inks according to the present invention, the amount of each of the (a) component to the (c) component and, if necessary, the (d) component and / or the (e) component is as follows: It is not specifically limited, What is necessary is just to determine suitably according to the kind of ink which uses this resin composition for printing inks. Usually, when the total of component (a), component (b), component (c), component (d) and component (e) is 100% by weight, the amount of component (a) used is 1 to 50% by weight. % (Preferably 10 to 50% by weight), the amount of component (b) used is about 10 to 90% by weight (preferably 20 to 90% by weight), and the amount of component (c) used is about 1 to 30% by weight. (Preferably 2 to 25% by weight), and when component (d) is used, it is about 1 to 50% by weight (preferably 10 to 50% by weight), and when component (e) is used, May be about 3 to 40% by weight (preferably 5 to 30% by weight). By adjusting to these numerical ranges, the balance of various performances of the ink can be kept moderate.

The manufacturing method of the resin composition for printing ink which concerns on this invention is not specifically limited, The manufacturing method of various well-known polyester resins is employable. In the reaction, there are no particular limitations on the raw material charging order, reaction conditions such as catalyst and reaction temperature. Specifically, for example, the (a) component, the (b) component, the (c) component, and the (d) component and / or the (e) component as required are charged into the reactor in a predetermined amount, and the acidic The reaction may be performed for about 1 to 20 hours in the temperature range of about 100 to 300 ° C. in the presence or absence of a basic catalyst. Moreover, as the preparation order of the said raw material, for example, after preparing (a) component, (b) component, and (d) component and / or (e) component as needed, these are melted. The order in which the component (c) is charged is preferable because the component (c) and other components can be reacted more uniformly.

Although the physical property of the resin composition for printing inks concerning this invention is not specifically limited, For example, it is preferable that a weight average molecular weight is about 30,000-400,000 normally, Preferably it is 50,000-200,000. When it is 30,000 or more, a desired softening point tends to be obtained, and when it is 400,000 or less, an insoluble matter tends to be hardly generated in the resin composition for printing ink. Moreover, the said resin composition for printing inks is characterized by having a high softening point, and specifically has a softening point of about 120-200 degreeC normally. By being 120 degreeC or more, the drying property of printed matter is kept moderately, and when it is 200 degrees C or less, the solubility to the ink solvent of the said resin composition can fully be kept. Further, the resin composition for printing ink has a 33% by weight linseed oil viscosity of usually about 1 to 15 Pa · s.

The binder for printing ink of this invention contains the said resin composition for printing inks, vegetable oil, a gelatinizer, and a solvent as needed, and takes the form of what is called a gel varnish. The content of the printing ink resin composition in the printing ink binder is not particularly limited, but is usually about 20 to 60% by weight, preferably about 30 to 50% by weight in consideration of workability during printing. Range.

The vegetable oils are not particularly limited, and various known oils can be used. Specifically, for example, linseed oil, tung oil or a polymerized oil thereof, safflower oil, dehydrated castor oil, soybean oil, soybean oil fatty acid monoester (soybean oil fatty acid methyl, soybean oil fatty acid ethyl, soybean oil fatty acid butyl, etc.) These can be used singly or in combination of two or more. Among these, vegetable oil having an unsaturated bond is preferable in consideration of drying properties of printed matter, and soybean oil and soybean oil fatty acid monoester are preferable in consideration of environmental aspects. In addition, content of this vegetable oil in the binder for printing inks is not specifically limited, What is necessary is just to determine suitably in consideration of the kind of ink.

The gelling agent is not particularly limited, and various known ones can be used. Specifically, for example, aluminum octylate, aluminum stearate, aluminum triisopropoxide, aluminum dipropoxide monoacetyl acetate and the like can be used, and these can be used alone or in combination of two or more. Can do. The content of the gelling agent in the printing ink binder is not particularly limited, and may be appropriately determined in consideration of the type of ink.

The solvent is not particularly limited, and various known solvents can be used. Specifically, for example, the above-mentioned various types can be used, and preferably a petroleum-based solvent having a boiling point of 200 ° C. or higher and an aromatic hydrocarbon content of 1% or less (for example, Nippon Oil Corporation ) No. 0 solvent, AF solvent Nos. 4-7, etc.) can be used. In addition, content of this solvent in the binder for printing inks is not specifically limited, What is necessary is just to determine suitably in consideration of the kind of ink.

In addition, the binder for printing ink may contain other binder resin as necessary to the extent that the performance of the printing ink is not impaired. Specific examples include petroleum resins, alkyd resins, rosin ester phenol resins, vinyl resins, acrylic resins, nitrocellulose, and the like, and these can be used alone or in combination of two or more. .

The viscosity of the binder for printing inks thus obtained is not particularly limited, but in consideration of practical use, the cone and plate viscometer measured value at 25 ° C. is usually in the range of about 10 to 5,000 Pa · s. Is preferred.

The printing ink of the present invention includes the printing ink binder (gel varnish), vegetable oils and / or petroleum solvents having a boiling point of 200 ° C. or higher and an aromatic hydrocarbon content of 1% or less, and pigments, if necessary. Containing various adjuvants. The vegetable oils and the petroleum solvent are the same as those described above, and these may be contained in a printing ink binder.

The pigment is not particularly limited, and various known pigments can be used. Specifically, for example, soluble azo pigments [C-based (β-naphthol-based) pigments, 2B-based pigments, 6B-based (β-oxynaphthoic pigments, etc.)] and insoluble azo pigments [β-naphthol-based pigments, β-oxynaphthoic acid] Anilide pigments, monoazo yellow pigments, disazo yellow pigments, pyrazolone pigments, etc.), phthalocyanine pigments (copper phthalocyanine (α blue, β blue, ε blue) pigments, halogenated copper phthalocyanine pigments, metal-free phthalocyanine pigments) Organic pigments such as lead, zinc yellow, bitumen, barium sulfate, cadmium red, titanium oxide, zinc white, bengara, alumina white, calcium carbonate, ultramarine, carbon black, graphite, aluminum powder, etc. Can be mentioned.

The adjuvant is not particularly limited, and various known ones can be used. Specifically, for example, plasticizers (phthalate ester plasticizers, fatty acid ester plasticizers, epoxy plasticizers, etc.), antioxidants (metal soaps, phenols, etc.), lubricants (paraffin wax, hydrocarbons, etc.) Resin, fatty acid-based resin, etc.] and antifoaming agents [alcohol-based antifoaming agents, fatty acid-based antifoaming agents, silicone oils, etc.], and these may be used alone or in combination of two or more. Can do.

The method for preparing the printing ink is not particularly limited, and various known means can be employed. Specifically, for example, each raw material of the printing ink described above is kneaded using a normal ink manufacturing apparatus such as a roll mill, a ball mill, an attritor, a sand mill, etc., and adjusted to an appropriate ink constant, thereby providing an offset sheet. Desired printing inks such as leaf ink (sheet-fed ink), offset rotary ink (off-wheel ink), waterless offset ink, and newspaper ink can be produced.

Moreover, the composition of the printing ink is not particularly limited, and may be appropriately determined according to the use of the ink. For example, the content of the binder for printing ink may be in a range where the solid content concentration is usually about 10 to 50% by weight.

EXAMPLES Hereinafter, although a manufacture example and an Example are given and this invention is demonstrated further more concretely, these do not limit this invention. Hereinafter, “parts” means parts by weight.

Production Example 1
(Manufacture of component (a))
A reaction vessel equipped with a stirrer, a reflux condenser with a water separator and a thermometer was charged with 3,000 parts of a terpene resin (trade name: YS Resin PX-1250, manufactured by Yasuhara Chemical Co., Ltd.), and the reaction system was placed under a nitrogen atmosphere. While stirring, the temperature was raised to 180 ° C. to melt it. Next, 150 parts of maleic anhydride was charged into the reaction vessel, and the reaction system was heated to 230 ° C. with stirring and kept warm for 3 hours. Thereafter, the reaction vessel was cooled to obtain 3080 parts of a solid carboxyl group-containing terpene resin (theoretical acid value 55, weight average molecular weight 1,200). The theoretical acid value is a value obtained as [(150 / 98.1) / 3150] × 2 × 56.1 × 1000≈55. (The same applies to the calculation method below.)

In addition, the weight average molecular weight of this carboxyl group-containing terpene resin means a polystyrene conversion value measured under a THF solvent by gel permeation chromatography (GPC), and as a GPC apparatus, HLC-8020 (manufactured by Tosoh Corporation) is used. As the column, a TSK-GEL column (manufactured by Tosoh Corporation) was used (the same applies hereinafter).

Production Example 2
(Production of component (b))
1,000 parts of gum rosin was charged into the same reaction vessel as in Production Example 1, and the temperature was raised to 180 ° C. while stirring the reaction system in a nitrogen atmosphere to melt it. Next, 267 parts of fumaric acid was charged in the same reaction vessel, and the reaction system was heated to 230 ° C. with stirring and kept warm for 1 hour. Thereafter, the reaction vessel was cooled to obtain 1240 parts of solid fumaric acid-modified rosin (acid value 342.0, softening point 148 ° C.). The acid value and softening point were measured according to JIS K5601 (the same applies hereinafter).

Production Example 3
(Production of component (d))
In a reaction vessel similar to Production Example 1, 1,000 parts of DCPD petroleum resin (trade name Quinton 1325, manufactured by Nippon Zeon Co., Ltd.) was charged, and the temperature was raised to 180 ° C. while stirring the reaction system in a nitrogen atmosphere. This was melted. Next, 70 parts of maleic anhydride was charged into the same reaction vessel, and the reaction system was heated to 230 ° C. with stirring and kept warm for 3 hours. Thereafter, the reaction vessel was cooled to obtain 1010 parts of a solid carboxyl group-containing petroleum resin (theoretical acid value 75, weight average molecular weight 4,000).

Production Example 4
(Production of component (e))
A reaction vessel similar to Production Example 1 was charged with 238 parts of an α-olefin having a carbon number of 16 to 18 (trade name: Dialene 168, manufactured by Mitsubishi Chemical Corporation), and a temperature of 155 to 180 ° C. while stirring in a nitrogen atmosphere. The temperature was raised to the range. Next, 98 parts of maleic anhydride and 13.5 parts of di-t-butyl peroxide (trade name Perbutyl D, manufactured by NOF Corporation) were continuously added to the reaction system over 1 hour, and then 155 The polymer was obtained by incubating at ˜160 ° C. for 1 hour. Next, 271 parts of stearyl alcohol was further added to the reaction system, and the reaction was allowed to proceed at 220 ° C. for 4 hours to obtain 580 parts of resin (I). The resin (I) had a weight average molecular weight of 30,000 and an acid value of 70.

Production Example 5
(Production of component (e))
A reaction vessel similar to Production Example 1 was charged with 230 parts of an α-olefin having a carbon number of 16 to 18 (trade name: Dialene 168, manufactured by Mitsubishi Chemical Corporation), and a temperature of 155 to 180 ° C. while stirring in a nitrogen atmosphere. The temperature was raised to the range. Next, 90 parts of maleic anhydride and 13.0 parts of di-t-butyl peroxide (trade name: Perbutyl D, manufactured by NOF Corporation) were continuously added over 1 hour. Furthermore, it kept at 155-160 degreeC for 1 hour, and obtained the polymer. Next, 260 parts of stearyl alcohol was further added to the reaction system, and the reaction was allowed to proceed at 220 ° C. for 4 hours to obtain 550 parts of resin (II). The resin (II) had a weight average molecular weight of 28,000 and an acid value of 65.

Production Example 6
(Production of alkylphenol-formaldehyde condensate)
Into a reaction vessel equipped with a stirrer, a reflux condenser with a water separator and a thermometer, 1,000 parts of nonylphenol, 270 parts of paraformaldehyde and 1,000 parts of water were charged, and the temperature was raised to 50 ° C. with stirring. Next, 100 parts of sodium hydroxide was charged into the same reaction vessel, the reaction system was gradually heated to 90 ° C. while cooling, and then kept warm for 2.5 hours, and sulfuric acid was added dropwise to adjust the pH to around 6. . Thereafter, 150 parts of xylene was added, the aqueous layer containing formaldehyde and the like was removed, and the contents were further cooled to obtain 1,200 of a 70% xylene solution of resol-type nonylphenol.

Example 1
In a reaction vessel equipped with a stirrer, a reflux condenser with a water separator and a thermometer, 424 parts of polar group-containing terpene resin obtained in Production Example 1, polymerized rosin (trade name: Silvatac 140, manufactured by Silvachem, acid value 140) 355 parts, 45 parts of fumaric acid-modified rosin obtained in Production Example 2, and 80 parts of alkenyl succinic anhydride (trade name: Paverus NP, manufactured by Shin Nippon Oil Co., Ltd.) were charged and stirred while stirring them under a nitrogen atmosphere. The temperature was raised to 0 ° C. to melt. Next, 29 parts of pentaerythritol and 29 parts of glycerin were charged, and the temperature was raised to 260 ° C. with stirring. Next, when the acid value of the composition of the reaction system became 30 or less, 1 part of paratoluenesulfonic acid was added, and the reaction was further continued until the acid value became 20 or less. Thereafter, the composition was adjusted so that the 33% by weight linseed oil viscosity was 8.0 Pa · s, further reduced in pressure at 0.02 MPa for 10 minutes, and then cooled to obtain a solid resin composition for printing ink. 910 parts of product (1-1) were obtained. The acid value of the resin composition for printing ink (1-1) was 12.5 (mgKOH / g), the softening point was 171 ° C., and the weight average molecular weight was 165,000. Moreover, the tolerance of the aliphatic hydrocarbon solvent (trade name: No. 0 Solvent, manufactured by Shin Nippon Oil Co., Ltd.) solution of the resin composition was 1.5 g / g. These physical properties are shown in Table 1.

Example 2
In the same reaction vessel as in Example 1, 424 parts of the carboxyl group-containing terpene resin obtained in Production Example 1, 341 parts of polymerized rosin (trade name Silvatac 140, manufactured by Silvachem, acid value 140) and Production Example 1 were obtained. 40 parts of fumaric acid-modified rosin was charged, and the mixture was heated to 180 ° C. and melted while stirring under a nitrogen atmosphere. Next, 69 parts of 1,2-epoxyoctadecanoic acid, 29 parts of pentaerythritol and 29 parts of glycerin were charged, and the temperature was raised to 260 ° C. with stirring. Next, when the acid value of the composition of the reaction system became 30 or less, 1 part of paratoluenesulfonic acid was added, and the reaction was further continued until the acid value became 20 or less. Thereafter, the composition was adjusted so that the 33% by weight linseed oil viscosity was 8.0 Pa · s, further reduced in pressure at 0.02 MPa for 10 minutes, and then cooled to obtain a solid resin composition for printing ink. 830 parts of thing (1-2) were obtained. Table 1 shows the physical properties of (1-2).

Example 3
In the same reaction vessel as in Example 1, 416 parts of the carboxyl group-containing terpene resin obtained in Production Example 1, 345 parts of polymerized rosin (trade name: Silvatac 140, manufactured by Silvachem, acid value 140), and Production Example 1 Fumaric acid-modified rosin 55 parts 90 parts of the resin (I) obtained in Production Example 4 were charged, and these were heated to 180 ° C. while being stirred in a nitrogen atmosphere and melted. Next, 29 parts of pentaerythritol and 29 parts of glycerin were charged, and the temperature was raised to 260 ° C. with stirring. Next, when the acid value of the composition of the reaction system became 30 or less, 1 part of paratoluenesulfonic acid was added, and the reaction was further continued until the acid value became 20 or less. Thereafter, the composition was adjusted so that the 33% by weight linseed oil viscosity was 8.0 Pa · s, further reduced in pressure at 0.02 MPa for 10 minutes, and then cooled to obtain a solid resin composition for printing ink. 900 parts of thing (1-3) were obtained. The physical properties of the (1-3) are shown in Table 1.

Example 4
In the same reaction vessel as in Example 1, 212 parts of carboxyl group-containing terpene resin of Production Example 1, 355 parts of polymerized rosin (trade name: Silvatac 140, manufactured by Silvachem, acid value 140), and fumaric acid-modified rosin of Production Example 2 45 parts, 212 parts of the carboxyl group-containing petroleum resin of Production Example 3 and 80 parts of alkenyl succinic anhydride (trade name: Paverus NP, manufactured by Shin Nippon Oil Co., Ltd.) were added up to 180 ° C. with stirring in a nitrogen atmosphere. The temperature was raised and melted. Next, 29 parts of pentaerythritol and 29 parts of glycerin were charged, and the temperature was raised to 260 ° C. with stirring. Next, when the acid value of the composition of the reaction system became 30 or less, 1 part of paratoluenesulfonic acid was added, and the reaction was further continued until the acid value became 20 or less. Thereafter, the composition was adjusted so that the 33% by weight linseed oil viscosity was 8.0 Pa · s, further reduced in pressure at 0.02 MPa for 10 minutes, and then cooled to obtain a solid resin composition for printing ink. 920 parts of product (1-4) were obtained. Table 1 shows the physical properties of (1-4).

Example 5
In the same reaction vessel as in Example 1, 208 parts of carboxyl group-containing terpene resin, 340 parts of polymerized rosin (trade name Silvatac 140, manufactured by Silvachem, acid value 140) and 60 parts of fumaric acid-modified rosin of Production Example 1 were produced. 208 parts of the carboxyl group-containing petroleum resin of Example 3 and 90 parts of the resin (II) of Production Example 5 were charged, and these were heated to 180 ° C. with stirring in a nitrogen atmosphere and melted. Next, 29 parts of pentaerythritol and 29 parts of glycerin were charged, and the temperature was raised to 0 ° C. with stirring. Next, when the acid value of the composition of the reaction system became 30 or less, 1 part of paratoluenesulfonic acid was added, and the reaction was further continued until the acid value became 20 or less. Thereafter, the composition was adjusted so that the 33% by weight linseed oil viscosity was 8.0 Pa · s, further reduced in pressure at 0.02 MPa for 10 minutes, and then cooled to obtain a solid resin composition for printing ink. 905 parts of product (1-5) was obtained. The physical properties of (1-5) are shown in Table 1.

Example 6
In the same reaction vessel as in Example 1, 212 parts of carboxyl group-containing terpene resin of Production Example 1, 355 parts of polymerized rosin (trade name: Silvatac 140, manufactured by Silvachem, acid value 140), and fumaric acid-modified rosin of Production Example 2 45 parts and 80 parts of alkenyl succinic anhydride (trade name: Paverus NP, manufactured by Shin Nippon Oil Co., Ltd.) were charged, and the mixture was heated to 180 ° C. with stirring in a nitrogen atmosphere and melted. Next, 10 parts of pentaerythritol and 10 parts of glycerin were added, and the reaction was started by raising the temperature to 260 ° C. with stirring in a nitrogen atmosphere. Next, when the acid value of the composition of the reaction system became 30 or less, 1 part of paratoluenesulfonic acid was charged, and the reaction was advanced until the acid value became 20 or less. Thereafter, the obtained resin composition was adjusted so that the 33 wt% linseed oil viscosity was 3.0 Pa · s, further reduced in pressure at 0.02 MPa for 10 minutes, and then cooled to obtain a solid printing ink. Resin composition (1-6) for 680 parts was obtained. The physical properties of (1-6) are shown in Table 1.

Example 7
In the same reaction vessel as in Example 1, 212 parts of carboxyl group-containing terpene resin of Production Example 1, 355 parts of polymerized rosin (trade name: Silvatac 140, manufactured by Silvachem, acid value 140), and fumaric acid-modified rosin of Production Example 2 45 parts, 212 parts of polar group-containing petroleum resin of Production Example 3 and 100 parts of alkenyl succinic anhydride (trade name Pavelas NP, manufactured by Nippon Oil Corporation) were stirred up to 180 ° C. while stirring them in a nitrogen atmosphere. The temperature was raised and melted. Next, 58 parts of pentaerythritol and 58 parts of glycerin were added, and the reaction was started by raising the temperature to 260 ° C. while stirring them under a nitrogen atmosphere. Next, when the acid value of the composition of the reaction system became 30 or less, 1 part of paratoluenesulfonic acid was charged, and the reaction was advanced until the acid value became 20 or less. Note that the viscosity of the reaction system was high, and stirring was somewhat difficult. Thereafter, the obtained resin composition was adjusted so that the 33% by weight linseed oil viscosity was 18.0 Pa · s, further reduced in pressure at 0.02 MPa for 10 minutes, and then cooled to obtain a solid printing ink. Resin composition (1-7) 980 parts was obtained. The physical properties of (1-7) are shown in Table 1.

Comparative Example 1
In a reaction vessel similar to that in Example 1, 552 parts of gum rosin was charged, and the mixture was heated to 230 ° C. while being stirred in a nitrogen atmosphere and melted. Subsequently, 52 parts of pentaerythritol and 2 parts of zinc oxide were added, the temperature was raised to 260 ° C. with stirring, and the reaction was continued until the acid value became 20 or less. Next, the reaction product was cooled to 230 ° C. and kept warm, and 394 parts of a 70% xylene solution of resole-type nonylphenol of Production Example 6 (276 parts of solid content) was placed in the temperature range of 230 to 260 ° C. over 4 hours. It was dripped in the reaction system. After completion of the dropwise addition, the reaction system was adjusted so that the 33 wt% linseed oil viscosity was 8.0 Pa · s, decompressed at 0.02 MPa for 10 minutes, and cooled to obtain 950 parts of rosin-modified phenolic resin. Table 1 shows the physical properties of the resin.

Comparative Example 2
In the same reaction vessel as in Example 1, 450 parts of polymerized rosin (trade name: Silvatac 140, manufactured by Silvachem, acid value 140), 120 parts of fumaric acid-modified rosin obtained in Production Example 2, and obtained in Production Example 3 298 parts of a carboxyl group-containing petroleum resin were charged, and these were heated to 180 ° C. and melted while stirring in a nitrogen atmosphere. Next, 29 parts of pentaerythritol and 31 parts of glycerin were added, and the reaction was started by raising the temperature to 260 ° C. while stirring them in a nitrogen atmosphere. Next, when the acid value of the composition of the reaction system became 30 or less, 1 part of paratoluenesulfonic acid was charged, and the reaction was advanced until the acid value became 20 or less. Thereafter, the obtained resin composition was adjusted so that the 33% by weight linseed oil viscosity was 8.0 Pa · s, further reduced in pressure at 0.02 MPa for 10 minutes, and then cooled to obtain a solid printing ink. Obtained 855 parts of a resin composition. Table 1 shows the physical properties of the resin composition.

Preparation of gel varnish A
180 parts of a resin composition for printing ink obtained in Example 1, 45 parts of soybean oil, 4 parts of soybean oil and 45.0 parts of an alicyclic hydrocarbon solvent (trade name: AF Solvent No. 7, manufactured by Shin Nippon Oil Co., Ltd.) And dissolved for 30 minutes to obtain a varnish. After cooling the varnish to 60 ° C., 1.0 part of aluminum ethyl acetoacetate diisopropylate (trade name: ALCH, manufactured by Kawaken Fine Chemical Co., Ltd.) was added and stirred, and the temperature was raised to 190 ° C. for 1 hour. It was kept warm to obtain a gel varnish. Gel varnishes were prepared by the same procedure for the resins obtained in Examples 2-7 and Comparative Examples 1-2. In addition, when the resin composition for printing inks of Example 7 was used, a part of insoluble matter was generated when the gel varnish was prepared.

Ink preparation A
Using each of the gel varnishes, a printing ink was prepared at a blending ratio shown in Table 2 so that the tack value of the printing ink was 6.5 ± 0.5 and the flow value was 41.0 ± 1.0 (three bottles) Use a roll mill).

Ink performance test A
(Glossy)
After 0.4 ml of ink was developed on art paper with an RI tester (product name “RI Tester”, Ishikawajima Industrial Machinery Co., Ltd.), it was exposed to an atmosphere of 160 ° C. for 10 seconds, 20 ° C., 65% R.D. H. After adjusting the humidity for 24 hours, the reflectance of 60 ° -60 ° was measured with a gloss meter (product name “Gloss meter”, manufactured by Nippon Denshoku Industries Co., Ltd.). The larger the value, the better the gloss. The results are shown in Table 3.
(Drying)
After 0.4 ml of ink was developed on art paper with an RI tester (product name “RI Tester”, manufactured by Ishikawajima Sangyo Co., Ltd.), it was exposed to an atmosphere of 160 ° C. for 2 seconds, 4 seconds, and 6 seconds, respectively. The state without stickiness due to finger touch was judged as dry. The smaller the value, the better the drying property. The results are shown in Table 3.
(Missing)
2.6 ml of ink was developed on an incometer (product name “DIGITAL INKOMETER” manufactured by Toyo Seiki Co., Ltd.), rotated at a roll temperature of 30 ° C. for 1 minute at 400 rpm, and further for 2 minutes at 1800 rpm, and placed directly under the roll. Evaluation was made by observing the degree of ink scattering on white paper. The larger the value, the better the misting.
(Emulsification rate)
3.9 ml of ink was developed on a dynamic emulsification tester (product name “ink emulsification tester”, manufactured by Nippon Rheology Equipment Co., Ltd.) and supplied with pure water at a roll temperature of 30 ° C. and 200 rpm at a rate of 5 ml / min. The water content in the ink was measured using an infrared moisture meter (product name “moisture meter IR-MF type”, manufactured by Chino Co., Ltd.). The smaller the value, the better the emulsification resistance of the printing ink. The results are shown in Table 3.
(Liquidity)
1.3 ml of ink was placed on the upper end of a glass plate inclined at 60 °, and the distance of the ink that flowed for 30 minutes was measured. It means that fluidity | liquidity is so favorable that a numerical value is large. The results are shown in Table 3.

Preparation of gel varnish B
A varnish was obtained by mixing and dissolving 45 parts of the resin composition for printing ink obtained in Example 1 and 55 parts of soybean oil at 180 ° C. for 30 minutes. After cooling the varnish to 60 ° C., 0.5 parts of aluminum ethyl acetoacetate diisopropylate (trade name: ALCH, manufactured by Kawaken Fine Chemical Co., Ltd.) was added and stirred, and the temperature was raised to 190 ° C. for 1 hour. It was kept warm to obtain a gel varnish. Moreover, the gel varnish was prepared according to the same procedure also about resin obtained in Examples 2-7 and Comparative Examples 1-2. In addition, when the resin composition for printing inks of Example 7 was used, a part of insoluble matter was generated when the gel varnish was prepared.

Ink Preparation B
Using each gel varnish, a printing ink was prepared at a blending ratio shown in Table 4 (using a three-roll mill).

上記配合に基づいてインキのタック値が７．０±０．５、フロー値が３５．０±１．０となるよう適宜調整した。

Based on the above formulation, the tack value of the ink was adjusted appropriately to 7.0 ± 0.5 and the flow value was adjusted to 35.0 ± 1.0.

Ink performance test B:
(Glossy)
Gloss was measured by the same method as described above using 0.27 ml of ink. The results are shown in Table 5.
(Drying)
After 0.27 ml of ink was developed on sulfuric acid paper using the RI tester, the sulfuric acid paper was applied to the C-type drying tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) with the sulfuric acid paper superimposed on the color development surface. It was wound around a rotating drum. Next, the weight and the pressure gear are gently lowered onto the sulfuric acid paper, the drum is rotated, and the time when the tooth profile of the pressure gear hardly shifts is defined as the drying time. The smaller the value, the better the drying property. The results are shown in Table 5.
(Missing)
2.6 ml of ink was developed on the incometer, rotated at a roll temperature of 30 ° C. for 1 minute at 400 rpm, and further rotated at 1200 rpm for 2 minutes, and evaluated by observing the degree of ink scattering on white paper placed directly under the roll. Went. The larger the value, the better the misting.
(Emulsification rate)
Emulsion resistance was measured by the same method as described above using 3.9 ml of ink. The results are shown in Table 5.
(Liquidity)
The fluidity was observed in the same manner as described above using 1.3 ml of ink. The results are shown in Table 5.

From the results of Tables 3 and 5, the printing ink using the resin composition for printing ink according to the present invention (Examples 1 to 7) has the same or higher performance as the rosin-modified phenolic resin (Comparative Example 1). It can be seen that it is particularly excellent in terms of fluidity. Moreover, the printing ink using the printing ink resin composition (Comparative Example 2) that does not use the polar group-containing terpene resins is more fluid than the printing ink resins (Examples 1 to 7) of the present invention. It turns out that it is inferior in terms of sex. In addition, as a resin composition for printing inks according to the present invention, those having a softening point higher than 120 ° C. (Examples 1 to 5) are dry as compared with those not being so (Example 6). It can be seen that is improved.

Claims (13)

The resin composition for printing inks which uses polar group containing terpene resins (a), rosins (b), and polyols (c) as reaction components. Furthermore, the resin composition for printing inks of Claim 1 which uses polar group containing petroleum resins (d) as a reaction component. Furthermore, fatty acids (e1), aliphatic polybasic acids (e2), aliphatic monoalcohols (e3), aliphatic dialcohols (e4), aliphatic monoamines (e5), aliphatic monoepoxies (e6) , And a polymer obtained by reacting an α, β-unsaturated carboxylic acid with a hydrophobic polymerizable unsaturated compound and a resin (e7) obtained by partially reacting the hydrophobic compound. The resin composition for printing ink according to claim 1 or 2, wherein at least one (e) is used as a reaction component. The resin composition for printing ink according to any one of claims 1 to 3, wherein the polar group-containing terpene resins (a) are obtained by reacting terpene resins with α, β-unsaturated carboxylic acids. The resin composition for printing ink according to any one of claims 1 to 4, wherein the polar group-containing petroleum resins (d) are obtained by reacting petroleum resins with α, β-unsaturated carboxylic acids. . The resin composition for printing ink according to any one of claims 1 to 5, wherein the resin component has a weight average molecular weight of 30,000 to 400,000. The resin composition for printing ink according to any one of claims 1 to 6, which has a softening point of 120C to 200C. A method for producing a resin composition for printing ink, comprising reacting polar group-containing terpene resins (a), rosins (b) and polyols (c). Furthermore, polar group containing petroleum resin (d) is made to react, The manufacturing method of Claim 8 characterized by the above-mentioned. Furthermore, fatty acids (e1), aliphatic polybasic acids (e2), aliphatic monoalcohols (e3), aliphatic dialcohols (e4), aliphatic monoamines (e5), aliphatic monoepoxies (e6) Selected from the group consisting of a polymer obtained by reacting an α, β-unsaturated carboxylic acid with a hydrophobic polymerizable unsaturated compound and a resin (e7) obtained by partially reacting the hydrophobic compound. 10. The method for producing a resin composition for printing ink according to claim 8, wherein at least one kind (e) is reacted. The binder for printing inks containing the resin composition for printing inks in any one of Claims 1-7, vegetable oil, a gelatinizer, and a solvent as needed. Printing ink containing the binder for printing inks of Claim 11. The printing ink according to claim 12, further comprising a vegetable oil and / or a petroleum solvent having a boiling point of 200 ° C. or higher and an aromatic hydrocarbon content of 1% or less, and a pigment.