JP2001233949A - Polyester resin composition, its production method, binder for printing ink, and printing ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester resin composition which has characteristics (high mol.wt., high softening point, high viscosity, high solubility, etc.), equal to those of a rosin-modified phenol resin though it is produced without using an alkylphenol-formaldehyde condensate; a production method thereof; a binder for a printing ink; and a printing ink which has printing characteristics (emulsifiability, gloss, dryability, misting, etc.), equal to or better than those of a conventionally known printing ink made by using a rosin-modified phenol resin. SOLUTION: This resin composition is produced by reacting (a) rosin, (b) a polar-group-containing petroleum resin, (c) a resin produced by partially reacting a polymer formed from a carboxylic acid and a hydrophobic polymerizable unsaturated compound with a hydrophobic compound reactive with carboxyl groups of the polymer, and (d) a polyol. A method for producing the composition, a binder of a printing ink prepared by using the composition, and a printing ink prepared by using the binder are also provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polyester resin composition, a method for producing the same, a binder for printing ink, and a printing ink. The polyester resin composition obtained according to the present invention is useful as a binder for printing ink. With respect to the type of printing ink, it can be particularly used as an offset printing ink, and can also be suitably used for newsprint ink, letterpress printing ink, and gravure printing ink.

[0002]

2. Description of the Related Art Conventionally, a rosin-modified phenol has been used as a binder for offset printing inks because it has various properties such as high molecular weight, high softening point, high viscosity and high solubility in ink solvents, and is excellent in printability. Resin is used. The resin is mainly composed of a rosin, an alkylphenol formaldehyde condensate and a polyol. However, rosin-modified phenolic resin generates formaldehyde-containing wastewater during the production of alkylphenol formaldehyde condensate, which is one of the main raw materials. Health and safety issues have been pointed out. It has also been pointed out that rosin-modified phenol resin generates formaldehyde in a heating and drying step of a printing ink using the resin.

Under such circumstances, development of a binder for offset printing inks that does not use harmful formaldehyde has been desired. Attempts have been made to use petroleum resins instead of rosin-modified phenolic resins in order to reduce the problems of these rosin-modified phenolic resins, but petroleum resins are generally low in molecular weight and cannot have many functional groups. Also, due to the small number of three-dimensional structures, the printability is insufficient, such as low gelling ability, large misting, insufficient gloss, and the like. It is not used as a binder for paper.

As a countermeasure, a method of using a rosin-based polyester resin has been considered. However, the conventional rosin-based polyester resin has a high softening point, but has a low molecular weight, has poor misting, and contains many polar groups. Therefore, printing suitability was insufficient such that the emulsification suitability was not at a practical level. As described above, since the required performance of the binder for the offset printing ink is diversified, it has been difficult to satisfy these performances with a resin other than the rosin-modified phenol resin so far.

[0005]

DISCLOSURE OF THE INVENTION The present inventors do not use an alkylphenol formaldehyde condensate as a raw material and have properties (high molecular weight, high softening point, high viscosity, high solubility, etc.) comparable to rosin-modified phenolic resins. Or higher than the printability (emulsifying properties, gloss, drying properties, misting, etc.) of a resin composition having the same, a method for producing the resin, a binder for a printing ink, and a printing ink using a conventionally known rosin-modified phenol resin. An object of the present invention is to provide a printing ink having printability.

[0006]

In view of the above problems, the present inventors have conducted intensive studies to find a resin which does not use an alkylphenol formaldehyde condensate as a raw material and has various properties comparable to rosin-modified phenolic resins. . As a result, it has reactivity with (a) a rosin, (b) a petroleum resin containing a polar group, (c) a polymer composed of a carboxylic acid and a hydrophobic polymerizable unsaturated compound, and a carboxylic acid in the polymer. The resin obtained by partially reacting with a hydrophobic compound and the polyester resin composition obtained by reacting (d) polyols meet the above-mentioned object, and the polyester resin is used as a binder for various printing inks. It has been found that it is suitable for use.

That is, the present invention provides (a) rosins,
(B) a polar group-containing petroleum resin, (c) a polymer comprising a carboxylic acid and a hydrophobic polymerizable unsaturated compound, and a hydrophobic compound having a reactivity with the carboxylic acid in the polymer partially reacted. And a polyester resin composition obtained by reacting (d) a polyol;
The present invention relates to a method for producing the polyester resin composition; a binder for a printing ink using the polyester resin; and a printing ink using the binder for the printing ink.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The polyester resin composition of the present invention comprises a rosin (hereinafter referred to as component (a)), a petroleum resin containing a polar group (hereinafter referred to as component (b)), a carboxylic acid and a hydrophobic polymer. Resin (hereinafter, referred to as a resin) obtained by partially reacting a polymer composed of a unsaturated compound with a hydrophobic compound having reactivity with carboxylic acids in the polymer.
(Referred to as component (c)), and polyols (hereinafter, referred to as components).
(Referred to as component (d)) as essential components, and by reacting these components.

The rosins as the component (a) include, for example, natural rosins such as gum rosin, tall oil rosin and wood rosin; polymerized rosins derived from the natural rosin;
Stabilized rosin obtained by disproportionation or hydrogenation of the above-mentioned natural rosin and polymerized rosin, and the like. In addition, unsaturated acid-modified rosins obtained by adding unsaturated carboxylic acids to the natural rosin or polymerized rosin by a Diels-Alder reaction or an ene reaction are exemplified.

The unsaturated acid-modified rosin includes, for example, maleic acid-modified rosin, maleic anhydride-modified rosin,
Fumaric acid-modified rosin, itaconic acid-modified rosin, crotonic acid-modified rosin, cinnamic acid-modified rosin, acrylic acid-modified rosin, methacrylic acid-modified rosin, and the like, and corresponding acid-modified polymerized rosin.
It is modified by using about 1 to 30 parts by weight of an unsaturated carboxylic acid with respect to 0 parts by weight.

Among the above-mentioned components (a), those containing a rosin having two or more carboxyl groups in the molecule are preferable because the obtained polyester resin can have a high molecular weight. In order to increase the molecular weight of the obtained polyester resin and to obtain a high melting point and a high softening point, among these components (a), those containing a polymerized rosin and / or an unsaturated acid-modified polymerized rosin are particularly desirable. It is preferred to use. In this case, the total content of the polymerized rosin and the unsaturated acid-modified polymerized rosin is about 40 parts by weight or more based on 100 parts by weight of the component (a). In the present invention, as the component (a), one of the above various types may be used alone,
More than one species can be used as appropriate. (A) to (d)
The amount of component (a) charged relative to the total amount of components is not particularly limited, but is preferably about 10 to 75% by weight.
When the content of the component (a) is 10% by weight or more, a desired molecular weight can be obtained. When the content is 75% by weight or less, the solubility of the resin is high, and the emulsification rate of the ink is appropriately adjusted. It is preferable because it can be performed.

The petroleum resin containing a polar group as the component (b) includes indene, methylindene, vinyltoluene, styrene, α-methylstyrene, β-methylstyrene, cyclopentadiene, dicyclopentadiene, methylbutene, isoprene, pentene, A petroleum resin having a double bond containing a cyclopentene, a pentadiene or the like as a component and having a polar group corresponds thereto. Examples of the petroleum resin having a double bond include DCPD petroleum resins made from cyclopentadiene and dicyclopentadiene; C5 petroleum resins such as pentene, pentadiene and isoprene; indene, methylindene, vinyltoluene, styrene, α-
C9-based petroleum resin using methylstyrene, β-methylstyrene or the like as a raw material, copolymerized petroleum resin composed of the DCPD-based material and C5-based material, copolymerized petroleum resin composed of the DCPD-based material and C9-based material, C5-based Copolymerized petroleum resin composed of a raw material and a C9-based raw material, and copolymerized petroleum resin composed of the DCPD-based raw material, a C5-based raw material and a C9-based raw material, and the like, using no catalyst or a Friedel-Crafts type catalyst (cationic polymerization). Manufactured. In particular, a petroleum resin obtained from a DCPD-based raw material is preferable because it is easy to add a polar group and easily adjust to a desired softening point.
Specific examples of petroleum resins obtained from DCPD raw materials include DCPD petroleum resins, copolymerized petroleum resins composed of DCPC raw materials and C5 raw materials, copolymerized petroleum resins composed of DCPD raw materials and C9 raw materials, and DCPD raw materials. C5 raw material and C
Copolymerized petroleum resin composed of ninth raw materials is exemplified.

The polar group in the component (b) includes a carboxyl group and a hydroxyl group. The method for providing a carboxyl group to the petroleum resin is not particularly limited, and a known method can be used. Specifically, the petroleum resin having a double bond and unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, crotonic acid, and cinnamic acid, and unsaturated acids such as acrylic acid and methacrylic acid. A method of radically copolymerizing a monocarboxylic acid with a radical initiator using a radical initiator, a method of adding the unsaturated carboxylic acid to the petroleum resin by an ene reaction or the like can be employed. From the viewpoint of improving the misting resistance of the obtained printing ink, it is preferable to employ a radical copolymerization method.

The amount of the unsaturated carboxylic acid used is preferably about 1 to 15 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the raw petroleum resin. When the component (b) obtained by modifying the resin is used, the molecular weight of the obtained polyester resin can be easily adjusted to a preferable range. More preferably, it is 1 to 10 parts by weight.

In addition, when the component (b) is obtained by giving a hydroxyl group as a polar group to the raw material petroleum resin, the reaction method is not particularly limited, and a known method can be used. . For example, a desired hydroxyl-containing petroleum resin can be obtained by adding water to a double bond of the petroleum resin or thermally polymerizing cyclopentadiene and allyl alcohol. For such a hydroxyl group-containing petroleum resin, a method of radical copolymerization using an unsaturated carboxylic acid and a radical initiator or a method of performing an ene addition reaction at a ratio of the number of equivalents of the carboxyl group smaller than the number of equivalents of the hydroxyl group. Is preferred because it can be easily made to have a high molecular weight. As the unsaturated carboxylic acids, various unsaturated dicarboxylic acids and unsaturated monocarboxylic acids described in paragraph 0013 correspond. From the viewpoint of improving the misting resistance of the obtained printing ink, it is more preferable to employ a radical copolymerization method.

Since the obtained polyester resin can have a high molecular weight, among the above-mentioned components (b), those containing a petroleum resin having two or more polar groups in the molecule are preferable. One of these polar group-containing petroleum resins may be used alone, or two or more different ones may be used in combination. The charging amount of the component (b) is not particularly limited, but is preferably about 19 to 64% by weight based on the total charging amount of the components (a) to (d). When the amount of the component (b) is less than 19% by weight, it is difficult to obtain an appropriate emulsifying property of the ink, and when it is more than 64% by weight, it is difficult to obtain a desired molecular weight. More preferably, the lower limit of the component (b) is 25% by weight, and the upper limit is 50% by weight.

The component (c), that is, a polymer comprising a carboxylic acid and a hydrophobic polymerizable unsaturated compound, and a hydrophobic compound having a reactivity with the carboxylic acid in the polymer are partially reacted. Specific examples of the carboxylic acids that are constituents of the resin include maleic acid, maleic anhydride, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid, methacrylic acid, and the like.
These can be used alone or in combination of two or more, and the amount of use can be arbitrarily changed within a range where the component (c) has an appropriate molecular weight.

Examples of the hydrophobic polymerizable unsaturated compound which is a component of the component (c) include the following various compounds. An aliphatic unsaturated hydrocarbon monomer having 2 to 50 carbon atoms, an alicyclic unsaturated hydrocarbon monomer having 5 to 50 carbon atoms, an aromatic hydrocarbon monomer having 8 to 50 carbon atoms,
Rosins, higher unsaturated fatty acids, unsaturated oils and the like. Specific examples of the above compounds include ethylene, propylene, 1-n-butene, dipropylene, diisobutylene, tripropylene, tribubutylene, 1-hexene,
-Octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docosene, 1-tetracosene, 1-hexacocene, 1-octacocene, 1-triaconten, 1-
Dotriaconten, 1-tetratriaceneten, 1-
Hexatria content, 1-octatria content, 1
Α-olefins such as tetracontain and butadiene,
And unsaturated polyolefins. Specific examples of the above compounds include cyclopentene, cyclohexene, allylcyclopentane, vinylcyclohexane and the like. Specific examples of the above compounds include styrene and α-methylstyrene.
Specific examples of the compound include the compound having an unsaturated bond described in the component (a). Specific examples of the above compounds include semi-dry oils or dry oils such as tung oil, linseed oil, safflower oil, soybean oil, and dehydrated castor oil, or higher unsaturated fatty acids obtained therefrom. The compounds (1) to (4) can be used alone or in combination of two or more, and other monomers and compounds can be used in combination as long as the features of the present invention are not impaired. Further, the amount used can be arbitrarily changed within a range where the component (c) has an appropriate molecular weight.

Examples of the hydrophobic compound having a reactivity with carboxylic acids, which is a component of the component (c), include the following various compounds. (I) carbon number 6 ~
50 aliphatic monoalcohols, (ii) an aliphatic dialcohol having 6 to 50 carbon atoms, (iii) an aliphatic monoamine having 6 to 50 carbon atoms, (iv) an aliphatic monoepoxy having 6 to 50 carbon atoms, and the like. . The structure of the compound (i) has 6 to 6 carbon atoms.
It is not particularly limited as long as it is 50, and may have any structure such as a linear structure, a branched structure, and a cyclic structure.
Specific examples include hexanol, octanol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, eicosanol, docosanol, tetracosanol, hexacosanol, octacosanol, triacontanol, oleyl alcohol, 2-ethylhexanol, Isotridecyl alcohol, isostearyl alcohol, geraniol, rosin alcohol, bisabolol, lanolin alcohol and the like. The structure of the compound (ii) is not particularly limited as long as it has 6 to 50 carbon atoms.
It may have any structure such as a branched structure and a cyclic structure. Specific examples include hexanediol, octanediol, decanediol, dodecanediol, tetradecanediol, hexadecanediol, octadecanediol, decenediol, dodecenediol, tetradecenediol, hexadecenediol, octadecenediol, lanolin alcohol, and dimer acid. And hydrogenated diols. The structure of the compound (iii) is not particularly limited as long as it has 6 to 50 carbon atoms, and may have any structure such as a linear structure, a branched structure, and a cyclic structure. Specific examples include hexylamine, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine,
Octadecenylamine, tallowalkylamine, soybean alkylamine, dioctadecylamine, dioctadecenylamine and the like can be mentioned. The structure of the compound (iv) is not particularly limited as long as it has 6 to 50 carbon atoms, and may have any structure such as a linear structure, a branched structure, and a cyclic structure. Specific examples include epoxy hexane, epoxy octane, epoxy decane, epoxy dodecane, epoxy tetradecane, epoxy hexadecane, epoxy octadecane, and ethylhexyl glycidyl ether.

The weight average molecular weight of the polymer as the component (c) (in terms of polystyrene by gel permeation chromatography; hereinafter, when referred to as weight average molecular weight, indicates the value in terms of polystyrene by gel permeation chromatography) is 2,000. If it is smaller than 2,000, the effect of improving the solubility by concentrating the hydrophobic groups is not sufficient, and if it is larger than 30,000, gelation, high viscosity, etc. Reaction control becomes difficult. The polymerization of the carboxylic acids and the hydrophobic polymerizable unsaturated compound, thermal polymerization,
It can be performed by a known method such as ionic polymerization or radical polymerization, and each reaction can be performed under known reaction conditions. For example, in the presence or absence of an initiator, a catalyst, and the like,
It can be performed in a solventless system or a solvent system. For example, preferred radical initiators used in the case of radical polymerization include azo-based initiators such as azobisisobutyronitrile,
Peroxides such as di-tert-butyl peroxide, benzoyl peroxide, dicumyl peroxide, potassium persulfate, and hydrogen peroxide can be used. Usually, the amount of the initiator is preferably in the range of about 0.01 to 10% by weight based on the total weight of the carboxylic acid and the hydrophobic polymerizable unsaturated compound.
The reaction temperature is also not particularly limited, but the optimum temperature may be appropriately determined according to the type of the radical initiator, and can be usually set appropriately from the range of about room temperature to about 200 ° C. When a solvent is used, it is preferable to use a solvent that can dissolve the starting materials and the reaction product at the employed polymerization temperature. Examples of the solvent include aromatic hydrocarbons such as toluene and xylene, alicyclic hydrocarbons such as methylcyclohexane and ethylcyclohexane, and aliphatic esters such as ethyl acetate, butyl acetate, amyl acetate, cellosolve acetate, and propylene glycol monomethyl ether acetate. And so on. In addition, it is not limited to such specific examples as long as it is inert to the unsaturated carboxylic acids as a raw material and does not significantly inhibit radical polymerization. As the cationic polymerization initiator used for the cationic polymerization, a known catalyst can be used. For example, a protonic acid such as sulfuric acid can be used, and a Lewis acid such as boron trifluoride and aluminum chloride and water, alcohol, ether and the like can be used. A cocatalyst can be used in combination. As the anionic polymerization initiator, known substances can be used, and specifically, NaR, RMgX, ROK
(R represents an alkyl group, X represents a halogen atom), pyridine and the like. As the coordination anion initiator, a Ziegler-Natta catalyst, a metallocene catalyst, or the like can be used.

In the component (c), the reaction between the polymer and a hydrophobic compound having a reactivity with the carboxylic acid is carried out by reducing a carboxyl group in the polymer by 20 to 8%.
The reaction is preferably performed at about 0%. When the polymer used has high hydrophobicity, a low modification rate is preferable, and when the polymer has low hydrophobicity, a high modification rate is preferable. It is also possible to use, as a polymerization reaction component, a carboxylic acid which is a component of the component (c) and a pre-esterified hydrophobic compound having reactivity with the carboxylic acid.

The charging amount of the component (c) is not particularly limited, but is 3 to the total charging amount of the components (a) to (d).
It is preferably about 15% by weight. (C) component is 3
When the amount is less than 15% by weight, the solubility of the obtained polyester resin is low, and when the amount of the component (c) is more than 15% by weight, it is difficult to obtain a desired molecular weight.

As the polyol as the component (d), dipentaerythritol, pentaerythritol,
Examples of various diols conventionally known as polyol components of rosin-modified phenol resins such as diglycerin, glycerin, ditrimethylolpropane, trimethylolpropane, ditrimethylolethane, trimethylolethane, ethylene glycol, diethylene glycol, and neopentyl glycol can be given. From the viewpoint of appropriately adjusting the softening point and molecular weight of the resin, it is preferable to use glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, diglycerin, ditrimethylolpropane, and ditrimethylolethane. (D)
Although the use amount of the component is not particularly limited, the total number of hydroxyl equivalents (OH) in each of the components (a) to (d) is set in order to give a desired molecular weight and an appropriate emulsifying property of the ink in designing the polyester resin. It is preferable to adjust the ratio of the total number of carboxyl groups (COOH) to OH / COOH = 0.50 to 1.00. The amount of component (d) to be charged is not particularly limited, but may be any of (a) to (d).
It is preferable that the amount is about 3 to 11% by weight based on the total charged amount of the components. If the amount of the component (d) is less than 3% by weight, it is difficult to obtain a desired molecular weight.
If the amount is more than the percentage by weight, it is difficult to obtain proper emulsifying properties of the ink. In the calculation of the OH / COOH (equivalent ratio), among the aliphatic monoamines in the component (c), secondary amines are regarded as monovalent, primary amines are regarded as divalent, and The number of equivalents = the number of equivalents of the OH,
The total number of OH equivalents including the number of equivalents of OH is used. In addition, the aliphatic monoepoxys in the component (c) are regarded as dihydric alcohols, and the total number of OH including the number of equivalents of OH is used.

As the reaction conditions of the components (a), (b), (c) and (d), a conventionally known method for producing a polyester resin can be adopted. For example,
Predetermined amounts of component (a), component (b), component (c) and component (d) are charged into a reactor at a temperature of about 230 to 300 ° C. in the presence or absence of a conventionally known acidic / basic catalyst. The reaction is performed for about 2 to 20 hours. The reaction order of each component is not particularly limited, and the components may be charged in any order. For example, as described above, the method of simultaneously charging the component (a), the component (b), the component (c) and the component (d), the reaction of the component (a) with the component (d), the component (b), ) Component and, if necessary, component (d). Examples of the catalyst include mineral acids such as hydrochloric acid and sulfuric acid, sulfonic acids such as methanesulfonic acid, paratoluenesulfonic acid and dodecylbenzenesulfonic acid, oxides such as zinc oxide, magnesium oxide and calcium oxide, magnesium hydroxide, and water. Hydroxides such as calcium oxide can be exemplified.

When the above-mentioned reaction method is adopted, a desired molecular weight and softening point are adjusted by adding a dicarboxylic acid such as phthalic acid or adipic acid at an arbitrary ratio before and / or during the esterification. You can also.

The resin of the present invention obtained by the above reaction method has a high softening point. Softening point is usually 120-200
° C, preferably about 140 to 200 ° C. This is because by setting the softening point to 120 ° C. or more, the drying property and the setting property can be kept good.
Also, considering the solubility in the ink solvent, 200 ° C. or less is appropriate. The weight average molecular weight of the polyester resin of the present invention is usually 40,000 to 400,
50,000, preferably 50,000 to 200,
000. If it is less than 40,000, it is difficult to obtain a desired viscosity, and if it is more than 400,000, it becomes high in viscosity, making stable production difficult. The resin of the present invention has good solubility, and has sufficient solubility even in petroleum-based ink solvents containing no aromatic component.
The resin of the present invention has a linseed oil viscosity of 33% by weight of 4-1.
It has a high viscosity of 5 Pa · s. The polyester resin of the present invention thus obtained is useful as a binder for printing ink.

The printing ink binder of the present invention is prepared, for example, by the following method. The polyester resin of the present invention is mixed with a vegetable oil, a gelling agent, and, if necessary, a solvent and the like, and is appropriately heated and dissolved or reacted to prepare a binder for a printing ink as a gel varnish. A petroleum resin, an alkyd resin, a rosin ester, a fatty acid ester, or the like may be appropriately used in the printing ink binder as long as the performance of the obtained printing ink is not impaired. The solid concentration of the polyester resin in the gel varnish is not particularly limited, but is appropriately determined in consideration of workability during printing and the like, and is usually about 20 to 60% by weight, preferably about 30 to 50% by weight. It is practical to adjust the varnish viscosity to a value measured by a cone-and-plate viscometer at 25 ° C. usually in the range of about 10 to 1000 Pa · s.

The vegetable oil used for preparing the printing ink binder of the present invention is not particularly limited, and various known oils can be used. Specific examples include linseed oil, tung oil or a polymerized oil thereof, safflower oil, dehydrated castor oil, soybean oil, etc., and vegetable oils having an unsaturated bond are preferred from the viewpoint of drying properties of printed matter. Soybean oil is particularly preferred from the viewpoint of environmental measures.

Examples of the gelling agent used for preparing the binder for printing ink of the present invention include known ones such as aluminum octylate, aluminum stearate, aluminum triisopropoxide, and aluminum dipropoxide monoacetyl acetate.

The solvent used for preparing the printing ink binder of the present invention is not particularly limited as long as it is a petroleum solvent having a boiling point of about 200 ° C. or more and an aromatic hydrocarbon content of about 1% by weight or less. And known ones can be used. Specifically, Nisseki Mitsubishi Corp. No. 0 solvent, Nisseki Mitsubishi Corp. AF4 solvent, Nisseki Mitsubishi Corp. AF5
No. Solvent, Nisseki Mitsubishi Corp. AF6 Solvent,
AF7 Solvent manufactured by Mitsubishi Nisseki Co., Ltd., and the like.

The gel varnish thus obtained, which is a binder for a printing ink of the present invention, contains a pigment such as yellow, red, indigo or black, a vegetable oil and / or a boiling point of 200.
A petroleum solvent having an aromatic hydrocarbon content of about 1% or less at about ℃ or higher, and a surfactant, wax, dryer, and other additives for improving ink fluidity and ink surface film as required Is appropriately blended. The thus obtained composition is kneaded using a usual ink production apparatus such as a roll mill, a ball mill, an attritor, a sand mill and the like, and is adjusted to an appropriate constant number of inks. (Sheet-fed ink),
A desired printing ink such as an offset rotary ink (off-wheel ink) and a waterless offset ink is manufactured. In addition,
The amount of the binder according to the present invention used in the production of the printing ink is such that the solid content of the polyester resin is 10 to 5%.
It is preferable to mix them so as to be about 0% by weight.

As for the type of printing ink, it can be used especially for offset printing ink, and can also be suitably used for newspaper ink, letterpress printing ink, and gravure printing ink.

[0033]

According to the present invention, there is provided a polyester resin which is environmentally preferable because an alkylphenol formaldehyde condensate is not used, and has a high molecular weight, a high softening point, a high viscosity and a high solubility comparable to those of a rosin-modified phenol resin. it can. Further, when the polyester resin of the present invention is used as a binder for offset printing ink, the emulsifying properties of the printing ink, gloss, drying properties, printing suitability such as misting are equal to or higher than conventionally known rosin-modified phenol resins. Therefore, a printing ink that meets today's requirements can be provided. Further, a binder for printing ink using the polyester resin, soybean oil and / or a boiling point of 200 ° C. or more and an aromatic hydrocarbon content of 1% by weight.
By using the following petroleum-based solvents and, if necessary, printing inks containing additives, it is possible to improve health and safety aspects such as environmental issues and working environments.

[0034]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but it is needless to say that the present invention is not limited to these examples. Hereinafter, "parts" means parts by weight.

Production Example 1 (Production of unsaturated acid-modified rosin) 1,000 parts of gum rosin was charged into a reaction vessel equipped with a stirrer, a reflux condenser equipped with a water separator, and a thermometer, and stirred at 180 ° C. under a nitrogen atmosphere. Until it was melted. Then, 267 parts of fumaric acid was added, the temperature was raised to 230 ° C. with stirring for 1 hour, and then cooled to obtain a solid resin (acid value:
342.0) was obtained. In addition, the said acid value is JISK56.
No. 01 (hereinafter, the acid value is a value measured by the same method).

Production Example 2 (Production of Polar Group-Containing Petroleum Resin) A DCPD petroleum resin (trade name: Quinton 1325, manufactured by Nippon Zeon Co., Ltd.)
000 parts, 180 ° C while stirring under a nitrogen atmosphere
Until it was melted. Then, maleic anhydride 70
Then, the mixture was heated to 230 ° C. under stirring for 3 hours, and then cooled to obtain a solid resin (theoretical acid value: 75, weight average molecular weight: 1,500). The theoretical acid value is
It is calculated from the number of carboxyl group equivalents of the raw material used (the same applies hereinafter). The weight average molecular weight refers to gel permeation chromatography (manufactured by Tosoh Corporation,
HLC-8020) and TSK-GE manufactured by Tosoh Corporation
It means a value in terms of polystyrene measured using a L column in a THF solvent (hereinafter, the weight average molecular weight is a value measured by the same method).

Production Example 3 (Production of Polar Group-Containing Petroleum Resin) In a reaction vessel similar to that of Production Example 1, DCPD petroleum resin (trade name: Quinton 1325, manufactured by Nippon Zeon Co., Ltd.)
000 parts and 100 parts of xylene were charged and heated to 150 ° C. while stirring under a nitrogen atmosphere to be melted. Then, 70 parts of maleic anhydride was charged and di-t-butyl peroxide (trade name: Perbutyl D, Nippon Oil & Fats Co., Ltd.)
6 parts continuously for 30 minutes, and xylene is added as needed to suppress thickening.
It was kept warm for 5 hours. After keeping the temperature, 200 ℃ to remove xylene
The pressure is reduced to 0.02 MPa for 10 minutes (the temperature is increased to 230 ° C. as needed to suppress thickening), and the solid resin is cooled (theoretical acid value: 75, weight average molecular weight: 5,000).
I got

Production Example 4 (Production of a 70% resole-type nonylphenol xylene solution) In the same reaction vessel as in Production Example 1, nonylphenol 1,0 was added.
00 parts, paraformaldehyde 270 parts and water 1,0
Then, the mixture was heated to 50 ° C. with stirring. 50 ℃
In the above, 100 parts of sodium hydroxide was charged, and the temperature was gradually raised to 90 ° C. while cooling, and the temperature was maintained for 2.5 hours, and the pH was adjusted to about 6 by dropwise addition of sulfuric acid. Thereafter, 150 parts of xylene was added, and the aqueous layer containing formaldehyde and the like was removed.
% Xylene solution was obtained.

Example 1 A reactor equipped with a stirrer, a reflux condenser with a water separator and a thermometer was charged with 238 parts of an α-olefin having 16 to 18 carbon atoms (trade name: Dialen 168, manufactured by Mitsubishi Chemical Corporation). The mixture was charged and heated to 155 to 160 ° C. while stirring under a nitrogen atmosphere. Then, 98 parts of maleic anhydride and di-t-
13.5 parts of butyl peroxide (trade name: Perbutyl D, manufactured by NOF Corporation) was continuously added in one hour.
After further keeping the temperature at 155 to 160 ° C for 1 hour, 271 parts of stearyl alcohol was added and reacted at 220 ° C for 4 hours. The resin thus obtained (weight average molecular weight: 4,3
00), polymerized rosin (trade name: Silvatac 1)
40, 359 parts of Silvachem, acid value: 140), 57 parts of the resin obtained in Production Example 1, and 433 parts of the resin obtained in Production Example 2 were stirred with a stirrer, a reflux condenser with a water separator, and a thermometer. , And heated to 180 ° C. while stirring under a nitrogen atmosphere to melt. Then, O
29 parts of pentaerythritol and 29 parts of glycerin were added so that H / COOH (equivalent ratio) = 0.90, and the mixture was heated to 260 ° C. with stirring and reacted until the acid value became 20 or less. After completion of the esterification reaction, the viscosity of the linseed oil of 33% by weight was adjusted to 8.0 Pa · s, and 0.02 MPa
For 10 minutes and cooled to obtain a solid resin. The resulting polyester resin solution of an aliphatic hydrocarbon solvent (trade name: No. Solvent, manufactured by Mitsubishi Nisseki Co., Ltd.) has a tolerance of 1.6 g / g, an acid value of 15.5, and a softening point of 165.
C., weight average molecular weight was 150,000 (see Table 1). The 33% by weight linseed oil viscosity is measured at 25 ° C. using a cone and plate type viscometer manufactured by Nippon Rheological Instruments Co., Ltd. by heating and mixing a resin and linseed oil in a 1: 2 weight ratio. (Hereinafter, the viscosity is a value measured by the same method). The tolerance (indicator of solubility) refers to the total weight of the solvent required for adding a No. 0 solvent at 25 ° C. to a mixture obtained by heating and mixing a resin and a No. 0 solvent at a weight ratio of 1: 1 and becoming cloudy. The softening point, which is a value calculated from the resin weight (hereinafter, the tolerance is a value measured by the same method), is defined as JIS K
5601 (hereinafter, the softening point is a value measured by the same method).

Example 2 A reaction apparatus similar to that of Example 1 was charged with α-C 16-18.
Olefin (trade name dialen 168, Mitsubishi Chemical Corporation)
238 parts) and stirring under a nitrogen atmosphere.
The temperature was raised to 55 to 160 ° C. 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 in one hour. After further keeping the temperature at 155 to 160 ° C. for one hour, a higher alcohol having about 50 carbon atoms (trade name: Unilin Alcohol 700, manufactured by Toyo Petrolite Co., Ltd.) 70
0 part was added and reacted at 220 ° C. for 4 hours. The resin (weight average molecular weight: 4,800) obtained in this manner was converted into 69
Parts, 365 parts of polymerized rosin (trade name: Silvatac 140, manufactured by Silvachem, acid value: 140), 69 parts of the resin obtained in Production Example 1, and 440 parts of the resin obtained in Production Example 2 were stirred with a stirrer. A reactor equipped with a reflux condenser with a water condenser and a thermometer was charged, and stirred under a nitrogen atmosphere.
The temperature was raised to ° C. to be melted. Then OH / COOH
29 parts of pentaerythritol and 29 parts of glycerin were added so that (equivalent ratio) = 0.90, and 2 parts were stirred.
The temperature was raised to 60 ° C., and the reaction was performed until the acid value became 20 or less. After the completion of the esterification reaction, the viscosity of the linseed oil of 33% by weight was adjusted to 8.0 Pa · s, and the pressure was reduced at 0.02 MPa for 10 minutes, followed by cooling to obtain a solid resin. Table 1 shows the tolerance, acid value, softening point and weight average molecular weight of the polyester resin thus obtained.

Example 3 In the same reactor as in Example 1, an alternating copolymer of an α-olefin having about 28 to 50 carbon atoms and maleic anhydride (trade name: Diacarna 30, manufactured by Mitsubishi Chemical Corporation, theoretical acid) Price:
150) 748 parts and heated to 180 ° C. while stirring under a nitrogen atmosphere. Then, 271 parts of isostearyl alcohol was added, the temperature was raised to 220 ° C, and the reaction was performed for 4 hours. The resin thus obtained (weight average molecular weight: 1
0,500) and 362 of polymerized rosin (trade name: Silvatack 140, manufactured by Silvachem, acid value: 140).
Parts, 57 parts of the resin obtained in Production Example 1, and 432 parts of the resin obtained in Production Example 2 were charged into a reactor equipped with a stirrer, a reflux condenser with a water separator, and a thermometer, and stirred under a nitrogen atmosphere. The temperature was raised to 180 ° C. while melting. Then, OH / COOH (equivalent ratio) = 0.90,
27 parts of pentaerythritol and 27 parts of glycerin were added, and the mixture was heated to 260 ° C. with stirring and reacted until the acid value became 20 or less. After completion of the esterification reaction, the viscosity of the linseed oil of 33% by weight was adjusted to 8.0 Pa · s, and 0.02 M
The pressure was reduced at Pa for 10 minutes and the mixture was cooled to obtain a solid resin. Table 1 shows the tolerance, acid value, softening point and weight average molecular weight of the polyester resin thus obtained.

Example 4 935 parts of an acid-modified low molecular weight polyethylene (trade name: High Wax 1105A, manufactured by Mitsui Petrochemical Industry Co., Ltd., theoretical acid value: 60) was charged into a reactor similar to that in Example 1, and the mixture was placed in a nitrogen atmosphere. The temperature was raised to 180 ° C. while stirring below. Next, 68 parts of oleyl alcohol was added, the temperature was raised to 220 ° C., and the reaction was performed for 4 hours. 118 parts of the resin thus obtained (weight average molecular weight: 2,400), polymerized rosin (trade name: Silvatack 140, manufactured by Silvachem, acid value: 1)
40) was 348 parts, and the resin obtained from Production Example 1 was
And 420 parts of the resin obtained in Production Example 2 were charged into a reactor equipped with a stirrer, a reflux condenser with a water separator, and a thermometer, and heated to 180 ° C. while stirring under a nitrogen atmosphere to melt. . Then, OH / COOH (equivalent ratio) = 0.
To the mixture, 27 parts of pentaerythritol and 27 parts of glycerin were added, and the mixture was heated to 260 ° C. with stirring and reacted until the acid value became 20 or less. After the completion of the esterification reaction, the viscosity of the linseed oil of 33% by weight was adjusted to 8.0 Pa · s, and the pressure was reduced at 0.02 MPa for 10 minutes, followed by cooling to obtain a solid resin. Table 1 shows the tolerance, acid value, softening point and weight average molecular weight of the polyester resin thus obtained.

Example 5 935 parts of an acid-modified low-molecular-weight polyethylene (trade name: High Wax 1105A, manufactured by Mitsui Petrochemical Industry Co., Ltd., theoretical acid value: 60) was charged into a reaction apparatus similar to that in Example 1, and a nitrogen atmosphere was used. The temperature was raised to 180 ° C. while stirring below. Then, after cooling to 150 ° C., cyclohexanol 50
The reaction mixture was heated at 150 ° C. for 3 hours, and then heated to 220 ° C. for 2 hours. 117 parts of the resin (weight average molecular weight: 2,100) thus obtained was polymerized rosin (trade name: Silvatack 140, manufactured by Silvachem, acid value: 14)
0) 346 parts, 66 parts of the resin obtained from Production Example 1,
417 parts of the resin obtained from Production Example 2 was charged into a reactor equipped with a stirrer, a reflux condenser with a water separator, and a thermometer,
The temperature was raised to 180 ° C. while stirring under a nitrogen atmosphere to melt. Then, OH / COOH (equivalent ratio) = 0.90
Then, 27 parts of pentaerythritol and 27 parts of glycerin were added, and the mixture was heated to 260 ° C. with stirring and reacted until the acid value became 20 or less. After the completion of the esterification reaction, the viscosity of the linseed oil of 33% by weight was adjusted to 8.0 Pa · s, and the pressure was reduced at 0.02 MPa for 10 minutes, followed by cooling to obtain a solid resin. Table 1 shows the tolerance, acid value, softening point and weight average molecular weight of the polyester resin thus obtained.

Example 6 In the same reactor as in Example 1, Chinese gum rosin 450 was added.
Parts, α-olefin having 16 to 18 carbon atoms (trade name: Dialen 168, manufactured by Mitsubishi Chemical Corporation) was charged with 238 parts,
The temperature was raised to 135 to 140 ° C. while stirring under a nitrogen atmosphere. Then, 230 parts of maleic anhydride and 27 parts of di-t-butyl peroxide (trade name: Perbutyl D, manufactured by NOF Corporation) were continuously added in one hour. Then 1
After keeping the temperature at 55 to 160 ° C. for 1 hour and at 220 ° C. for 1 hour, 543 parts of stearyl alcohol was added and the mixture was heated at 230 ° C.
For 4 hours. 157 parts of the resin (weight average molecular weight: 3,500) thus obtained, polymerized rosin (trade name: Silvatack 140, manufactured by Silvachem, acid value: 14)
0) and 431 parts of the resin obtained in Production Example 2 were charged into a reactor equipped with a stirrer, a reflux condenser equipped with a water separator and a thermometer, and stirred at 180 ° C. under a nitrogen atmosphere.
Until it was melted. Then, pentaerythritol 2 was added so that OH / COOH (equivalent ratio) = 0.90.
7 parts and 27 parts of glycerin are added, and
The temperature was raised to ° C., and the reaction was carried out until the acid value became 20 or less.
After completion of the esterification reaction, the linseed oil viscosity of 33% by weight was 8.
Adjusted to 0 Pa · s, reduced pressure at 0.02 MPa for 10 minutes,
Upon cooling, a solid resin was obtained. Table 1 shows the tolerance, acid value, softening point and weight average molecular weight of the polyester resin thus obtained.

Example 7 The same reactor as in Example 1 was charged with 250 parts of xylene, heated to 130 to 135 ° C. under a nitrogen stream, and 600 parts of styrene, 37.5 parts of methacrylic acid, and 2-ethylhexyl acrylate were added. After continuously adding 112.5 parts of the mixed solution and 52.5 parts of di-t-butyl peroxide (trade name: Perbutyl D, manufactured by NOF Corporation) for 4 hours,
It was kept at the same temperature for 2 hours. Next, 30 parts of stearyl alcohol was added and reacted at 230 ° C. for 4 hours. The resin (weight average molecular weight: 3,600) thus obtained was added to 11
7 parts, 346 parts of polymerized rosin (trade name: Silvatac 140, manufactured by Silvachem, acid value: 140), 66 parts of the resin obtained from Production Example 1, and resin 41 obtained from Production Example 2
7 parts were charged into a reactor equipped with a stirrer, a reflux condenser equipped with a water separator and a thermometer, and stirred under a nitrogen atmosphere.
The temperature was raised to 80 ° C. to be melted. Then OH / COO
27 parts of pentaerythritol and 27 parts of glycerin were added so that H (equivalent ratio) = 0.90, and the mixture was heated to 260 ° C. with stirring and reacted until the acid value became 20 or less. After the completion of the esterification reaction, the viscosity of the linseed oil of 33% by weight was adjusted to 8.0 Pa · s, and the pressure was reduced at 0.02 MPa for 10 minutes, followed by cooling to obtain a solid resin. Table 1 shows the tolerance, acid value, softening point and weight average molecular weight of the polyester resin thus obtained.

Example 8 The same reactor as in Example 1 was charged with α-α having 16 or 18 carbon atoms.
238 parts of an olefin (trade name: Dialen 168, manufactured by Mitsubishi Chemical Corporation) were charged, and the temperature was raised to 155 to 160 ° C while stirring under a nitrogen atmosphere. 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 in one hour. After further keeping the temperature at 155 to 160 ° C. for 1 hour, 392 parts of distearylamine was added to add 2 hours.
The reaction was performed at 20 ° C. for 4 hours. 94 parts of the resin thus obtained (weight average molecular weight: 4,500), polymerized rosin (trade name: Silvatack 140, manufactured by Silvachem, acid value: 1)
40) was used in 359 parts, and the resin obtained in Production Example 1 was used in 57 parts.
And 433 parts of the resin obtained in Production Example 2 were charged into a reactor equipped with a stirrer, a reflux condenser equipped with a water separator, and a thermometer, and heated to 180 ° C. while stirring under a nitrogen atmosphere to melt. . Then, OH / COOH (equivalent ratio) = 0.
29 parts of pentaerythritol and 29 parts of glycerin were added to 90, and the mixture was heated to 260 ° C. with stirring and reacted until the acid value became 20 or less. After completion of the esterification reaction, the viscosity of the linseed oil at 33% by weight was increased to 8.0 Pa · s.
The pressure was reduced at 0.02 MPa for 10 minutes and cooled to obtain a solid resin. Table 1 shows the tolerance, acid value, softening point and weight average molecular weight of the polyester resin thus obtained.

Example 9 The same reactor as in Example 1 was charged with α-α having 16 to 18 carbon atoms.
Olefin (trade name dialen 168, Mitsubishi Chemical Corporation)
238 parts) and stirring under a nitrogen atmosphere.
The temperature was raised to 55 to 160 ° C. 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 in one hour. After further keeping the temperature at 155 to 160 ° C for 1 hour, 300 parts of 1,2-epoxyoctadecane was added and reacted at 220 ° C for 4 hours. 96 parts of the resin thus obtained (weight average molecular weight: 6,500), 364 parts of polymerized rosin (trade name: Silvatac 140, manufactured by Silvachem, acid value: 140), and 46 parts of the resin obtained from Production Example 1 Parts, 439 parts of the resin obtained from Production Example 2,
The mixture was charged into a reactor equipped with a reflux condenser with a water separator and a thermometer, and heated to 180 ° C. with stirring under a nitrogen atmosphere to be melted. Then, OH / COOH (equivalent ratio) =
28 parts of pentaerythritol and 28 parts of glycerin were added so as to obtain 0.90, and the mixture was heated to 260 ° C. with stirring and reacted until the acid value became 20 or less. After completion of the esterification reaction, the viscosity of the linseed oil at 33% by weight was increased to 8.0 Pa · s.
The pressure was reduced at 0.02 MPa for 10 minutes and cooled to obtain a solid resin. Table 1 shows the tolerance, acid value, softening point and weight average molecular weight of the polyester resin thus obtained.

Example 10 A reaction apparatus similar to that of Example 1 was charged with α-C 16-18.
Olefin (trade name dialen 168, Mitsubishi Chemical Corporation)
238 parts) and stirring under a nitrogen atmosphere.
The temperature was raised to 55 to 160 ° C. 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 in one hour. After further keeping the temperature at 155 to 160 ° C. for 1 hour, 271 parts of stearyl alcohol was added and
The reaction was performed at 4 ° C. for 4 hours. 94 parts of the resin (weight average molecular weight: 4,300) thus obtained, polymerized rosin (trade name: Silvatack 140, manufactured by Silvachem, acid value: 140)
359 parts of the resin obtained in Production Example 1, 57 parts of the resin obtained in Production Example 3, and 433 parts of the resin obtained in Production Example 3 were charged into a reactor equipped with a stirrer, a reflux condenser with a water separator, and a thermometer. The temperature was raised to 180 ° C. with stirring to melt. Then, 29 parts of pentaerythritol and 29 parts of glycerin were added so that OH / COOH (equivalent ratio) = 0.90, and the mixture was heated to 260 ° C. with stirring and reacted until the acid value became 20 or less. After the end of the esterification reaction,
33% by weight linseed oil viscosity was adjusted to 8.0 Pa · s,
The pressure was reduced at 0.02 MPa for 10 minutes, followed by cooling to obtain a solid resin. The tolerance of the polyester resin thus obtained,
Table 1 shows the acid value, softening point and weight average molecular weight.

Comparative Example 1 552 parts of gum rosin were charged into the same reactor as in Example 1, and the mixture was heated to 230 ° C. while stirring under a nitrogen atmosphere to be melted. Then, 52 parts of pentaerythritol and 2 parts of zinc oxide were added, and the mixture was heated to 260 ° C. with stirring, and reacted until the acid value became 20 or less. Further 230
After cooling to ℃, 394 parts (276 parts solids) of a 70% xylene solution of resole nonylphenol obtained from Production Example 4 was dropped into the system over a period of 4 hours within a temperature range of 230 to 260 ° C. while keeping the temperature. did. After dropping, 33
The weight% linseed oil viscosity was adjusted to 8.0 Pa · s,
The pressure was reduced at 2 MPa for 10 minutes, followed by cooling to obtain a solid resin. Table 1 shows the tolerance, acid value, softening point and weight average molecular weight of the rosin-modified phenol resin thus obtained.

[0050]

[Table 1]

(Preparation A of gel varnish) 45 parts of the resin obtained in Example 1, 10 parts of soybean oil and an alicyclic hydrocarbon solvent (trade name: AF Solvent 7, manufactured by Mitsubishi Nisseki Co., Ltd.)
45 parts were mixed and dissolved at 180 ° C. for 30 minutes to obtain a varnish.
After cooling this varnish to 60 ° C., aluminum chelate (trade name: ALCH, manufactured by Kawaken Fine Chemical Co., Ltd.) 1.0
Then, the mixture was heated to 190 ° C. and kept for 1 hour to obtain a gel varnish. For each resin obtained in Examples 2 to 10 and Comparative Example 1, gel varnish was prepared in the same manner as described above.

(Preparation of Ink A) A printing ink was prepared by using the above-mentioned gel varnish and kneading with a mixing ratio shown in Table 1 using a three-roll mill.

[0053]

[Table 2] The tack value of the ink is 6.5 ± 0.5 based on the above composition.
5. The flow value was appropriately adjusted to be 41.0 ± 1.0.

(Ink Performance Test A) Tack value: 1.3 ml of ink was spread on an incometer (manufactured by Toyo Seiki Co., Ltd.), and roll temperature was 30 ° C. and 400 r.
Spin at pm for 1 minute and read the value. The results are shown in Table 3. Flow value: About 2 ml of the ink was put into a sample hole of a spread meter (manufactured by Kumagai Riki Kogyo Co., Ltd.), the upper surface of the ink was scraped off with a spatula so as to be flush with the upper surface of the fixing plate, and the load plate was dropped. The diameter value of the concentric ink spread one minute later was read. The results are shown in Table 3. Gloss: After 0.4 ml of ink was spread on art paper with an RI tester (manufactured by Ishikawajima Sangyo Kikai Co., Ltd.), the temperature was increased to 20 ° C and 65 ° C.
% R. H. For 24 hours, and the reflectance at 60 ° to 60 ° was measured with a gloss meter. The larger the value of the gloss, the better the gloss. The results are shown in Table 3. Drying property: After 0.4 ml of ink was spread on art paper with an RI tester (manufactured by Ishikawajima Sangyo Kikai Co., Ltd.), it was exposed to an atmosphere of 160 ° C. for 2 seconds, 4 seconds, and 6 seconds, respectively. A state without stickiness was judged as dry. The smaller the value, the better the drying property. The results are shown in Table 3.
It was shown to. Misting: 2.6 ml of ink was spread on an incometer (manufactured by Toyo Seiki Co., Ltd.) and roll temperature was 30 ° C., 400
1 minute at rpm and 2 minutes at 1800 rpm,
Evaluation was performed by observing the degree of scattering of the ink on white paper placed directly under the roll. Misting shows that the larger the numerical value, the better, and the results are shown in Table 3. Emulsification rate: 3.9 ml of ink was spread on a dynamic emulsification tester (manufactured by Nippon Rheological Instruments Co., Ltd.), and roll temperature was 30 ° C.
Pure water was supplied at a rate of 5 ml / min at 200 rpm, and the amount of water in the ink was measured by an infrared moisture meter. The smaller the numerical value of the emulsification ratio, the better, and the results are shown in Table 3.

[0055]

[Table 3]

(Preparation B of Gel Varnish) 45 parts of the resin obtained in Example 1 and 55 parts of soybean oil were mixed and dissolved at 180 ° C. for 30 minutes to obtain a varnish. After cooling this varnish to 60 ° C,
Add 0.5 part of aluminum chelate (trade name: ALCH, manufactured by Kawaken Fine Chemicals Co., Ltd.), raise the temperature to 190 ° C.,
The mixture was kept warm for a time to obtain a gel varnish. For the resins obtained in Examples 2 to 10 and Comparative Example 1, gel varnishes were prepared in the same manner as described above.

(Preparation of Ink B) A printing ink was prepared by using the above-mentioned gel varnish to prepare a printing ink in a mixing ratio shown in Table 3 using a three-roll mill.

[0058]

[Table 4] Based on the above composition, the tack value of the ink is 7.0 ± 0.
5. The flow value was adjusted appropriately so as to be 34.0 ± 1.0.

(Ink Performance Test B) Tack value: 1.3 ml of ink was spread on an incometer (manufactured by Toyo Seiki Co., Ltd.), and roll temperature was 30 ° C. and 400 r.
Spin at pm for 1 minute and read the value. Table 5 shows the results. Flow value: About 2 ml of the ink was put into a sample hole of a spread meter (manufactured by Kumagai Riki Kogyo Co., Ltd.), the upper surface of the ink was scraped off with a spatula so as to be flush with the upper surface of the fixing plate, and the load plate was dropped. The diameter value of the concentric ink spread one minute later was read. Table 5 shows the results. Gloss: 0.27 ml of ink was spread on art paper with an RI tester (manufactured by Ishikawajima Sangyo Kikai Co., Ltd.), and then coated at 20 ° C., 6
5% R. H. For 24 hours, and the reflectance at 60 ° to 60 ° was measured with a gloss meter. The larger the value of the gloss, the better the gloss. The results are shown in Table 5. Drying property: 0.27 ml of ink was spread on parchment paper using RI tester (manufactured by Ishikawajima Sangyo Kikai Co., Ltd.). (Manufactured by Seisakusho Co., Ltd.) and wound around a rotating drum such that the paper sulfuric acid paper was on the outside. The weight and the pressing gear are gently lowered onto the paper parchment paper, and the drum is rotated. The time when the tooth profile of the pressing gear hardly shifts is defined as the drying time. The smaller the value, the better the drying property,
Table 5 shows the results. Misting: 2.6 ml of ink was spread on an incometer (manufactured by Toyo Seiki Co., Ltd.) and roll temperature was 30 ° C., 400
rpm for 1 minute at 1200 rpm and 2 minutes at 1200 rpm,
Evaluation was performed by observing the degree of scattering of the ink on white paper placed directly under the roll. Misting shows that the larger the numerical value, the better, and the results are shown in Table 5. Emulsification rate: 3.9 ml of ink was spread on a dynamic emulsification tester (manufactured by Nippon Rheological Instruments Co., Ltd.), and roll temperature was 30 ° C.
Pure water was supplied at a rate of 5 ml / min at 200 rpm, and the amount of water in the ink was measured by an infrared moisture meter. The smaller the value of the emulsification ratio, the better the results. The results are shown in Table 5.

[0060]

[Table 5]

From the results in Tables 3 and 5, the printing ink using the polyester resin of the present invention (Examples 1 to 10) was the same as or similar to the printing ink of the present invention using the rosin-modified phenol resin (Comparative Example 1). It can be seen that it has higher performance. Further, in the present invention, in terms of printability, a printing ink using a resin (Example 10) using a radical copolymerization type as the component (b) is:
It can be seen that, compared to the printing ink using the resin (Examples 1 to 9) in which the component (b) uses an addition reaction type, the misting and the emulsification resistance are more excellent.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 AF02W BA01X CF00Y CF01Y GH00 4J029 AA01 AB01 AB04 AC02 AD01 AD05 AE11 CA02 FC02 FC03 FC04 FC05 FC07 FC08 GA11 GA12 GA13 GA14 GA15 GA16 GA17 GA32 GA42 GA43 GA81 GA82 GA83 GA84 HA01B 4J039 AB08 AD18 AE06 BE01 CA07 DA02 EA10 EA33 EA44 GA01 GA03 GA04

Claims (11)

[Claims] 1. A polymer comprising (a) a rosin, (b) a petroleum resin containing a polar group, (c) a carboxylic acid and a hydrophobic polymerizable unsaturated compound, and a polymer having a reactivity with the carboxylic acid in the polymer. And a polyester resin composition obtained by reacting (d) a polyol. 2. The composition according to claim 1, wherein the component (a) contains a rosin having two or more carboxyl groups in the molecule.
The polyester resin composition as described in the above. 3. The polyester resin composition according to claim 1, wherein the component (b) contains a petroleum resin having two or more polar groups in the molecule. 4. Component (c) having a weight average molecular weight of 2,000
The polyester resin composition according to any one of claims 1 to 3, wherein the polyester resin composition is from 0 to 30,000. 5. The component (c) is a hydrophobic polymerizable unsaturated compound having 2 to 50 carbon atoms, an aliphatic unsaturated hydrocarbon monomer, 5 to 50 carbon atoms, an alicyclic unsaturated hydrocarbon monomer, An aromatic hydrocarbon monomer having a number of 8 to 50,
The polyester resin composition according to any one of claims 1 to 4, comprising at least one selected from rosins, higher unsaturated fatty acids, and unsaturated oils. 6. The component (c) is a hydrophobic compound having reactivity to carboxylic acids (i) an aliphatic monoalcohol having 6 to 50 carbon atoms, and (ii) an aliphatic dialcohol having 6 to 50 carbon atoms. And (iii) at least one selected from aliphatic monoamines having 6 to 50 carbon atoms and (iv) aliphatic monoepoxy having 6 to 50 carbon atoms. The polyester resin composition according to the above. 7. The polyester resin composition according to claim 1, which has a softening point of 120 to 200 ° C. 8. A weight average molecular weight of 40,000 to 40.
The polyester resin composition according to any one of claims 1 to 7, which has a molecular weight of 000. 9. A polymer comprising (a) a rosin, (b) a petroleum resin containing a polar group, (c) a carboxylic acid and a hydrophobic polymerizable unsaturated compound, and reactive with the carboxylic acid in the polymer. And (d) a method of producing a polyester resin composition obtained by reacting a polyol with a hydrophobic compound. 10. A binder for printing ink using the polyester resin composition according to claim 1. 11. The printing ink binder, the pigment and the vegetable oil according to claim 10 and / or a boiling point of 200.
A printing ink containing a petroleum solvent having an aromatic hydrocarbon content of 1% or less at a temperature of not less than ° C.