JP2001233947A - Polyester resin, its production method, binder for printing ink, and printing ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester resin 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 prepared without using an alkylphenol- formaldehyde condensate as a raw material; 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: The polyester resin is produced by reacting (a) rosin, (b) a polar-group-containing petroleum resin, (c) at least one substance selected from among aliphatic monohydric alcohols, aliphatic dihydric alcohols, aliphatic monoamines, and aliphatic monoepoxides, and (d) a polyol. The amount of component (a) is 12-75 wt.% of the sum of amounts of components (a) to (d). A production method of the polyester resin, a binder for a printing ink prepared from the resin, and a printing ink prepared by using the binder are also provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyester resin, a method for producing the same, a binder for a printing ink, and a printing ink. The polyester resin 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 used especially for 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, binders for offset printing inks have various properties such as high molecular weight, high softening point, high viscosity, and high solubility in ink solvents, and are excellent in printability. Phenolic 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. Resin,
A method for producing the resin, and a binder for printing ink,
Another object of the present invention is to provide a printing ink having a printability (emulsifying property, gloss, drying property, misting, etc.) equal to or higher than that of a conventionally known rosin-modified phenol resin.

[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 is selected from the group consisting of (a) rosins, (b) a polar group-containing petroleum resin, (c) aliphatic monoalcohols, aliphatic dialcohols, aliphatic monoamines and aliphatic monoepoxys. A specific polyester resin obtained by reacting at least one kind and (d) a polyol at a specific ratio is suitable for the above purpose, and the polyester resin is suitable for various printing ink binder applications. Was found.

That is, the present invention provides (a) rosins,
(B) a polar group-containing petroleum resin, (c) at least one selected from the group consisting of aliphatic monoalcohols, aliphatic dialcohols, aliphatic monoamines and aliphatic monoepoxys, and (d) polyol And the amount of the component (a) is 1 to the total amount of the components (a) to (d).
A polyester resin characterized by being 2 to 75% by weight. The present invention also relates to a method for producing the polyester resin, a binder for a printing ink using the polyester resin, and a printing ink.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The polyester resin of the present invention comprises rosins (hereinafter referred to as component (a)), petroleum resins containing a polar group (hereinafter referred to as component (b)), (c) aliphatic monoalcohols, At least one selected from the group consisting of aliphatic dialcohols, aliphatic monoamines and aliphatic monoepoxys (hereinafter, referred to as component (c)), and polyols (hereinafter, referred to as component (d)) are essential. It is a constituent element and is obtained by reacting these components at a specific ratio described below.

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 components (a), those containing a rosin having two or more carboxyl groups in the molecule are preferable from the viewpoint of increasing the molecular weight of the obtained polyester resin. In order to obtain a high melting point and a high softening point in addition to the high molecular weight of the obtained polyester resin, among these components (a), particularly, polymerized rosin and / or unsaturated acid-modified polymerized rosin is contained. Are preferred. In this case, the total content of the polymerized rosin and the unsaturated acid-modified polymerized rosin is 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-mentioned various types may be used alone, or two or more types may be appropriately used in combination. The charged amount of the component (a) is preferably 12 to 75% by weight based on the total charged amount of the components (a) to (d). If the content of the component (a) is less than 12% by weight, it is difficult to obtain a desired molecular weight.
If the amount is larger, the solubility of the resin is low, and it is difficult to obtain an appropriate emulsification rate of the ink.

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 petroleum resin using methylstyrene, β-methylstyrene or the like as a raw material, copolymerized petroleum resin composed of the DCPD type and C5 type raw material, copolymerized petroleum resin composed of the DCPD type and C9 type raw material, C5 type and C9 Copolymerized petroleum resin composed of a base material, and a copolymerized petroleum resin composed of the DCPD-based, C5-based, and C9-based raw materials, etc., and are produced using no catalyst or Friedel-Crafts type catalyst (cationic polymerization). In particular, it is easy to add a polar group and easily adjust to a desired softening point.
Petroleum resin composed of DC5 and C5 series raw materials, copolymerized petroleum resin composed of DCPD and C9 series raw materials, DCPD series and C5
A copolymerized petroleum resin comprising a C9-based and a C9-based material is preferred.

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 more preferable to employ a radical copolymerization method.

When the component (b) is produced by a radical copolymerization method, a radical initiator and, if necessary, a solvent are used. The type of the radical initiator is not particularly limited, and various known ones can be appropriately selected and used. Specifically, azo-based initiators such as azobisisobutyronitrile, di-t
-Peroxides such as butyl peroxide, benzoyl peroxide, dicumyl peroxide, potassium persulfate, ammonium persulfate and aqueous hydrogen peroxide can be used. The amount of the initiator used is usually in the range of 0.01 to 10% by weight, and preferably 0.1 to 5% by weight, based on the total weight of the raw material petroleum resin and the unsaturated carboxylic acids. Although the reaction temperature is not particularly limited, the optimum temperature may be appropriately determined according to the type of the radical initiator, and can be appropriately set in the range of room temperature to 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 copolymerization 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 the like. The solvent is not limited to the specific examples as long as it is a solvent which is inactive with respect to the unsaturated carboxylic acids as a raw material and does not significantly inhibit radical polymerization.

The amount of the unsaturated carboxylic acid used is preferably 1 to 15 parts by weight based on 100 parts by weight of the starting petroleum resin, and 1 to 15 parts by weight of the unsaturated petroleum resin is used. When the component (b) obtained by modifying 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. In particular, from the viewpoint of improving the misting resistance of the obtained printing ink, it is particularly preferable to employ a radical copolymerization method, and the conditions are also described in paragraphs 0014 to 0.
The reaction conditions are the same as described in 015.

From the viewpoint of increasing the molecular weight of the obtained polyester resin, among the components (b), those containing a petroleum resin having two or more polar groups in the molecule are preferable. These polar group-containing petroleum resins are one of the above.
The species can be used alone, or two or more different species can be used in combination. The charged amount of the component (b) is 19 to the total charged amount of the components (a) to (d).
It is preferably set to ~ 66% by weight. When the amount of the component (b) is less than 19% by weight, it is difficult to obtain proper emulsifying properties of the ink, and when it is more than 66% 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.

As the above-mentioned component (c), aliphatic monoalcohols, aliphatic dialcohols, aliphatic monoamines and aliphatic monoepoxys, the following various ones can be exemplified. Aliphatic monoalcohols having a total carbon number of 10 to 40, aliphatic dialcohols having a total carbon number of 10 to 40, aliphatic monoamines having a total carbon number of 10 to 40, and fats having a total carbon number of 10 to 40 Group epoxys. Specific examples of the compound include decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, eicosanol, docosanol, tetracosanol, hexacosanol, octacosanol, triacontanol,
Oleyl alcohol, isotridecyl alcohol, isostearyl alcohol, geraniol, rosin alcohol, bisabolol, lanolin alcohol and the like can be mentioned. Specific examples of the compound include decanediol, dodecanediol, tetradecanediol, hexadecanediol, octadecanediol, decenediol, dodecenediol, tetradecenediol, hexadecenediol, octadecenediol, lanolin alcohol, and dimer acid. Diols and the like. Specific examples of the compound include decylamine,
Dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, octadecenylamine, tallowalkylamine, soybean alkylamine, dioctadecylamine, dioctadecenylamine and the like can be mentioned. Specific examples of the above compounds include epoxy decane, epoxide decane, epoxy tetradecane, epoxy hexadecane, epoxy octadecane, ethylhexyl glycidyl ether and the like.

The amount of component (c) charged is (a) to (d)
The content is preferably 3 to 11% by weight based on the total charged amount of the components. When the component (c) is less than 3% by weight, the solubility of the obtained polyester resin is low, and when the component (c) is more than 11% by weight, it is difficult to obtain a desired molecular weight. More preferably, the lower limit of the component (c) is 5% by weight and the upper limit is 10% by 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. If a polyol having a long carbon chain is used alone, the softening point of the resin will be low, and if a divalent polyol is used, it will be difficult to form a three-dimensional structure and the molecular weight will be low. Cannot be adjusted. From such a viewpoint, the component (d) includes trihydric alcohols having the longest carbon chain of the molecule having 4 or less carbon atoms, such as glycerin, trimethylolpurpan, and trimethylolethane,
It is preferable to use a tetrahydric alcohol having 4 or less carbon atoms in the longest carbon chain of the molecule, such as pentaerythritol, diglycerin, ditrimethylolpropane, and ditrimethylolethane.

The amount of the component (d) used is determined by the total number of hydroxyl equivalents in each of the components (a) to (d) in order to give a desired molecular weight and proper emulsifying properties of the ink in designing the polyester resin. OH) and the total number of carboxyl equivalents (COOH) are preferably adjusted so that OH / COOH = 0.50 to 1.00. The amount of the component (d) is preferably 3 to 11% by weight based on the total amount of the components (a) to (d). If the component (d) is less than 3% by weight, it is difficult to obtain a desired molecular weight, and if the component (d) is more than 11% by weight, it is difficult to obtain appropriate emulsifying properties of the ink. The OH /
In the calculation of COOH (equivalent ratio), secondary amines among the aliphatic monoamines in the component (c) are regarded as monovalent,
The primary amine is regarded as divalent, and the number of equivalents of the amino group = the number of equivalents of the OH.
Let H be the total equivalent number. 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, a method of simultaneously charging the component (a), the component (b), the component (c) and the component (d), the component (a) and a reaction product of the component (c) with the component (a) A method of charging components (b) and (c), a method of charging components (a) and (c) to a reaction product of components (b) and (c), a part of component (a) and (d) )), A reactant of the components (b) and (c), and a method of charging the components (a) and (d) as necessary. As the catalyst, mineral acids such as hydrochloric acid and sulfuric acid,
Examples thereof include sulfonic acids such as methanesulfonic acid, paratoluenesulfonic acid and dodecylbenzenesulfonic acid, oxides such as zinc oxide, magnesium oxide and calcium oxide, and hydroxides such as magnesium hydroxide and calcium hydroxide.

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 drying property by setting the softening point to 120 ° C or higher,
This is because good setting properties can be maintained, and 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 30,000 to 300,000.
And preferably in the range of 50,000 to 200,000.
It is in the range of 0. If it is less than 30,000, it is difficult to obtain a desired viscosity, and if it is more than 300,000, the viscosity becomes high and stable production is 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 to 15% by weight.
It has a high viscosity of Pa · s. The polyester resin of the present invention thus obtained is useful as a binder for printing ink.

The binder for printing ink 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 200 ° C. or more and an aromatic hydrocarbon content of 1% by weight or less. Can be used. Specific examples include No. 0 solvent and AF Nos. 4 to 7 solvents manufactured by Mitsubishi Nisseki Co., Ltd.

The thus obtained gel varnish, 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 1% or less at a temperature of not less than 1 ° C., and a surfactant, a wax, a dryer, and other additives for improving the ink fluidity and the ink surface film as required. Be blended. Roll mill,
The compound is kneaded using a normal ink manufacturing apparatus such as a ball mill, attritor, sand mill or the like, and is adjusted to an appropriate constant. Ink), desired printing inks such as waterless offset inks are produced. The amount of the binder according to the present invention used in the production of the printing ink is preferably such that the solid content of the polyester resin is 10 to 50% by weight.

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

[0032]

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.

[0033]

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.
01 (hereinafter the same).

Production Example 2 (Production of rosin ester) Polymerized rosin (trade name: Silvatack 140, manufactured by Silvachem, acid value: 140) was placed in the same reaction vessel as in Production Example 1.
Charge 1,000 parts and stir in a nitrogen atmosphere for 18
The temperature was raised to 0 ° C. to melt. Then, 43 parts of pentaerythritol was added, and the mixture was stirred at 275 ° C. for 5 hours.
Then, the reaction was continued until the acid value became 70 or less, followed by cooling to obtain a solid resin (acid value: 69.5).

Production Example 3 (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 an L column in a THF solvent (hereinafter the same).

Production Example 4 (Production of Polar Group-Containing Petroleum Resin) A 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 5 (Production of 70% resol-type nonylphenol xylene solution) Nonylphenol 1,0 was placed in the same reaction vessel as in Production Example 1.
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 polymerization rosin (trade name: Silvatack 140, trade name) was placed in a reaction vessel equipped with a stirrer, a reflux condenser with a water separator, and a thermometer.
353 parts by Silvachem, acid value: 140) 353 parts, 101 parts of resin obtained from Production Example 1, resin 4 obtained from Production Example 3
26 parts were charged, and the temperature was raised to 180 ° C. while stirring under a nitrogen atmosphere to melt. Then, pentaerythritol 22 was added so that OH / COOH (equivalent ratio) = 0.90.
Parts, glycerin 22 parts and 1,2-octadecanediol 76 parts were added, and the mixture was heated to 260 ° C. with stirring. When the acid value became 30 or less, 1 part of paratoluenesulfonic acid was charged, and the acid value was 20 or less. It reacted until it became. After completion of the esterification reaction, the viscosity of the linseed oil of 33% by weight was increased 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. The thus obtained polyester resin solution of an aliphatic hydrocarbon solvent (trade name: No. Solvent, manufactured by Mitsubishi Nisseki Co., Ltd.) has a tolerance of 1.4 g / g, an acid value of 14.2 and a softening point of 168 ° C. , Weight average molecular weight is 10
3,000 (see Table 1). Here, 33% by weight
Linseed oil viscosity refers to a mixture of resin and linseed oil heated and mixed at a weight ratio of 1: 2 by Corn Rheology Instruments Co., Ltd.
This refers to the viscosity measured at 25 ° C. using an AND-plate viscometer (hereinafter the same). 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. It is a value calculated from the resin weight (hereinafter the same). The softening point is based on JIS K5601 (the same applies hereinafter).

Example 2 Polymerized rosin (trade name: Silvatack 140, manufactured by Silvachem, acid value: 140) was placed in the same reaction vessel as in Example 1.
53 parts, 101 parts of resin obtained from Production Example 1, Production Example 4
The obtained resin (426 parts) was charged and heated to 180 ° C. while being stirred in a nitrogen atmosphere to be melted. Then, O
22 parts of pentaerythritol, 22 parts of glycerin and 1,2 so that H / COOH (equivalent ratio) = 0.90
76 parts of hexadecanediol are added and 26
The temperature was raised to 0 ° C., and when the acid value became 30 or less, 1 part of paratoluenesulfonic acid was charged 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 3 Polymerized rosin (trade name: Silvatack 140, manufactured by Silvachem, acid value: 140) was placed in the same reaction vessel as in Example 1.
55 parts, 101 parts of resin obtained from Production Example 1, Production Example 4
The obtained resin (429 parts) was charged and heated to 180 ° C. while stirring under a nitrogen atmosphere to be melted. Then, O
22 parts of pentaerythritol, 22 parts of glycerin and 1,2 so that H / COOH (equivalent ratio) = 0.90
-Add 72 parts of epoxy octadecane and add 26
The temperature was raised to 0 ° C., and when the acid value became 30 or less, 1 part of paratoluenesulfonic acid was charged 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. Note that the above OH / COO
In the calculation of H (equivalent ratio), 1,2-epoxyoctadecane was regarded as a dihydric alcohol, and the total number of OH including the number of OH equivalents was used.

Example 4 The same reaction vessel as in Example 1 was charged with 420 parts of the resin obtained from Production Example 4, and stirred under a nitrogen atmosphere for 200 hours.
The temperature was raised to ° C. to be melted. Then, 58 parts of octadecylamine was added, and after keeping the temperature at 200 ° C. for 2 hours, 348 parts of polymerized rosin (trade name: Silvatack 140, manufactured by Silvachem, acid value: 140), resin 12 obtained from Production Example 1
Four parts were charged and melted. Then, pentaerythritol 2 was added so that OH / COOH (equivalent ratio) = 0.90.
5 parts and 25 parts of glycerin are added and
When the temperature was raised to 0 ° C. and the acid value became 30 or less, 1 part of paratoluenesulfonic acid was charged 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. Note that the above OH / COOH
In the calculation of (equivalent ratio), octadecylamine is 2
The number of equivalents of the amino group = the number of equivalents of OH, and the total number of equivalents of OH including the number of equivalents of OH.

Example 5 The same reaction vessel as in Example 1 was charged with 413 parts of the resin obtained in Production Example 4, and stirred under a nitrogen atmosphere for 200 hours.
The temperature was raised to ° C. to be melted. Then, 57 parts of isostearyl alcohol was added, and after keeping the temperature at 200 ° C. for 2 hours, 370 parts of the resin obtained from Production Example 2 and 122 parts of the resin obtained from Production Example 1 were charged and melted. Then, OH / C
14 parts of pentaerythritol and 29 parts of glycerin were added so that OOH (equivalent ratio) = 0.90, the temperature was raised to 260 ° C. with stirring, and when the acid value became 30 or less, 8 parts of isophthalic acid and paratoluene sulfone were added. Charge 1 part of acid,
The reaction was continued 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.

Comparative Example 1 552 parts of gum rosin were charged into the same reaction vessel as in Example 1, and the mixture was heated to 230 ° C. and melted while stirring under a nitrogen atmosphere. 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-type nonylphenol obtained from Production Example 5 obtained in Production Example 5 was dropped into the system over a period of 4 hours within a temperature range of 230 to 260 ° C. 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.

Comparative Example 2 Polymerized rosin (trade name: Silvatack 140, manufactured by Silvachem, acid value: 140) 4 was placed in the same reaction vessel as in Example 1.
64 parts, 309 parts of resin obtained from Production Example 1, Production Example 4
The obtained resin (116 parts) was charged and heated to 180 ° C. while stirring under a nitrogen atmosphere to be melted. Then, O
46 parts of pentaerythritol, 46 parts of glycerin and 19 parts of isostearyl alcohol were added so that H / COOH (equivalent ratio) = 0.90, and the mixture was stirred at 260 ° C.
When the temperature was raised until the acid value became 30 or less, 1 part of paratoluenesulfonic acid was charged 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.

Comparative Example 3 Polymerized rosin (trade name: Silvatack 140, manufactured by Silvachem, acid value: 140) was placed in the same reaction vessel as in Example 1.
09 parts and 711 parts of the resin obtained in Production Example 4 were charged, and the mixture was heated to 180 ° C. and melted while stirring under a nitrogen atmosphere. Then, 15 parts of glycerin and 164 parts of isostearyl alcohol were added so that OH / COOH (equivalent ratio) = 0.90, and the temperature was raised to 260 ° C. with stirring.
Gelled during esterification. When component (a) was used in combination with polymerized rosin and Production Example 1 (fumarated rosin), or when component (d) was used in combination with glycerin and pentaerythritol, gelation occurred in a shorter time than the above.

[0047]

[Table 1]

In Table 1, Comparative Example 1 shows a rosin-modified phenol resin which is a conventional resin for printing ink,
Comparative Example 2 shows a polyester resin in which the charged amount of the component (a) exceeds 75% by weight based on the total charged amount of the components (a) to (d), and Comparative Example 3 shows that the charged amount of the component (a) is 12%.
Shows less than% by weight polyester resin.

(Preparation of Gel Varnish A) 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 5 and Comparative Examples 1 and 2, gel varnish was prepared in the same manner as described above. In Comparative Example 3, a gel varnish could not be prepared due to gelation.

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

[0051]

[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.

[0053]

[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 5 and Comparative Examples 1 and 2, gel varnishes were prepared in the same manner as described above. In Comparative Example 3, gel varnish could not be prepared because of gelation.

(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.

[0056]

[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.

[0058]

[Table 5]

From the results shown in Tables 3 and 5, the printing ink using the polyester resin of the present invention (Examples 1 to 5) 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, the printing ink using the polyester resin (Comparative Example 2) exceeding the upper limit (75% by weight) of the numerical limitation of the present invention in terms of the charged amount of the component (a), compared with the printing ink of the present invention, Polyester resin (Comparative Example 3), which is inferior in emulsification resistance and less than the lower limit (12% by weight) of the numerical limitation of the present invention (Comparative Example 3) in terms of the charged amount of component (a), was gelled and thus used as a printing ink. Could not be evaluated. In the present invention, (b)
The printing ink using the resin (Examples 2 to 5) using the radical copolymer type as the component used the resin (Example 1) using the component (b) of the addition reaction type. It is clear that misting and emulsification resistance are more excellent than printing ink.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J029 AA00 AB01 AC02 AD01 AD05 AE18 BA01 FA02 FC03 FC04 FC05 FC08 FC41 JB242 JC012 4J039 AB04 AB08 AD18 AE06 BC03 BE01 BE12 EA23 GA01 GA02 GA03

Claims (16)

[Claims] 1. A resin selected from the group consisting of (a) rosins, (b) a petroleum resin containing a polar group, (c) aliphatic monoalcohols, aliphatic dialcohols, aliphatic monoamines and aliphatic monoepoxys. And (d) a polyester resin obtained by reacting a polyol, wherein the amount of the component (a) is 12 to 75% by weight based on the total amount of the components (a) to (d). A polyester resin, which is 2. The polyester resin according to claim 1, wherein the component (a) contains a rosin having two or more carboxyl groups. 3. The polyester resin according to claim 1, wherein the component (b) contains a petroleum resin having two or more polar groups. 4. The polyester resin according to claim 1, wherein the component (b) is obtained by subjecting a petroleum resin and an unsaturated carboxylic acid to a radical copolymerization or an addition reaction. 5. The amount of the component (b) charged is (a) to (a).
The polyester resin according to any one of claims 1 to 4, wherein the amount is 19 to 66% by weight based on the total amount of the component (d). 6. An aliphatic monoalcohol having a total of 10 to 40 carbon atoms, an aliphatic dialcohol having a total of 10 to 40 carbon atoms, and an aliphatic monoamine having a total carbon number of 10 to 40. The polyester resin according to any one of claims 1 to 5, wherein the polyester resin is at least one selected from the group consisting of monoepoxys and monoepoxys having a total carbon number of 10 to 40. 7. The amount of component (c) charged is from (a) to
The polyester resin according to any one of claims 1 to 6, wherein the amount of the polyester resin is 3 to 11% by weight based on the total amount of the component (d). 8. The polyester resin according to claim 1, wherein the component (d) is a trihydric and / or tetrahydric alcohol. 9. The polyester resin according to claim 1, wherein the component (d) has 4 or less carbon atoms in the longest carbon chain of the molecule. 10. A ratio (OH / C) of the total number of hydroxyl equivalents to the total number of carboxyl equivalents in each of the components (a) to (d).
OOH) is in the range of 0.50 to 1.00. 11. The amount of the component (d) charged is from (a) to (a).
The polyester resin according to any one of claims 1 to 10, wherein the amount is 3 to 11% by weight based on the total amount of the component (d). 12. The polyester resin according to claim 1, which has a softening point of 120 ° C. to 200 ° C. 13. A weight average molecular weight of 30,000 to 30.
The polyester resin according to any one of claims 1 to 12, which has a molecular weight of 000. 14. A compound selected from the group consisting of (a) a rosin, (b) a petroleum resin having a polar group, (c) an aliphatic monoalcohol, an aliphatic dialcohol, an aliphatic monoamine and an aliphatic monoepoxy. And at least one of (d) polyols is used in an amount of 12 to 75 based on the total amount of the components (a) to (d).
A method for producing a polyester resin, wherein the reaction is carried out at a ratio of weight%. 15. A printing ink binder comprising the polyester resin according to claim 1. Description: 16. The binder for a printing ink according to claim 15, a pigment, and a vegetable oil and / or a boiling point of 20.
A printing ink comprising a petroleum solvent having an aromatic hydrocarbon content of 1% or less at 0 ° C. or higher.