CN104487528A - Resin for offset printing ink - Google Patents

Abstract

This resin for offset printing ink comprises a resin which is obtained by reacting a resin raw material which contains rosins, an alpha,beta-unsaturated carboxylic acid or an anhydride thereof, a metal compound, a fatty acid or fat and oil, and a polyalcohol, wherein the fatty acid or fat and oil are contained in an amount of 10 to 50 mass% with respect to the total amount of the resin raw material, and the metal compound is contained in an amount of 0.5 to 5 mass% with respect to the total amount of the resin raw material in terms of the metal amount of the metal compound.

Description

Resins for offset printing inks

technical field

The present invention relates to rosin-modified polyesters having high solubility in lacquering, imparting good gloss to printed matter, and having excellent drying properties and anti-fogging properties during printing, for use in offset printing inks resin.

Background technique

Offset printing is suitable for color printing, gradation expression, etc., and can realize vivid printing, and is also suitable for mass printing. Therefore, it is widely used in the printing of newspapers, leaflets, catalogs, books, etc. Currently, rosin-modified phenolic resins are mainly used as binder resins for offset printing. The reason for this is that the rosin-modified phenolic resin has the following features (A) to (C).

(A) It has high pigment dispersibility and can impart good gloss.

(B) It is easy to adjust the viscoelasticity of the ink.

(C) It is easy to adjust the balance of hardness and softness of the printed film.

Usually, the phenol-formaldehyde precondensate is modified with rosin, and esterified with polyhydric alcohol if necessary to obtain a rosin-modified phenolic resin. As such, since formaldehyde is used as a raw material, rosin-modified phenolic resins have problems in terms of the environment, work sanitation, and the like. In addition, it has been reported that alkylphenol components exhibit environmental hormone effects.

On the other hand, a rosin-modified polyester-based binder resin for offset ink that does not use aldehydes and phenols as a raw material is being developed (Patent Document 1).

The rosin-modified polyester resin is obtained, for example, by reacting rosin with a polyhydric alcohol, a polybasic acid, a fatty acid, and the like. However, rosin-modified polyester resins are not as good as rosin-modified polyester resins in setting the gloss of ink, the balance of various physical properties such as solubility and drying properties in ink solvents, and the balance of hardness and flexibility of printing coatings. Bakelite is so easy. Generally, in offset printing, good gloss and flexibility of paint film are required to be imparted to printed matter, and compatibility with non-aromatic ink solvents (aliphatic hydrocarbon solvents) or oils and fats is also required during varnishing. Therefore, it is sufficient to increase the amount of fatty acid in the raw material, especially higher fatty acid, and this formulation is also economical.

However, if the conventional rosin-modified phenolic resin is used, its alkylphenol component can achieve a balance of hardness, flexibility, hydrophilicity, lipophilicity, and the like. However, if the amount of fatty acid used is increased, the hardness and dryness of the ink will be greatly reduced, and the anti-fogging property during printing will also be reduced. This is because although the long-chain alkyl group derived from higher fatty acid contributes to lipophilicity and plasticity, on the other hand, the part related to hardness and hydrophilicity is insufficient in the resin used for ink.

prior art literature

patent documents

Patent Document 1 Japanese Patent Laid-Open Publication "JP-A-2000-159867"

Contents of the invention

The problem to be solved by the invention

The subject of the present invention is to provide a resin for offset printing ink which has high solubility when lacquered and can impart a printed matter, and an offset printing ink using the resin for offset printing ink. Good gloss, and has excellent drying and anti-fogging properties when printing.

Another object of the present invention is to provide a method for easily preparing the above-mentioned resin for offset printing ink.

means of solving problems

In order to solve the above-mentioned problems, the inventors of the present invention conducted intensive studies, and as a result, found a solution including the following ideas, and completed the present invention.

(1) Resins for offset printing inks comprising resins obtained by reacting resin raw materials containing rosins, α,β-unsaturated carboxylic acids or anhydrides thereof, metal compounds, fatty acids, or oils and fats , and polyols, characterized in that,

Relative to the total amount of the resin raw material, the fatty acid or the oil is contained in an amount of 10% by mass to 50% by mass, and if the metal compound is calculated as the amount of metal in the metal compound, relative to the The total amount of the resin raw material contains 0.5 mass% to 5 mass% metal.

(2) The resin for offset printing ink as described in (1), wherein the main component of the fatty acid is a fatty acid having 12 or more carbon atoms.

(3) The resin for offset printing ink as described in (1) or (2), which comprises a cross-linked body composed of the fatty acid and

At least one selected from the rosins, the α, β-unsaturated carboxylic acids or their anhydrides, and the adducts formed from the rosins and the α, β-unsaturated carboxylic acids or their anhydrides kind,

Formed by metal ion crosslinking from the metal compound.

(4) The resin for offset printing ink as described in (3), wherein the cross-linked body is composed of the carboxyl group present in the fatty acid and the

At least one selected from the rosins, the α, β-unsaturated carboxylic acids or their anhydrides, and the adducts formed from the rosins and the α, β-unsaturated carboxylic acids or their anhydrides carboxyl group

Formed by metal ions from the metal compound.

(5) The resin for offset printing ink according to (1), wherein the fat is a triglyceride formed of fatty acid and glycerin, and at least one fatty acid has 12 or more carbon atoms.

(6) The resin for offset printing ink as described in (1) or (5), which comprises a cross-linked body made of a resin selected from the group consisting of the rosin, the α,β-unsaturated carboxyl At least one of acid or anhydride thereof, and at least one of adducts formed from said rosins and said α,β-unsaturated carboxylic acid or anhydride thereof,

Formed by metal ion crosslinking from the metal compound.

(7) The resin for offset printing ink as described in (6), wherein the cross-linked body is selected from the group consisting of the rosin, the α,β-unsaturated carboxylic acid or its anhydride, and the the carboxyl group present in at least one of the adducts formed of the rosins and the α, β-unsaturated carboxylic acids or their anhydrides,

Formed by metal ions from the metal compound.

(8) The resin for offset printing ink according to any one of (1) to (7), wherein the resin raw material further contains an aromatic carboxylic acid.

(9) The resin for offset printing ink according to any one of (1) to (8), wherein the metal compound contains a divalent or higher metal compound.

(10) The preparation method of the resin that is used for offset printing ink, is characterized in that, comprises:

The first step is to form a cross-linked body, the cross-linked body is composed of fatty acids and selected from rosins, α, β-unsaturated carboxylic acids or their anhydrides, and the rosins and the α, β-unsaturated carboxylic acids At least one of the adducts formed by acids or anhydrides thereof, formed by cross-linking of metal ions from metal compounds; and

In the second step, at least one selected from the rosin, the α, β-unsaturated carboxylic acid or its anhydride, the adduct, the cross-linked body, and the fatty acid and the polyhydric alcohol carry out an esterification reaction to form an ester,

The proportion of the fatty acid is 10 relative to the total amount of the resin raw material containing the rosin, the α, β-unsaturated carboxylic acid or its anhydride, the metal compound, the fatty acid, and the polyol. % by mass to 50% by mass, and if the metal compound is calculated as the amount of metal in the metal compound, the proportion of the metal is 0.5% by mass to 5% by mass.

(11) The preparation method of the resin that is used for offset printing ink, is characterized in that, comprises:

Step A, forming a cross-linked body, the cross-linked body is selected from rosin, α, β-unsaturated carboxylic acid or its anhydride, and the rosin and the α, β-unsaturated carboxylic acid or its anhydride at least one of anhydride-formed adducts formed by crosslinking metal ions from said metal compound;

In the B step, at least one selected from the rosin, the α, β-unsaturated carboxylic acid or its anhydride, the adduct, and the cross-linked body is subjected to an esterification reaction with a polyhydric alcohol. form esters; and

C step, making the ester obtained in the B step and the oil undergo transesterification reaction, and introducing the alkyl group in the oil into the ester,

The proportion of the fatty acid is 10 relative to the total amount of the resin raw material including the rosin, the α, β-unsaturated carboxylic acid or its anhydride, the metal compound, the fat, and the polyol. % by mass to 50% by mass, and if the metal compound is calculated as the amount of metal in the metal compound, the proportion of the metal is 0.5% by mass to 5% by mass.

(12) An ink for offset printing comprising the resin for offset printing ink described in any one of (1) to (9) above, a drying oil or a semi-drying oil, a solvent, and a pigment.

Beneficial effect

Resins for offset printing inks having high solubility in varnishing can be obtained according to the invention. In addition, the ink for offset printing obtained by using this resin can impart good gloss to printed matters, and has excellent drying properties and anti-fogging properties at the time of printing. According to the production method of a resin for offset printing ink of the present invention, such a resin for offset printing ink can be easily obtained.

Detailed ways

The resin for offset printing ink of the present invention includes a resin obtained by reacting a resin raw material including rosin, α,β-unsaturated carboxylic acid or anhydride thereof, metal compound, fatty acid or oil, and Polyol. Hereinafter, the resin for offset printing ink of the present invention will be described in detail.

(rosin)

In the present invention, as the resin raw material (including rosin, fatty acid or oil, α, β-unsaturated carboxylic acid or its anhydride, polyhydric alcohol, and metal compound, and if necessary, aromatic carboxylic acid. The same below.) The rosins used include rosin and rosin derivatives. In general, rosin refers to resin oil obtained from pinaceae plants as a raw material, and residual resin obtained by distilling off volatile substances such as essential oils. The resin is a mixture containing resin acid, the main component of which is abietic acid and its analogues, and a small amount of neutral components.

Examples of the rosin include gum rosin, tall oil rosin, wood rosin, and the like. In addition, examples of derivatives of rosin include polymerized rosin, acrylic rosin, hydrogenated rosin, disproportionated rosin, and the like. These rosins may be used alone or in combination of two or more.

Rosins are preferably contained in an amount of 20% by mass to 60% by mass, more preferably 30% by mass to 50% by mass, based on the total amount of the resin raw material.

(α,β-Unsaturated carboxylic acid or its anhydride)

In the present invention, the α,β-unsaturated carboxylic acid or its anhydride used as the resin raw material is used for increasing the molecular weight of the resin used in offset printing ink. That is, α, β-unsaturated carboxylic acid or its anhydride and rosin undergo addition reaction (Alder-ene reaction or Diels-Alder reaction) to generate α, β-unsaturated carboxylic acid or its anhydride and rosin Class adducts. Since this adduct has at least two carboxyl groups in the molecule, it forms an ester bond with a polyhydric alcohol described later to increase its molecular weight. Thus, by increasing the molecular weight, a resin having desired viscoelasticity can be obtained.

Examples of α, β-unsaturated carboxylic acids or their anhydrides include chain α, β-unsaturated monocarboxylic acids or their anhydrides having 3 to 5 carbon atoms, and chain α having 3 to 5 carbon atoms. α,β-unsaturated dicarboxylic acids or their anhydrides, aromatic α,β-unsaturated carboxylic acids, and the like. Specifically, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, crotonic acid, cinnamic acid, etc. are mentioned. These α,β-unsaturated carboxylic acids or their anhydrides may be used alone or in combination of two or more.

The α,β-unsaturated carboxylic acid or its anhydride is preferably contained in a ratio of 1% by mass to 15% by mass, more preferably 3% by mass to 10% by mass, based on the total amount of the resin raw material. If the α,β-unsaturated carboxylic acid or its anhydride is contained within the above range, the molecular weight can be easily controlled, and a resin having desired viscoelasticity necessary for the ink can be obtained more easily.

(metal compound)

In the present invention, the metal compound used as the resin raw material is used as a crosslinking agent that crosslinks carboxyl groups (—COOH) present in compounds contained in the resin raw material to increase molecular weight and the like. For example, in the case of using a fatty acid described later as a resin raw material, a cross-linked body formed from fatty acid and rosins, α, β-unsaturated carboxylic acids or their anhydrides, and rosins and At least one of the adducts of α,β-unsaturated carboxylic acids or their anhydrides is formed by crosslinking metal ions derived from metal compounds.

More specifically, for example, a cross-linked body or the like shown in the following (i) to (iv) is formed.

(i) A cross-linked body in which a fatty acid and an adduct are cross-linked by a metal ion.

(ii) A cross-linked body in which fatty acid and unreacted rosin are cross-linked by metal ions.

(iii) A crosslinked body in which fatty acid and unreacted α,β-unsaturated carboxylic acid or anhydride thereof are crosslinked by metal ions.

(iv) A cross-linked body in which a fatty acid and an aromatic carboxylic acid as an optional component described later are cross-linked by metal ions.

On the other hand, in the case of using oils and fats described later as resin raw materials, a cross-linked body is formed, and the cross-linked body is formed from rosins, α, β-unsaturated carboxylic acids or their anhydrides, and rosins and α , at least one of adducts of β-unsaturated carboxylic acids or anhydrides thereof formed by crosslinking metal ions derived from metal compounds.

More specifically, for example, a cross-linked body shown in (i') to (x') below is formed.

(i') A cross-linked body in which adducts are cross-linked by metal ions.

(ii') A cross-linked product in which the adduct and unreacted rosin are cross-linked by metal ions.

(iii') A crosslinked product in which an adduct and unreacted α,β-unsaturated carboxylic acid or anhydride thereof are crosslinked by metal ions.

(iv') A cross-linked product in which an adduct and an aromatic carboxylic acid as an optional component described later are cross-linked by metal ions.

(v') A cross-linked body in which unreacted rosins are cross-linked by metal ions.

(vi') A crosslinked product in which unreacted rosin and unreacted α,β-unsaturated carboxylic acid or anhydride thereof are crosslinked by metal ions.

(vii') A cross-linked product in which unreacted rosin and an aromatic carboxylic acid as an optional component described later are cross-linked by metal ions.

(viii') A crosslinked product in which unreacted α,β-unsaturated carboxylic acids or their anhydrides are crosslinked by metal ions.

(ix') A crosslinked product in which unreacted α,β-unsaturated carboxylic acid or its anhydride and aromatic carboxylic acid as an optional component described later are crosslinked by metal ions.

(x') A cross-linked body in which aromatic carboxylic acids, which will be described later as optional components, are cross-linked by metal ions.

As described above, the molecular weight of the cross-linked body formed by cross-linking the carboxyl groups present in the resin raw material by the metal ions increases, and as a result, the dryness and anti-fogging properties of the ink are improved. In addition, by including the metal compound, the affinity with the pigment can be improved and the dispersibility can be improved when the ink is prepared.

Examples of metal compounds include hydroxides, oxides, and the like of divalent or higher metals such as calcium, zinc, magnesium, aluminum, cobalt, copper, lead, and manganese. Among them, calcium hydroxide, calcium oxide, zinc hydroxide, zinc oxide, magnesium hydroxide, magnesium oxide and the like are preferred because of high reactivity to carboxyl groups present in the resin raw material and high affinity with pigments. compounds, zinc compounds or magnesium compounds. These metal compounds may be used alone or in combination of two or more.

When the metal compound is calculated as the amount of metal in the metal compound with respect to the total amount of the resin raw material (mass ratio corresponding to the metal part. The same applies below.), the metal is contained in an amount of 0.5% by mass to 5% by mass. By including the metal compound in the above ratio, a resin having an excellent balance between hydrophilicity and lipophilicity can be obtained. When the content of the metal is less than 0.5% by mass based on the amount of the metal in the metal compound, the molecular weight becomes small, and the anti-fogging property during printing and the drying property of the ink deteriorate. On the other hand, when the content of the metal exceeds 5% by mass, the solubility to the aliphatic hydrocarbon solvent decreases due to the increase in the amount of the metal salt, and the pigment dispersibility and the gloss of the printed matter deteriorate. Moreover, there will be a problem that the ink is easy to emulsify in printing with water. The content calculated as the amount of metal in the metal compound is preferably 1% by mass to 3% by mass.

In particular, in the above range, in order to obtain a resin with a better balance, it is preferable to set the content of the metal compound at a ratio of about 2 parts by mass to about 15 parts by mass when the fatty acid or oil described later is 100 parts by mass. More preferably, it is set at about 3 parts by mass to 10 parts by mass.

In addition, in gravure printing, rosin-based metal salts are generally used as ink resins. However, gravure printing is a printing method completely different in format from offset printing. Therefore, even if resins for gravure printing inks are used as resins for offset printing inks, the solubility in aliphatic hydrocarbon solvents will deteriorate, and further problems such as easy emulsification of inks will arise in printing with water.

In addition, in general, a metal compound may be used as an esterification catalyst when producing a rosin-modified polyester resin. Since the metal catalyst used for esterification is reused many times in the reaction system, a very small amount is sufficient. If a large amount of metal is added before the alcohol is added, insoluble matter of the metal is precipitated and the performance of the resin for ink is deteriorated. In this regard, it is better to use more metal compounds in the present invention. The reason is that although a very small part of the metal compound may be used as an esterification catalyst, the main purpose of using the metal compound is to crosslink the carboxyl groups present in the resin raw material by metal ions derived from the metal compound. For example, in the case of using a fatty acid, since the fatty acid is used in a relatively large amount, the metal compound dissolves quickly even though a large amount of metal is used, and a cross-linked structure via metal ions can be formed.

(fatty acid)

In the present invention, the fatty acid used as a resin raw material is used to impart lipophilicity to the resin. That is, the cross-linked body shown in (i) to (iv) above is formed, and lipophilicity is imparted. Since the lipophilicity of the fatty acid depends on the alkyl portion of the fatty acid, a higher fatty acid having many carbon atoms is preferred, and a fatty acid having 12 or more carbon atoms is preferred as the main component. Examples of fatty acids include fatty acids derived from animal fats and oils, fatty acids derived from vegetable fats and the like, which will be described later.

As the fatty acid having 12 or more carbon atoms, both saturated fatty acid and unsaturated fatty acid may be used. Examples of saturated fatty acids include lauric acid (12 carbon atoms), myristic acid (14 carbon atoms), palmitic acid (16 carbon atoms), and stearic acid (18 carbon atoms). In addition, examples of unsaturated fatty acids include α-linolenic acid (18 carbon atoms), linoleic acid (18 carbon atoms), oleic acid (18 carbon atoms), and the like. Among the above-mentioned fatty acids, saturated fatty acids such as stearic acid are preferable because they are excellent in various physical properties such as solubility in ink solvents and drying properties.

The fatty acid does not have to be a purified fatty acid, but can also be a mixed fatty acid. Examples of the mixed fatty acid include a mixture of two or more fatty acids, fatty acids derived from animal fats and oils, fatty acids derived from vegetable fats and oils, and the like.

Fatty acids derived from animal fats and oils whose main components are fatty acids having 12 or more carbon atoms include tallow fatty acid, lard fatty acid, fish oil fatty acid, and hydrogenated (solidified) fatty acids.

In addition, fatty acids derived from vegetable oils whose main components are fatty acids having 12 or more carbon atoms include tall oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, tung oil fatty acid, coconut oil fatty acid, and castor oil fatty acid. wait.

(grease)

In the present invention, the fats and oils used as the raw material of the resin are used to impart lipophilicity to the resin. When lipophilicity is imparted, the solubility with respect to the solvent etc. used for ink preparation can be improved. Lipophilicity can be obtained by introducing an alkyl group derived from oil (triglyceride) into a polyester resin composed of rosin, α,β-unsaturated carboxylic acid, and or its anhydride, the above-mentioned adduct, the above-mentioned cross-linked body, the aromatic carboxylic acid (used if necessary) described later, and the polyhydric alcohol described later.

Fats and oils are not particularly limited, and examples thereof include animal fats and vegetable fats and oils. Among these fats and oils, fats and oils containing at least triglycerides composed of at least one of three fatty acids having 12 or more carbon atoms are preferable. Examples of the above-mentioned animal fats and oils include tallow, lard, and fish oil. Examples of vegetable fats and oils include soybean oil, linseed oil, tung oil, coconut oil, castor oil, palm oil, and rapeseed oil. In addition, regenerated oil that is recovered and regenerated after eating tempura oil and the like can also be used. As a regeneration treatment method, generally, removal of a precipitate by filtration etc., decolorization, etc. are mentioned. These fats and oils may be used alone or in combination of two or more.

Fatty acid or fat is contained in the ratio of 10 mass % to 50 mass % with respect to the total amount of resin raw materials. When the content of the fatty acid or fat is less than 10% by mass, the solubility with respect to solvents and the like used in the preparation of the ink decreases, the dispersibility of the pigment deteriorates, or the gloss imparted to the printed matter deteriorates. On the other hand, when the content of fatty acid or oil exceeds 50% by mass, the resin becomes soft, and the anti-fogging and ink drying properties during printing deteriorate.

The fatty acid or fat is preferably contained in a ratio of 20% by mass to 40% by mass based on the total amount of the resin raw material. In addition, the fatty acid or oil used as the raw material of the resin should be used differently from the solvent used in the preparation of the ink, such as the varnish of the resin.

In the present invention, fatty acids and fats and oils may be used alone, or fatty acids and fats and oils may be used together. When fatty acids are used together with oils and fats, the fatty acids and oils and fats are contained in a total of 10 to 50 mass %, preferably 20 to 40 mass %, based on the total amount of the resin raw material.

(Polyol)

In the present invention, polyhydric alcohols used as resin raw materials and the above-mentioned adducts, unreacted rosins, unreacted α, β-unsaturated carboxylic acids or their anhydrides, the above-mentioned crosslinked products, fatty acids, and Aromatic carboxylic acids described later react to form esters. For example, if there are many carboxyl groups remaining in the resin, the ink tends to be easily emulsified in printing with water.

Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, hexanediol, glycerin, trimethylolpropane, pentaerythritol, Pentaerythritol, D-sorbitol, etc. Among them, polyhydric alcohols having a trivalent or higher valence are preferable in terms of achieving a high molecular weight of the resin and making it easier for the ink to obtain the necessary viscoelasticity. Polyols may be used alone or in combination of two or more.

The amount of polyhydric alcohol contained is preferably 0.5 to 2 equivalents, more preferably 0.9 to 1.3 equivalents, based on 1 equivalent of carboxyl groups present in the resin raw material. When the polyhydric alcohol in the above-mentioned range is included, it is possible to more easily obtain a resin that imparts the desired viscoelasticity necessary for the ink. In addition, the solubility to solvents and the like used in the preparation of the ink becomes better, and the ink becomes difficult to emulsify even in printing with water.

In addition, examples of the carboxyl group present in the resin raw material include carboxyl groups derived from rosins, carboxyl groups derived from α,β-unsaturated carboxylic acids or their anhydrides, carboxyl groups derived from fatty acids, and those derived from aromatic carboxylic acids described later. carboxyl.

(aromatic carboxylic acid)

In the present invention, an aromatic carboxylic acid may also be contained in the resin raw material as needed. In general, if a resin used in offset printing ink has high solubility to a solvent or the like used in preparing the ink, fluidity is good, and good gloss is imparted to printed matters. However, the solvent detachment during printing is slow, and the drying property of the ink is deteriorated. By using an aromatic carboxylic acid, it is possible to adjust the solubility to a solvent or the like used in the preparation of the ink, and to adjust the molecular weight of the resin.

In particular, aromatic monocarboxylic acids are used to adjust the solubility to solvents and the like used in the preparation of ink, and aromatic dicarboxylic acids or aromatic polycarboxylic acids are used to adjust the molecular weight of resins.

Examples of the aromatic carboxylic acid include benzoic acid, salicylic acid, naphthoic acid, phthalic acid, phthalic anhydride, trimellitic acid, trimellitic anhydride, and the above examples in which at least one alkyl group is introduced into the aromatic ring. substitutes. These aromatic carboxylic acids may be used alone or in combination of two or more.

When used as needed, the aromatic carboxylic acid is contained in a ratio of preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 4% by mass to 10% by mass, based on the total amount of the resin raw material.

(other ingredients)

Other components may be added to the raw material of the resin for offset printing ink of the present invention within the range that does not impair the effects of the present invention. As other components, petroleum resin etc. are mentioned, for example.

(Preparation method of resin for offset printing ink)

The preparation method of the resin for offset printing ink of the present invention is not particularly limited. In the case of using a fatty acid, the resin for offset printing ink of the present invention is obtained, for example, by the following first step and second step.

The first step: forming a cross-linked body, the cross-linked body is composed of fatty acid and selected from rosin, α, β-unsaturated carboxylic acid or its anhydride, and the rosin and the α, β-unsaturated carboxylic acid At least one of the adducts formed by acids or anhydrides thereof, formed by cross-linking of metal ions from metal compounds;

The second step: making at least one selected from the rosin, the α, β-unsaturated carboxylic acid or its anhydride, the adduct, the cross-linked body, and the fatty acid with a polyhydric alcohol An esterification reaction is carried out to form an ester.

The reaction temperature in the first step and the second step varies depending on the composition of the raw materials, and is preferably at 100°C to 290°C, more preferably at 200°C to 270°C. The reaction time is preferably 2 to 20 hours, more preferably 3 to 10 hours, for example, in the case of sequential addition of raw materials, the reaction time is the total time from the start of addition of raw materials to the final product. By carrying out the reaction under the above conditions, α, β-unsaturated carboxylic acid or its anhydride and rosin with unsaturated bond undergo addition reaction (Alder-ene reaction or Diels-Alder reaction) to generate α, Adducts of β-unsaturated carboxylic acids or their anhydrides with rosin.

In the first step, after the above-mentioned addition reaction is completed, or while the addition reaction is proceeding, a compound selected from the above-mentioned adduct, unreacted rosin, and unreacted α, β-unsaturated carboxylic acid or At least one of the acid anhydrides forms a cross-linked body with the fatty acid via metal ions derived from the metal compound.

In addition, in the second step, after the cross-linking reaction in the first step is completed, or while the cross-linking reaction is progressing, a fatty acid, the above-mentioned adduct, the above-mentioned cross-linked body, unreacted rosin, and unreacted At least one of the reacted α,β-unsaturated carboxylic acids or their anhydrides is reacted with a polyol to form an ester. Since the adduct has two or more carboxyl groups in the molecule, it can be reacted with a polyol to form an ester, and a high molecular weight resin (rosin-modified polyester resin) can be obtained. Moreover, the crosslinked body which has a carboxyl group in a molecule reacts with a polyhydric alcohol and is esterified.

On the other hand, in the case of using fats and oils, the resin for offset printing ink of the present invention is obtained, for example, by the following A step to C step.

A step: forming a cross-linked body, the cross-linked body is selected from rosin, α, β-unsaturated carboxylic acid or its anhydride, and the rosin and the α, β-unsaturated carboxylic acid or its anhydride at least one of anhydride-formed adducts formed by crosslinking metal ions from said metal compound;

Step B: making an adduct selected from the rosins, the α, β-unsaturated carboxylic acid or its anhydride, the rosin and the α, β-unsaturated carboxylic acid or its anhydride, and At least one of the cross-linked bodies undergoes an esterification reaction with a polyol to form an ester;

In step C, the ester and oil obtained in step B are subjected to a transesterification reaction, and the alkyl group in the oil is introduced into the ester.

The reaction temperature and the reaction time in the A step to the C step are the same as the temperature and time when using fatty acid. By carrying out the reaction under the above conditions, α, β-unsaturated carboxylic acid or its anhydride and rosin with unsaturated bond undergo addition reaction (Alder-ene reaction or Diels-Alder reaction) to generate α, Adducts of β-unsaturated carboxylic acids or their anhydrides and rosins.

In the A step, after the above-mentioned addition reaction is completed, or while the addition reaction is proceeding, a compound selected from the above-mentioned adduct, unreacted rosin, and unreacted α, β-unsaturated carboxylic acid or its At least one of the acid anhydrides forms a cross-linked body with metal ions derived from the metal compound.

In the B step, after the cross-linking reaction in the A step is completed, or while the cross-linking reaction is progressing, the above-mentioned adduct, the above-mentioned cross-linked body, unreacted rosin, and unreacted α, β- At least one of an unsaturated carboxylic acid or an anhydride thereof reacts with a polyhydric alcohol to form an ester. Since the adduct has two or more carboxyl groups in the molecule, it can react with a polyhydric alcohol to form an ester, and a high molecular weight resin (rosin-modified polyester resin) can be obtained. As mentioned above, the crosslinked body which has a carboxyl group in a molecule reacts with a polyhydric alcohol, and is esterified.

In step C, after the esterification reaction in step B is completed, or while the esterification reaction is in progress, the alkyl group in the oil is introduced into the rosin-modified polyester resin through the transesterification reaction between the generated ester and the oil middle. Through the C step, at least a part of the ester formed in the B step is transesterified with the oil, thereby obtaining a rosin-modified polyester resin in which an alkyl group (for example, an alkyl group having 12 or more carbon atoms) from the oil is introduced .

In the range that does not affect the effect of the present invention, in addition to the above-mentioned rosin-modified polyester resin, the resin for offset printing ink of the present invention may also contain shellac, hard pitch, alkyd resin, rosin-modified phenolic resin, etc. Other ink resins such as resins.

(Inks for Offset Printing)

Next, an offset printing ink using the resin for offset printing ink of the present invention will be described. To prepare a varnish, the resin for offset printing ink of the present invention is usually mixed with a drying or semi-drying oil (for example, linseed oil, tung oil, soybean oil, refined soybean oil, etc.) and a solvent (for example, an aliphatic hydrocarbon solvent etc.) mixed together.

Various gelling agents may be added when preparing a varnish using the resin for offset printing ink of the present invention in consideration of viscoelasticity within a range that does not affect the effect of the present invention. The gelling agent is not particularly limited, and examples thereof include aluminum compounds such as aluminum alkoxides and aluminum soaps; metal soaps such as manganese, cobalt, and zirconium; and alkanolamines. The gelling agents may be used alone or in combination of two or more.

Since the resin for offset printing ink of the present invention does not use aldehydes and phenols, there is no need to synthesize a resole phenolic resin. In addition, since a metal compound is used to form a crosslinked body, the resin for offset printing ink of the present invention can be varnished in a relatively short time compared with a rosin-modified phenolic resin.

A pigment of a desired color (black pigment, blue pigment, red pigment, etc.) is dispersed in the obtained varnish to prepare an offset printing ink.

The offset printing ink obtained by using the resin for offset printing ink of the present invention has excellent drying properties and anti-fogging properties during printing, and can replace existing rosin-modified phenolic resins. Furthermore, when this offset printing ink is used, a printed matter having a good gloss and a soft coating can be obtained.

Example

Hereinafter, although an Example and a comparative example are given and this invention is concretely demonstrated, this invention is not limited to these Examples.

(Example 1)

When the whole resin raw material was taken as 100% by mass, gum rosin as rosin and soybean oil fatty acid as fatty acid were put into the reaction container at a ratio of 38% by mass and 36.8% by mass, respectively, nitrogen gas was blown in, and the temperature was raised to 200° C. It dissolves. After dissolution, maleic anhydride which is an α,β-unsaturated carboxylic acid or an anhydride thereof and zinc oxide which is a metal compound were added in proportions of 7.6% by mass and 2.8% by mass, respectively, and reacted for 1 hour. Next, pentaerythritol as a polyhydric alcohol was added in a ratio of 14.8% by mass, the temperature was raised to 270° C., and the mixture was reacted for about 7 hours to obtain a resin for offset printing ink.

In the obtained resin, the amount of the metal was about 6.3 parts by mass based on the amount of the metal in the metal compound relative to 100 parts by mass of the fatty acid. In addition, 1.1 equivalents of polyhydric alcohol (pentaerythritol) is contained with respect to 1 equivalent of carboxyl groups present in the resin raw material.

Next, the obtained resin for offset printing ink, soybean refined oil, and AF7 (manufactured by Shin Nippon Petrochemical Co., Ltd., free of aromatic hydrocarbons) were added in proportions of 50 mass %, 15 mass %, and 35 mass %, respectively, at 180 The mixture was stirred at °C for 1 hour to obtain a varnish.

The obtained varnish and blue pigment were mixed at a ratio of 70% by mass and 19% by mass, respectively, and the blue pigment was dispersed in the in varnish. Next, varnish and AF7 were added in proportions of 4% by mass and 7% by mass to adjust the adhesion at 25° C. to 6 to 7 to obtain offset printing inks.

(Examples 2 to 8 and Comparative Examples 1 to 5)

Resins for offset printing inks were respectively obtained in the same procedure as in Example 1 except that the components shown in Table 1 were used in the ratios shown in Table 1. In Examples 2 to 8 and Comparative Examples 1 to 5, 1.0 to 1.3 equivalents of polyhydric alcohol are contained with respect to 1 equivalent of carboxyl groups present in the resin raw material.

Next, a varnish was obtained in the same procedure as in Example 1 except that the resin for offset printing ink obtained separately was used. In addition, since the solubility of the resin obtained in Comparative Example 1 to AF7 was too low, cloudiness occurred in the resin of Comparative Example 1, and a varnish could not be obtained.

Offset printing inks were respectively obtained in the same procedure as in Example 1, except that the obtained varnishes were used and the ratios shown in Table 2 were used for the varnishes, AF7, and blue pigments. The content of the varnish in Table 2 is the total amount, and 70% by mass is used for dispersing the blue pigment, and the balance is used for adjusting the adhesion.

(reference example)

Except using the existing rosin-modified phenolic resin (produced by Halima Chemical Synthesis Co., Ltd., Halifax phenol P-600) as the resin for offset printing ink, the varnish was prepared in the same order as in Example 1, as shown in Table The ratio shown in 2 uses varnish, AF and blue pigment, resulting in offset printing ink. In addition, Halifax phenol P-600 is a resin obtained by reacting the pentaerythritol ester of rosin and the initial condensation product of phenol formaldehyde.

The offset printing inks obtained in Examples 1 to 8, Comparative Examples 2 to 5, and Reference Examples were evaluated for (1) gloss value, (2) dryness, (3) anti-fogging property, and (4) maximum amount of emulsification. The results are shown in Table 2.

(1) gloss value

0.2 ml of offset printing ink was developed on coated paper (manufactured by Mitsubishi Paper Co., Ltd., pearlescent coating) using a RI tester (manufactured by Ishikawajima Sangyo Machinery Co., Ltd., RI-2) with double separation rollers. The gloss of the ink 24 hours after the color development was measured using a 60°-60° gloss meter (manufactured by Taiwoo Kisai Co., Ltd., micro-TRI-gloss). When the measured value was 50 or more, it was evaluated as having glossiness.

(2) dryness

0.2 ml of offset printing ink was developed on coated paper (manufactured by Mitsubishi Paper Co., Ltd., pearlescent coating) using RI tester double separation rollers. Install the front end of the exhaust port of a heat gun (manufactured by Ishizaki Electric Manufacturing Co., Ltd., Plastic jet PJ-208A) at a position 30 cm away from the printed matter, blow hot air onto the printed matter, and touch the printed surface with your fingers to confirm the adhesion. attachment. The time until the stickiness can no longer be sensed by fingers was measured, and five-level evaluation was performed according to the following criteria. Usually, among these evaluations, an evaluation of level 3 or higher is considered to be a usable level.

5: The case where the drying property was very good within 2 minutes

4: When the dryness is good within 3 minutes

3: In the case of average drying within 5 minutes

2: When the dryness is slow within 7 minutes

1: The case where the drying property is remarkably delayed for 7 minutes or more

(3) Anti-fogging ink

2 cups (360 ml) of offset printing ink were placed on an ink viscometer (manufactured by Toyo Seiki Co., Ltd.), and rotated at 2000 rpm for 2 minutes. The splash state of the ink on the white paper placed on the front and the bottom of the drum was observed with the naked eye, and the following 5 grades were used for evaluation. A case of 3 or more was evaluated as having excellent anti-fogging property.

5: No splash at all

4: When a small amount of splash is generated

3: The case where it can be used despite splashing

2: A case where a large amount of spatter is generated

1: A case where very violent splashing is generated

(4) Maximum amount of emulsification

Using an electromagnetic resonance type (resotronic) emulsification tester (manufactured by Novocontrol), water was added to 25 g of offset printing ink at a rate of 2 g/minute at 40° C. to emulsify it. The number of revolutions of the emulsification tester was set at 1200 rpm. Measure the water content (g) at which the ink no longer absorbs water (no longer emulsifies) and the ink and water begin to separate. The obtained water content was divided by 25, and the value expressed in percentage was made into the maximum emulsification amount. The case where the maximum emulsification amount is 50 to 100% is called an allowable range.

As shown in Table 2, compared with the offset printing ink (reference example) using the conventional rosin-modified phenolic resin, the offset printing inks of Examples 1 to 8 were improved in (1) gloss value, (2) dryness , (3) anti-fogging property, and (4) maximum emulsification amount, are equal to or better than it.

On the other hand, in the offset printing ink of Comparative Example 2, since the content of fatty acid in the resin was too small, the solubility to the solvent was lowered, and the glossiness was poor. Since the offset printing ink of Comparative Example 3 has a large content of fatty acid, although the glossiness is good, the dryness and anti-fogging properties are poor. In the offset printing ink of Comparative Example 4, since the content of the metal compound was too small relative to the content of the fatty acid, the dryness and anti-fogging properties were poor. In the offset printing ink of Comparative Example 5, since the content of the metal compound was too large relative to the content of the fatty acid, the maximum emulsification amount increased.

(Example 9)

When the whole resin raw material was 100% by mass, gum rosin and soybean oil were put into the reaction container at a ratio of 41.0% by mass and 38.0% by mass, respectively, and the temperature was raised to 200° C. while blowing nitrogen gas to dissolve it. After dissolution, maleic anhydride and zinc oxide were added in proportions of 7.6% by mass and 2.8% by mass, respectively, and reacted for 2 hours. Next, pentaerythritol was added as a polyhydric alcohol in a ratio of 10.6% by mass, the temperature was raised to 270° C., and the mixture was reacted for about 7 hours to obtain a resin for offset printing ink.

In the obtained resin, calculated as the amount of the metal in the metal compound, the amount of the metal was 6.1 parts by mass relative to 100 parts by mass of the fats and oils. In addition, 1.1 equivalents of polyhydric alcohol (pentaerythritol) is contained with respect to 1 equivalent of carboxyl groups present in the resin raw material.

Next, the obtained offset printing ink resin, soybean refined oil, and AF7 were added in proportions of 50 mass %, 15 mass %, and 35 mass %, respectively, and stirred at 180° C. for 1 hour to obtain a varnish.

The obtained varnish and blue pigment were mixed at a ratio of 70% by mass and 19% by mass, respectively, and the blue pigment was dispersed in the varnish using the above-mentioned three-roll mill. Next, varnish and AF7 were added in proportions of 4% by mass and 7% by mass to adjust the adhesion at 25° C. to 6 to 7 to obtain offset printing inks.

(Examples 10 to 16 and Comparative Examples 6 to 10)

Resins for offset printing inks were respectively obtained in the same procedure as in Example 9 except that the components shown in Table 3 were used in the ratios shown in Table 3. In addition, Comparative Example 6 is the same as Comparative Example 1 described above. In Examples 10 to 16 and Comparative Examples 6 to 10, 1.0 to 1.2 equivalents of polyhydric alcohol are contained with respect to 1 equivalent of carboxyl groups present in the resin raw material.

Next, a varnish was obtained in the same procedure as in Example 9 except that the obtained resin for offset printing ink was used. Similar to Comparative Example 1, since the solubility of the resin of Comparative Example 6 to AF7 was too low, cloudiness occurred in the resin of Comparative Example 6, and a varnish could not be obtained. Offset printing inks were respectively obtained in the same procedure as in Example 9, except that the obtained varnishes were used and the ratios shown in Table 4 were used for the varnishes, AF7, and blue pigments. The content of the varnish in Table 4 is the total amount, and 70% by mass is used for dispersing the blue pigment, and the balance is used for adjusting the adhesion.

The offset printing inks obtained in Examples 9 to 16 and Comparative Examples 7 to 10 were evaluated by the same method as in Example 1 for (1) gloss value, (2) dryness, (3) anti-fogging property, and (4) ) the maximum amount of emulsification. The results are shown in Table 4. In addition, the reference example of Table 4 is the same as the reference example of Table 2.

As shown in Table 4, compared with the offset printing ink (reference example) using the conventional rosin-modified phenolic resin, the offset printing inks of Examples 9 to 16 were improved in (1) gloss value, (2) dryness , (3) anti-fogging property, and (4) maximum emulsification amount, are equal to or better than it.

On the other hand, in the offset printing ink of Comparative Example 7, since the content of the fatty acid in the resin was too small, the solubility to the solvent decreased, and the glossiness deteriorated. The offset printing ink of Comparative Example 8 had a large amount of oil and fat, so although the glossiness was good, the dryness and anti-fogging properties were poor. In the offset printing ink of Comparative Example 9, since the content of the metal compound was too small relative to the content of the fats and oils, the dryness and anti-fogging properties were poor. In the offset printing ink of Comparative Example 10, since the content of the metal compound was too large relative to the content of the fats and oils, the maximum emulsification amount increased.

Claims (12)

1. A resin for offset printing ink comprising a resin obtained by reacting a resin raw material comprising rosins, α,β-unsaturated carboxylic acids or anhydrides thereof, metal compounds, fatty acids or fats and oils, and polyols, characterized in that, Relative to the total amount of the resin raw material, the fatty acid or the oil is contained in an amount of 10% by mass to 50% by mass, and if the metal compound is calculated as the amount of metal in the metal compound, relative to the The total amount of the resin raw material contains 0.5 mass% to 5 mass% metal. 2. The resin for offset printing ink according to claim 1, wherein the main component of the fatty acid is a fatty acid having 12 or more carbon atoms. 3. The resin for offset printing ink as claimed in claim 1 or 2, which comprises a cross-linked body composed of the fatty acid and At least one selected from the rosins, the α, β-unsaturated carboxylic acids or their anhydrides, and the adducts formed from the rosins and the α, β-unsaturated carboxylic acids or their anhydrides kind, Formed by metal ion crosslinking from the metal compound. 4. The resin for offset printing ink as claimed in claim 3, wherein the cross-linked body consists of carboxyl groups present in the fatty acid and At least one selected from the rosins, the α, β-unsaturated carboxylic acids or their anhydrides, and the adducts formed from the rosins and the α, β-unsaturated carboxylic acids or their anhydrides carboxyl group Formed by metal ions from the metal compound. 5. The resin for offset printing ink according to claim 1, wherein the fat is triglyceride formed of fatty acid and glycerin, and at least one fatty acid has 12 or more carbon atoms. 6. The resin for offset printing ink according to claim 1 or 5, comprising a cross-linked body selected from the group consisting of the rosin, the α, β-unsaturated carboxylic acid, or at least one of acid anhydrides, and adducts formed from said rosins and said α,β-unsaturated carboxylic acids or their anhydrides, Formed by metal ion crosslinking from the metal compound. 7. The resin for offset printing ink as claimed in claim 6, wherein the cross-linked body is selected from the group consisting of the rosins, the α, β-unsaturated carboxylic acid or its anhydride, and the carboxyl groups present in at least one of the adducts of rosins and said α,β-unsaturated carboxylic acids or their anhydrides, Formed by metal ions from the metal compound. 8. The resin for offset printing ink according to any one of claims 1 to 7, wherein the resin raw material further contains an aromatic carboxylic acid. 9. The resin for offset printing ink according to any one of claims 1 to 8, wherein the metal compound contains a divalent or higher metal compound. 10. The preparation method of the resin that is used for offset printing ink, is characterized in that, comprises: The first step is to form a cross-linked body, which is composed of fatty acids and rosins, α, β-unsaturated carboxylic acids or their anhydrides, and rosins and the α, β-unsaturated carboxylic acids At least one of the adducts formed by acids or anhydrides thereof, formed by cross-linking of metal ions from metal compounds; and In the second step, at least one selected from the rosin, the α, β-unsaturated carboxylic acid or its anhydride, the adduct, the cross-linked body, and the fatty acid and the polyhydric alcohol carry out an esterification reaction to form an ester, The ratio of the fatty acid to the total amount of the resin raw material containing the rosin, the α,β-unsaturated carboxylic acid or its anhydride, the metal compound, the fatty acid, and the polyol is 10 % by mass to 50% by mass, and if the metal compound is calculated as the amount of metal in the metal compound, the proportion of the metal is 0.5% by mass to 5% by mass. 11. A method for preparing a resin for offset printing ink, characterized in that it comprises: Step A, forming a cross-linked body, the cross-linked body is selected from rosins, α, β-unsaturated carboxylic acids or their anhydrides, and the rosins and the α, β-unsaturated carboxylic acids or their anhydrides at least one of anhydride-formed adducts formed by crosslinking metal ions from said metal compound; In the B step, at least one selected from the rosin, the α, β-unsaturated carboxylic acid or its anhydride, the adduct, and the crosslinked body is subjected to an esterification reaction with a polyhydric alcohol. form esters; and C step, making the ester obtained in the B step and the oil undergo transesterification reaction, and introducing the alkyl group in the oil into the ester, The ratio of the fatty acid to the total amount of the resin raw material including the rosin, the α,β-unsaturated carboxylic acid or its anhydride, the metal compound, the fat, and the polyol is 10 % by mass to 50% by mass, and if the metal compound is calculated as the amount of metal in the metal compound, the proportion of the metal is 0.5% by mass to 5% by mass. 12. An ink for offset printing comprising the resin for offset printing ink according to any one of claims 1 to 9, a drying oil or a semi-drying oil, a solvent, and a pigment.