JP3446728B2 - Polyester resin composition, production method thereof, binder for printing ink and printing ink - Google Patents

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 printing ink binder and a printing ink. The polyester resin composition obtained by the present invention is useful as a binder for printing ink. As a kind of printing ink, it can be particularly favored as an offset printing ink, and can also be suitably used as a newspaper ink, a letterpress printing ink, and a gravure printing ink.

[0002]

2. Description of the Related Art Conventionally, rosin-modified phenol has been used as a binder for offset printing ink because of its various properties such as high molecular weight, high softening point, high viscosity, and high solubility in ink solvent, and excellent printability. Resin is used. The resin is mainly composed of rosins, alkylphenol-formaldehyde condensate and polyol. However, the rosin-modified phenol resin generates formaldehyde-containing wastewater during the production of an alkylphenol-formaldehyde condensate, which is one of the main raw materials, so in recent years, environmental problems such as air pollution due to volatile organic compounds (VOC) and work environment Problems related to health and safety have been pointed out. It has also been pointed out that the rosin-modified phenolic resin generates formaldehyde in the step of heating and drying a printing ink using the resin.

Under such circumstances, the development of a binder for offset printing ink which 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 alleviate the problems of these rosin-modified phenolic resins, but in general, petroleum resins have a low molecular weight and cannot have many functional groups. Also, due to the small three-dimensional structure, the gelling ability is low, the misting is large, the gloss is insufficient, and the printability is insufficient. Therefore, the petroleum resin alone is used as an offset printing ink. It is never used as a binder.

As a countermeasure against the above problem, 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, so that misting is poor and it contains many polar groups. Therefore, the printability was insufficient such that the emulsification suitability was not at a practical level. As described above, since the performance requirements for the binder for offset printing inks are diverse, it has been difficult to satisfy these performances with resins other than the rosin-modified phenol resin so far.

[0005]

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

[0006]

In view of the above problems, the present inventors have conducted diligent studies to find a resin which does not use an alkylphenol formaldehyde condensate as a raw material and has various performances comparable to those of a rosin-modified phenol resin. . As a result, (a) a rosin, (b) a polar group-containing petroleum resin, (c) a polymer composed of a carboxylic acid and a hydrophobic polymerizable unsaturated compound, and reactivity with the carboxylic acid in the polymer. A resin obtained by partially reacting a hydrophobic compound and a polyester resin composition obtained by reacting (d) a polyol meet the above-mentioned object, and the polyester resin is a binder for various printing inks. It was found to be suitable for the application.

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

[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 polar group-containing petroleum resin (hereinafter referred to as component (b)), a carboxylic acid and hydrophobic polymerization. Of a polymer containing a polyunsaturated compound and a hydrophobic compound having reactivity with carboxylic acids in the polymer (hereinafter,
(C) component), and polyols (hereinafter,
It is obtained by reacting these components with (d) component as an essential component.

The rosins as the component (a) are, for example, natural rosins such as gum rosin, tall oil rosin and wood rosin; polymerized rosins derived from the natural rosins;
Examples thereof include a stabilized rosin obtained by disproportionating or hydrogenating the natural rosin or the polymerized rosin. In addition, unsaturated acid-modified rosins obtained by adding unsaturated carboxylic acids to the natural rosin or polymerized rosin by the Diels-Alder reaction or the ene reaction are also included.

Examples of the unsaturated acid-modified rosin include maleic acid-modified rosin, maleic anhydride-modified rosin,
Examples thereof include fumaric acid-modified rosin, itaconic acid-modified rosin, crotonic acid-modified rosin, cinnamic acid-modified rosin, acrylic acid-modified rosin, and methacrylic acid-modified rosin, and acid-modified polymerized rosins corresponding thereto.
The unsaturated carboxylic acid is usually modified in an amount of about 1 to 30 parts by weight with respect to 0 parts by weight.

Among the above components (a), those containing a rosin having two or more carboxyl groups in the molecule are preferable because the polyester resin obtained can have a high molecular weight. Further, in order to obtain a polyester resin having a high molecular weight and to have a high solubility and a high softening point, among those components (a), those containing a polymerized rosin and / or an unsaturated acid-modified polymerized rosin are particularly preferable. Preference is given to using. 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 in 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 or 2
It is also possible to appropriately use one or more species together. (A)-(d)
The amount of the component (a) charged relative to the total amount of the components charged 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, and when it is 75% by weight or less, the solubility of the resin is high, and the emulsification rate of the ink is properly adjusted. It is possible to do so, which is preferable.

The polar group-containing petroleum resin which is the component (b) is indene, methylindene, vinyltoluene, styrene, α-methylstyrene, β-methylstyrene, cyclopentadiene, dicyclopentadiene, methylbutene, isoprene, pentene, The petroleum resin having a double bond containing cyclopentene, pentadiene and the like and having a polar group is applicable. Examples of the petroleum resin having a double bond include cyclopentadiene and DCPD petroleum resin using dicyclopentadiene as a raw material; C5 petroleum resin such as pentene, pentadiene and isoprene; indene, methylindene, vinyltoluene, styrene, α-
C9 petroleum resin made from methyl styrene, β-methyl styrene, etc., copolymerized petroleum resin made from the DCPD raw material and C5 raw material, copolymerized petroleum resin made from the DCPD raw material and C9 raw material, C5 type Copolymerized petroleum resin composed of raw material and C9 raw material, copolymerized petroleum resin composed of the DCPD raw material, C5 raw material and C9 raw material, and the like are used, and non-catalyst or Friedel-Crafts type catalyst (cationic polymerization) is used. Manufactured. In particular, a petroleum resin obtained from a DCPD-based raw material is preferable because it is easy to apply a polar group and easily adjust to a desired softening point.
Specific examples of petroleum resins obtained from DCPD-based raw materials include DCPD-based petroleum resins, copolymerized petroleum resins composed of DCPC-based raw materials and C5 raw materials, copolymerized petroleum resins composed of DCPD-based raw materials and C9-based raw materials, and DCPD-based raw materials. C5-based raw material and C
Copolymerized petroleum resins made of 9-based raw materials may be mentioned.

Examples of the polar group in the component (b) include a carboxyl group and a hydroxyl group. The method of imparting 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 with a monocarboxylic acid 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 adopted. From the viewpoint of improving the misting resistance of the obtained printing ink, it is preferable to adopt the radical copolymerization method.

The amount of unsaturated carboxylic acids used is preferably about 1 to 15 parts by weight per 100 parts by weight of the raw material petroleum resin, and 1 part by weight or more and 15 parts by weight or less of the unsaturated carboxylic acids are used as the raw material petroleum oil. 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.

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

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

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

The following various compounds can be exemplified as the hydrophobic polymerizable unsaturated compound which is a constituent component of the component (c). Aliphatic unsaturated hydrocarbon monomer having 2 to 50 carbon atoms, alicyclic unsaturated hydrocarbon monomer having 5 to 50 carbon atoms, aromatic hydrocarbon monomer having 8 to 50 carbon atoms,
Examples include rosins, higher unsaturated fatty acids, and unsaturated oils. Specific examples of the above compounds include ethylene, propylene, 1-n-butene, dipropylene, diisobutylene, tripropylene, tributylene, 1-hexene, 1
-Octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-dococene, 1-tetracocene, 1-hexacocene, 1-octacocene, 1-triacontene, 1-
Dotria content, 1-Tetratri-air conditioning, 1-
Hexatriacontane, 1-octatriacontene, 1
-Α-olefins such as tetracontene and butadiene,
An unsaturated polyolefin etc. can be mentioned. 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 above-mentioned compound are the compounds having an unsaturated bond described in the above-mentioned component (a). Specific examples of the above and compounds include semi-drying oils or drying 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 (2) can be used alone or in combination of two or more, and it is also possible to use other monomers or compounds in combination as long as the characteristics of the present patent are not impaired. Further, the amount used can be arbitrarily changed within the range where the component (c) has an appropriate molecular weight.

The following various compounds can be exemplified as the hydrophobic compound which is a component of the above-mentioned component (c) and has reactivity with carboxylic acids. (I) 6 to 6 carbon atoms
50 aliphatic monoalcohol, (ii) aliphatic dialcohol having 6 to 50 carbon atoms, (iii) aliphatic monoamine having 6 to 50 carbon atoms, (iv) 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 thereof include hexanol, octanol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, eicosanol, docosanol, tetracosanol, hexacosanol, octacosanol, triacontanol, oleyl alcohol, 2-ethylhexanol, Examples include isotridecyl alcohol, isostearyl alcohol, geraniol, rosin alcohol, bisabolol and lanolin alcohol. The structure of the compound (ii) is not particularly limited as long as it has 6 to 50 carbon atoms, and a linear structure,
It may have any structure such as a branched chain 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. Examples include 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, tallow alkylamine, soybean alkylamine, dioctadecylamine, dioctadecenylamine and the like. 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 epoxyhexane, epoxyoctane, epoxydecane, epoxydodecane, epoxytetradecane, epoxyhexadecane, epoxyoctadecane, and ethylhexylglycidyl ether.

The weight average molecular weight (polystyrene-equivalent value by gel permeation chromatography. Hereinafter, when referred to as weight-average molecular weight, the polystyrene-equivalent value by gel permeation chromatography) of the polymer as the component (c) is 2,000. It is preferably about 30,000, and when it is less than 2,000, the effect of improving the solubility by concentrating the hydrophobic groups is not sufficient, and when it is more than 30,000, gelation and viscosity increase, etc. The reaction becomes difficult to control. The polymerization of the carboxylic acids and the hydrophobic polymerizable unsaturated compound is a thermal polymerization,
It can be carried out by a known method such as ionic polymerization or radical polymerization, and each reaction can be carried out under known reaction conditions. For example, in the presence or absence of an initiator, a catalyst, etc.,
It can be carried out solvent-free or solvent-based. For example, as a preferable radical initiator used in the case of radical polymerization, an azo-based initiator such as azobisisobutyronitrile,
Peroxides such as ditertiary butyl peroxide, benzoyl peroxide, dicumyl peroxide, potassium persulfate, and hydrogen peroxide solution 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 radical initiator, and can be appropriately set within the range of usually 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 adopted 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. It should be noted that the specific examples are not limited as long as they are inactive to unsaturated carboxylic acids as a raw material and do not significantly inhibit radical polymerization. As the cationic polymerization initiator used in the cationic polymerization, known catalysts can be used, for example, protic acids such as sulfuric acid can be used, and Lewis acids such as boron trifluoride and aluminum chloride and water, alcohols, ethers, etc. It can be used in combination with a cocatalyst. As the anionic polymerization initiator, known substances can be used, specifically NaR, RMgX, ROK.
(R represents an alkyl group, X represents a halogen atom), pyridine and the like. As the coordinating anion initiator, a Ziegler-Natta catalyst or a metallocene catalyst can be used.

In the component (c), the reaction between the polymer and the hydrophobic compound having reactivity with the carboxylic acids is carried out by converting the carboxyl group in the polymer to 20 to 8
The reaction is preferably carried out at about 0%, and a low modification rate is preferable when the polymer used has a high hydrophobicity, and a high modification rate is preferable when the polymer has a low hydrophobicity. Further, it is also possible to use, as a polymerization reaction component, a product obtained by previously esterifying a carboxylic acid which is a constituent component of the component (c) and a hydrophobic compound having reactivity with the carboxylic acid.

The amount of the component (c) charged is not particularly limited, but is 3 with respect to the total amount of the components (a) to (d) charged.
It is preferably about 15 to 15% by weight. (C) component is 3
When the amount is less than 10% 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 thereof include diglycerin, glycerin, ditrimethylolpropane, trimethylolpropane, ditrimethylolethane, trimethylolethane, ethylene glycol, diethylene glycol and neopentyl glycol, which are conventionally known as the polyol component of the rosin-modified phenol resin. From the viewpoint of appropriately adjusting the softening point and the molecular weight of the resin, it is preferable to use glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, diglycerin, ditrimethylolpropane, and ditrimethylolethane. (D)
The amount of the component used is not particularly limited, but in order to give a desired molecular weight and appropriate emulsification characteristics of the ink in the design of the polyester resin, the total number of hydroxyl equivalents (OH) in each component of the components (a) to (d) (OH) It is preferable to adjust the ratio of the total number of carboxyl group equivalents (COOH) so that OH / COOH is usually about 0.50 to 1.00. Further, the charging amount of the component (d) is not particularly limited, but (a) to (d)
It is preferably about 3 to 11% by weight based on the total charged amount of the components. When the component (d) is less than 3% by weight, it is difficult to obtain a desired molecular weight, and the component (d) is 11
If the amount is more than weight%, it is difficult to obtain the proper emulsification characteristics of the ink. In the calculation of the OH / COOH (equivalent ratio), the secondary amine among the aliphatic monoamines in the component (c) is regarded as monovalent, and the primary amine is regarded as divalent, so that Equivalent number = equivalent number of the OH,
The total equivalent number of OH including the equivalent number of OH. In addition, the aliphatic monoepoxys in the component (c) are regarded as dihydric alcohols, and the total equivalent number of OH including the equivalent number of OH is set.

As the reaction conditions of the above-mentioned components (a), (b), (c) and (d), conventionally known methods for producing polyester resins can be adopted. For example,
Predetermined amounts of the components (a), (b), (c) and (d) are charged into a reaction apparatus, and the mixture is heated at about 230 to 300 ° C. in the presence or absence of a conventionally known acidic / basic catalyst. React 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 components (a), (b), (c) and (d), the reaction products of the components (a) and (d) with the components (b) and (c). Component) and, if necessary, a method of charging the 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 reaction method is adopted, the desired molecular weight and softening point are adjusted by adding dicarboxylic acids such as phthalic acid and 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. is about 140.degree. C., preferably about 140 to 200.degree. This is because by setting the softening point to 120 ° C. or higher, the drying property and setting property can be kept good,
Also, considering the solubility in the ink solvent, 200 ° C. or lower is suitable. The weight average molecular weight of the polyester resin of the present invention is usually 40,000 to 400,
000, preferably 50,000 to 200,
The range is 000. This is because if it is less than 40,000, it is difficult to obtain a desired viscosity, and if it is more than 400,000, the viscosity becomes high and stable production is difficult. The resin of the present invention has good solubility and also has sufficient solubility in a petroleum-based ink solvent containing no aromatic component.
The resin of the present invention has a 33% by weight linseed oil viscosity of 4 to 1
High viscosity of 5 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 vegetable oil, a gelling agent and, if necessary, a solvent and the like, and is appropriately heated and dissolved or reacted to prepare a gel varnish for a printing ink. A petroleum resin, an alkyd resin, a rosin ester, a fatty acid ester or the like may be appropriately used in the binder for the printing ink as long as the performance of the obtained printing ink is not impaired. The polyester resin solid content concentration 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. Further, it is practical that the varnish viscosity is adjusted within a range in which a cone-and-plate type viscometer measurement value at 25 ° C. is usually about 10 to 1000 Pa · s.

The vegetable oil used for preparing the binder for printing ink of the present invention is not particularly limited, and various known ones can be used. Specific examples include linseed oil, tung oil or their polymerized oils, safflower oil, dehydrated castor oil, soybean oil and the like, but vegetable oils having unsaturated bonds are preferable from the viewpoint of the dryness of printed matter, and in recent years Soybean oil is particularly preferable from the viewpoint of environmental protection.

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 binder for the printing ink 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. Well-known ones can be used. Specifically, Mitsubishi Nisseki No. 0 solvent, Mitsubishi Nisseki AF4 solvent, Mitsubishi Nisseki AF5
No. Solvent, Mitsubishi Nisseki AF6 Solvent,
Examples include AF7 solvent manufactured by Mitsubishi Nisseki Co., Ltd.

The gel varnish thus obtained as a binder for printing inks of the present invention contains a pigment such as yellow, crimson, indigo or black, vegetable oil and / or a boiling point of 200.
A petroleum solvent having an aromatic hydrocarbon content of about 1% or less at a temperature of about ℃ or more, and if necessary, a surfactant, a wax, a dryer, and other additives for improving ink fluidity and an ink surface film. Are appropriately mixed. An offset sheet-fed ink is prepared by kneading the compound thus obtained using a conventional ink manufacturing device such as a roll mill, a ball mill, an attritor, or a sand mill, and adjusting the ink constant to an appropriate value. (Sheet-fed ink),
A desired printing ink such as offset rotary ink (off-wheel ink) and waterless offset ink is manufactured. In addition,
The binder of the present invention used in the production of printing ink has a polyester resin solid content concentration of 10 to 5
It is preferable to mix them so as to be about 0% by weight.

As a kind of printing ink, it can be particularly favored as an offset printing ink, and can also be suitably used as a newspaper ink, a letterpress printing ink and a gravure printing ink.

[0033]

Industrial Applicability According to the present invention, a polyester resin which is environmentally preferable because it does not use an alkylphenol-formaldehyde condensate, and has a high molecular weight, a high softening point, a high viscosity and a high solubility comparable to that of a rosin-modified phenol resin is provided. it can. Further, when the polyester resin of the present invention is used as a binder for offset printing inks, the printability of the emulsification properties, gloss, drying properties, misting, etc. of the printing ink is equal to or higher than that of the conventionally known rosin-modified phenol resin. 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 content of aromatic hydrocarbon having a boiling point of 200 ° C. or higher of 1% by weight.
By using the following petroleum solvents and printing inks containing additives as required, safety and hygiene aspects such as environmental problems and working environment can be improved.

[0034]

The present invention will be described in more detail with reference to the following examples, but it goes without saying that the present invention is not limited to these examples. In the following, “parts” means parts by weight.

Production Example 1 (Production of Unsaturated Acid-Modified Rosin) A reaction vessel equipped with a stirrer, a reflux condenser with a water diverter and a thermometer was charged with 1,000 parts of gum rosin and stirred at 180 ° C. under a nitrogen atmosphere. The temperature was raised to melt. Then, 267 parts of fumaric acid was added, the temperature was raised to 230 ° C. with stirring, the temperature was kept for 1 hour, and then cooled to obtain a solid resin (acid value:
342.0) was obtained. The acid value is JIS K56.
It was measured according to No. 01 (hereinafter, the acid value shows the 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.) 1 was placed in the same reaction vessel as in Production Example 1.
000 parts charged, 180 ℃ with stirring under nitrogen atmosphere
The temperature was raised to melt. Then, maleic anhydride 70
Parts were added, the temperature was raised to 230 ° C. with stirring, the temperature was kept 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 (hereinafter the same). Further, the weight average molecular weight means gel permeation chromatography (manufactured by Tosoh Corporation,
HLC-8020) and TSK-GE manufactured by Tosoh Corporation.
It means the value measured by polystyrene conversion using a L column in a THF solvent (hereinafter, the weight average molecular weight shows the value measured by the same method).

Production Example 3 (Production of polar group-containing petroleum resin) A DCPD petroleum resin (trade name: Quinton 1325, manufactured by Nippon Zeon Co., Ltd.) 1 was placed in the same reaction vessel as in Production Example 1.
Then, 000 parts and 100 parts of xylene were charged and the temperature was raised to 150 ° C. with stirring in a nitrogen atmosphere to melt. Then, 70 parts of maleic anhydride was charged, and di-t-butyl peroxide (trade name: Perbutyl D, NOF Corporation).
(Manufactured by Mitsui Chemicals Co., Ltd.) 6 parts continuously over 30 minutes, xylene is added as necessary to suppress thickening, and 150 ° C. to 160 ° C. 2.
It was kept warm for 5 hours. After heat retention, 200 ℃ for removing xylene
To 0.02MPa for 10 minutes under reduced pressure (230 ° C if necessary to suppress thickening), and cooled to solid resin (theoretical acid value: 75, weight average molecular weight: 5,000).
Got

Production Example 4 (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
00 parts were charged and the temperature was raised to 50 ° C. with stirring. 50 ° C
In 100 parts of sodium hydroxide was charged, the temperature was gradually raised to 90 ° C. with cooling, the temperature was kept for 2.5 hours, and sulfuric acid was added dropwise to adjust the pH to around 6. After that, 150 parts of xylene was added to remove the aqueous layer containing formaldehyde and the like, and the mixture was cooled to 70 parts of resol-type nonylphenol.
% Xylene solution was obtained.

Example 1 A reactor equipped with a stirrer, a reflux condenser with a water divider and a thermometer was charged with 238 parts of an α-olefin having 16 to 18 carbon atoms (trade name: Diarene 168, manufactured by Mitsubishi Chemical Corporation). After charging, the temperature was raised to 155 to 160 ° C. with 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) were continuously added in 1 hour.
After further maintaining 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. Resin thus obtained (weight average molecular weight: 4, 3
00) 94 parts, polymerized rosin (trade name Silva Tuck 1
40, manufactured by Silvachem, acid value: 140), 359 parts, resin obtained from Production Example 1 (57 parts), resin obtained from Production Example 2 (433 parts), a stirrer, a reflux condenser with a water divider and a thermometer. Was charged into a reactor equipped with and heated to 180 ° C. under a nitrogen atmosphere with stirring 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 the completion of the esterification reaction, the viscosity of the 33% by weight linseed oil was adjusted to 8.0 Pa · s, and 0.02 MPa
At 10 minutes, the pressure was reduced and cooled to obtain a solid resin. The aliphatic hydrocarbon solvent (trade name 0 solvent, manufactured by Nisseki Mitsubishi Corp.) solution of the polyester resin thus obtained has a tolerance of 1.6 g / g, an acid value of 15.5, and a softening point of 165.
C., the weight average molecular weight was 150,000 (see Table 1). Here, the 33 wt% linseed oil viscosity is measured at 25 ° C. by using a cone and plate type viscometer manufactured by Nippon Rheology Equipment Co., Ltd., which is obtained by heating and mixing a resin and linseed oil at a ratio of 1: 2. (Hereinafter, the viscosity shows a value measured by the same method). Tolerance (indicator of solubility) is based on the total weight of the solvent required to become cloudy by adding No. 0 solvent at 25 ° C. to a mixture of resin and No. 0 solvent heated at a weight ratio of 1: 1. The softening point, which is a value calculated from the resin weight (hereinafter, tolerance shows a value measured by the same method), is defined by JIS K
5601 (hereinafter, the softening point shows the value measured by the same method).

Example 2 A reactor similar to that used in Example 1 was charged with α-containing 16 to 18 carbon atoms.
Olefin (brand name Dialen 168, Mitsubishi Chemical Corporation)
(Manufactured) 238 parts, and while stirring under a nitrogen atmosphere 1
The temperature was raised to 55 to 160 ° C. Then, 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 1 hour. Furthermore, after incubating at 155 to 160 ° C. for 1 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 the mixture was reacted at 220 ° C. for 4 hours. The resin (weight average molecular weight: 4,800) thus obtained was 69
Parts, polymerized rosin (trade name: SilvaTac 140, manufactured by Silvachem, acid value: 140), 365 parts, 69 parts of the resin obtained from Production Example 1, and 440 parts of the resin obtained from Production Example 2 with a stirrer, A reactor equipped with a reflux condenser with a water heater and a thermometer was charged, and the mixture was stirred under a nitrogen atmosphere while stirring 180
The temperature was raised to 0 ° C. to melt. Then, OH / COOH
29 parts of pentaerythritol and 29 parts of glycerin were added so that the (equivalent ratio) = 0.90, and the mixture was stirred to 2
The temperature was raised to 60 ° C., and the reaction was carried out until the acid value became 20 or less. After the completion of the esterification reaction, the 33 wt% linseed oil viscosity was adjusted to 8.0 Pa · s, and the solid resin was obtained by reducing the pressure at 0.02 MPa for 10 minutes and cooling. The tolerance, acid value, softening point and weight average molecular weight of the polyester resin thus obtained are shown in Table 1.

Example 3 In the same reactor as in Example 1, an alternating copolymer of α-olefin having about 28 to 50 carbon atoms and maleic anhydride (trade name: Diakarna 30, manufactured by Mitsubishi Chemical Corporation, theoretical acid) was used. Value:
150) 748 parts were charged, and the temperature was raised to 180 ° C. with stirring under a nitrogen atmosphere. Then, 271 parts of isostearyl alcohol was added, the temperature was raised to 220 ° C., and the reaction was carried out for 4 hours. Resin thus obtained (weight average molecular weight: 1
0,500) and 362 polymerized rosin (trade name: SilvaTac 140, manufactured by Silvachem, acid value: 140).
Parts, 57 parts of the resin obtained from Production Example 1 and 432 parts of the resin obtained from Production Example 2 were charged into a reactor equipped with a stirrer, a reflux condenser with a water divider and a thermometer, and stirred under a nitrogen atmosphere. Meanwhile, the temperature was raised to 180 ° C. to melt. Then, so that 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 33% by weight linseed oil was adjusted to 8.0 Pa · s, and 0.02M was obtained.
A solid resin was obtained by reducing the pressure at Pa for 10 minutes and then cooling. The tolerance, acid value, softening point and weight average molecular weight of the polyester resin thus obtained are shown in Table 1.

Example 4 A reactor similar to that of Example 1 was charged with 935 parts of acid-modified low-molecular-weight polyethylene (trade name: Hiwax 1105A, manufactured by Mitsui Petrochemical Co., Ltd., theoretical acid value: 60), and the atmosphere was nitrogen. The temperature was raised to 180 ° C. with stirring below. Then, 68 parts of oleyl alcohol was added, the temperature was raised to 220 ° C., and the reaction was carried out for 4 hours. 118 parts of the resin (weight average molecular weight: 2,400) thus obtained, polymerized rosin (trade name: SilvaTac 140, manufactured by Silvachem, acid value: 1)
40) and 348 parts of resin obtained from Production Example 1
Parts, 420 parts of the resin obtained from Production Example 2 were charged into a reactor equipped with a stirrer, a reflux condenser with a water divider and a thermometer, and heated to 180 ° C. with stirring under a nitrogen atmosphere to melt. . Then, OH / COOH (equivalent ratio) = 0.
27 parts of pentaerythritol and 27 parts of glycerin were added so that the ratio reached 90, the temperature was raised to 260 ° C. with stirring, and the reaction was carried out until the acid value became 20 or less. After the completion of the esterification reaction, the 33 wt% linseed oil viscosity was adjusted to 8.0 Pa · s, and the solid resin was obtained by reducing the pressure at 0.02 MPa for 10 minutes and cooling. The tolerance, acid value, softening point and weight average molecular weight of the polyester resin thus obtained are shown in Table 1.

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

Example 6 A reactor similar to that in Example 1 was used, except that Chinese gum rosin 450 was used.
Part, 238 parts of α-olefin having 16 to 18 carbon atoms (trade name: Diarene 168, manufactured by Mitsubishi Chemical Corporation),
The temperature was raised to 135 to 140 ° C with 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 1 hour. Then 1
After incubating at 55-160 ° C for 1 hour and 220 ° C for 1 hour, 543 parts of stearyl alcohol are added to 230 ° C.
And reacted for 4 hours. 157 parts of the resin (weight average molecular weight: 3,500) thus obtained, polymerized rosin (trade name: SilvaTac 140, manufactured by Silvachem, acid value: 14)
0) 357 parts, and 431 parts of the resin obtained from Production Example 2 were charged into a reactor equipped with a stirrer, a reflux condenser with a water divider and a thermometer, and stirred at 180 ° C. under a nitrogen atmosphere.
The temperature was raised to melt. Then, pentaerythritol 2 was added so that OH / COOH (equivalent ratio) = 0.90.
7 parts and 27 parts of glycerin are added and stirred under 260
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 viscosity of 33% by weight linseed oil was adjusted to 8.
Adjust to 0 Pa · s, depressurize at 0.02 MPa for 10 minutes,
Cooling gave a solid resin. The tolerance, acid value, softening point and weight average molecular weight of the polyester resin thus obtained are shown in Table 1.

Example 7 The same reactor as in Example 1 was charged with 250 parts of xylene and heated to 130 to 135 ° C. under a nitrogen stream to obtain 600 parts of styrene, 37.5 parts of methacrylic acid and 2-ethylhexyl acrylate. After continuously adding 112.5 parts of a mixed solution and 52.5 parts of di-t-butyl peroxide (trade name: Perbutyl D, manufactured by NOF CORPORATION) for 4 hours,
The temperature 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 used as 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
Charge 7 parts to a reactor equipped with a stirrer, a reflux condenser with a water divider, and a thermometer, and stir in a nitrogen atmosphere while stirring 1
The temperature was raised to 80 ° C. to melt it. Then, OH / COO
27 parts of pentaerythritol and 27 parts of glycerin were added so that H (equivalent ratio) = 0.90, the temperature was raised to 260 ° C. with stirring, and the reaction was carried out until the acid value became 20 or less. After the completion of the esterification reaction, the 33 wt% linseed oil viscosity was adjusted to 8.0 Pa · s, and the solid resin was obtained by reducing the pressure at 0.02 MPa for 10 minutes and cooling. The tolerance, acid value, softening point and weight average molecular weight of the polyester resin thus obtained are shown in Table 1.

Example 8 A reactor similar to that used in Example 1 was charged with α-containing 16 and 18 carbon atoms.
238 parts of olefin (trade name: Diarene 168, manufactured by Mitsubishi Chemical Corporation) was charged, and the temperature was raised to 155 to 160 ° C. with stirring under a nitrogen atmosphere. Then, 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 1 hour. After further maintaining the temperature at 155 to 160 ° C. for 1 hour, 392 parts of distearylamine was added to the mixture, and 2
The reaction was carried out at 20 ° C for 4 hours. 94 parts of the resin (weight average molecular weight: 4,500) thus obtained, polymerized rosin (trade name: SilvaTac 140, manufactured by Silvachem, acid value: 1)
40) and 359 parts of the resin obtained from Production Example 1
Part, 433 parts of the resin obtained from Production Example 2 was charged into a reactor equipped with a stirrer, a reflux condenser with a water divider, and a thermometer, and heated to 180 ° C. with stirring under a nitrogen atmosphere to be melted. . Then, OH / COOH (equivalent ratio) = 0.
29 parts of pentaerythritol and 29 parts of glycerin were added so as to be 90, the temperature was raised to 260 ° C. with stirring, and the reaction was carried out until the acid value became 20 or less. After completion of the esterification reaction, the 33% by weight linseed oil viscosity was adjusted to 8.0 Pa · s.
The pressure was adjusted to 0.02 MPa, the pressure was reduced to 0.02 MPa for 10 minutes, and the solid resin was obtained by cooling. The tolerance, acid value, softening point and weight average molecular weight of the polyester resin thus obtained are shown in Table 1.

Example 9 A reactor similar to that of Example 1 was charged with α-containing 16 to 18 carbon atoms.
Olefin (brand name Dialen 168, Mitsubishi Chemical Corporation)
(Manufactured) 238 parts, and while stirring under a nitrogen atmosphere 1
The temperature was raised to 55 to 160 ° C. Then, 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 1 hour. After further maintaining 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. The resin thus obtained (weight average molecular weight: 6,500) was 96 parts, polymerized rosin (trade name: SilvaTac 140, manufactured by Silvachem, acid value: 140) was 364 parts, and the resin obtained from Production Example 1 was 46 parts. Parts, 439 parts of the resin obtained from Production Example 2 with a stirrer,
A reactor equipped with a reflux condenser with a water separator and a thermometer was charged, and the temperature was raised to 180 ° C. with stirring under a nitrogen atmosphere to melt. Then, OH / COOH (equivalent ratio) =
28 parts of pentaerythritol and 28 parts of glycerin were added so that it might become 0.90, and it heated up to 260 degreeC under stirring, and it reacted until the acid value became 20 or less. After completion of the esterification reaction, the 33% by weight linseed oil viscosity was adjusted to 8.0 Pa · s.
The pressure was adjusted to 0.02 MPa, the pressure was reduced to 0.02 MPa for 10 minutes, and the solid resin was obtained by cooling. The tolerance, acid value, softening point and weight average molecular weight of the polyester resin thus obtained are shown in Table 1.

Example 10 The same reactor as in Example 1 was charged with an α-containing 16 to 18 carbon atoms.
Olefin (brand name Dialen 168, Mitsubishi Chemical Corporation)
(Manufactured) 238 parts, and while stirring under a nitrogen atmosphere 1
The temperature was raised to 55 to 160 ° C. Then, 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 1 hour. After further maintaining the temperature at 155 to 160 ° C for 1 hour, add 271 parts of stearyl alcohol and add 220
The reaction was carried out at 0 ° C for 4 hours. 94 parts of the resin (weight average molecular weight: 4,300) thus obtained, polymerized rosin (trade name: SilvaTac 140, manufactured by Silvachem, acid value: 140)
359 parts, 57 parts of the resin obtained from Production Example 1 and 433 parts of the resin obtained from Production Example 3 were charged into a reactor equipped with a stirrer, a reflux condenser with a water divider and a thermometer, and the mixture was placed under a nitrogen atmosphere. While stirring, the temperature was raised to 180 ° C. to melt. Then, 29 parts of pentaerythritol and 29 parts of glycerin were added so that OH / COOH (equivalent ratio) = 0.90, the temperature was raised to 260 ° C. with stirring, and the reaction was carried out until the acid value became 20 or less. After completion of the esterification reaction,
33% by weight linseed oil viscosity adjusted to 8.0 Pa · s,
The solid resin was obtained by reducing the pressure at 0.02 MPa for 10 minutes and cooling. Tolerance of the polyester resin thus obtained,
The acid value, softening point and weight average molecular weight are shown in Table 1.

Comparative Example 1 552 parts of gum rosin were charged in the same reactor as in Example 1 and heated to 230 ° C. with stirring under a nitrogen atmosphere to melt. Next, 52 parts of pentaerythritol and 2 parts of zinc oxide were added, the temperature was raised to 260 ° C. with stirring, and the reaction was carried out until the acid value became 20 or less. Further 230
After cooling to 0 ° C, 394 parts of a 70% xylene solution of resole-type nonylphenol obtained from Production Example 4 (solid content: 276 parts) was added dropwise to the system within a temperature range of 230 to 260 ° C over 4 hours in a heat retaining state. did. 33 after dropping
Adjust the weight% linseed oil viscosity to 8.0 Pas,
The solid resin was obtained by reducing the pressure at 2 MPa for 10 minutes and cooling. The tolerance, acid value, softening point and weight average molecular weight of the rosin-modified phenol resin thus obtained are shown in Table 1.

[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 No. 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 Chemicals Co., Ltd.) 1.0
Parts were added and the temperature was raised to 190 ° C. and kept for 1 hour to obtain a gel varnish. Gel varnishes were prepared in the same manner as above for the resins obtained in Examples 2 to 10 and Comparative Example 1.

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

[0053]

[Table 2] Based on the above composition, the tack value of the ink was 6.5 ± 0.
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 the roll temperature was 30 ° C. and 400 r
The value was read by rotating at pm for 1 minute. The results are shown in Table 3. Flow value: About 2 ml of 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 that the upper surface was flush with the upper surface of the fixing plate, and the load plate was dropped. The diameter value of the ink spread concentrically after 1 minute was read. The results are shown in Table 3. Gloss: 0.4 ml of ink was spread on art paper with RI tester (manufactured by Ishikawajima Sangyo Kikai Co., Ltd.), then at 20 ° C., 65
% R. H. The humidity was adjusted for 24 hours, and the reflectance at 60 ° -60 ° was measured by a gloss meter. The larger the value, the better the gloss, and the results are shown in Table 3. Drying property: 0.4 ml of ink was developed on an art paper with a RI tester (manufactured by Ishikawajima Sangyo Kikai Co., Ltd.), and then exposed to an atmosphere of 160 ° C. for 2 seconds, 4 seconds, and 6 seconds, respectively, and then finger-etched. The state without stickiness was judged as dry. The smaller the value is, the better the drying property is, and 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 the roll temperature was 30 ° C., 400
Rotate at rpm for 1 minute, then at 1800 rpm for 2 minutes,
Evaluation was performed by observing the degree of ink scattering on the white paper placed directly under the roll. The larger the numerical value, the better the misting, 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 Rheology Equipment Co., Ltd.) and the 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 this ink was measured by an infrared moisture meter. The smaller the numerical value, the better the emulsification rate, 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 parts of aluminum chelate (trade name: ALCH, Kawaken Fine Chemicals Co., Ltd.) and raise the temperature to 190 ° C. 1
It was kept warm for a time to obtain a gel varnish. Gel varnishes were prepared in the same manner as above for the resins obtained in Examples 2 to 10 and Comparative Example 1.

(Preparation B of Ink) A printing ink was prepared by kneading the gel varnish in a mixing ratio shown in Table 3 with a three-roll mill.

[0058]

[Table 4] Based on the above composition, the tack value of the ink was 7.0 ± 0.
5, the flow value was appropriately adjusted 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 the roll temperature was 30 ° C. and 400 r
The value was read by rotating at pm for 1 minute. The results are shown in Table 5. Flow value: About 2 ml of 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 that the upper surface was flush with the upper surface of the fixing plate, and the load plate was dropped. The diameter value of the ink spread concentrically after 1 minute was read. The results are shown in Table 5. Gloss: 0.27 ml of ink was spread on the art paper by RI tester (manufactured by Ishikawajima Sangyo Kikai Co., Ltd.), then at 20 ° C., 6
5% R. H. The humidity was adjusted for 24 hours, and the reflectance at 60 ° -60 ° was measured by a gloss meter. The larger the value, the better the gloss, and the results are shown in Table 5. Drying property: 0.27 ml of ink was developed by using a RI tester (manufactured by Ishikawajima Sangyo Kikai Co., Ltd.) to develop color on sulfuric acid paper, and the sulfuric acid paper was overlaid on the surface to be developed, and a C-type drying tester (Toyo Seiki Co., Ltd.) was used. (Manufactured by Seisakusho Co., Ltd.) and wound on a rotary drum so that the sulfuric acid paper for paper was on the outside. Gently lower the weight and the pressing gear onto the sulfuric acid paper for pressure paper, rotate the drum, and set the time when the tooth profile of the pressing gear hardly moves as the drying time. The smaller the numerical value, the better the drying property.
The results are shown in Table 5. Misting: 2.6 ml of ink was spread on an incometer (manufactured by Toyo Seiki Co., Ltd.) and the roll temperature was 30 ° C., 400
Rotate at rpm for 1 minute, then at 1200 rpm for 2 minutes,
Evaluation was performed by observing the degree of ink scattering on the white paper placed directly under the roll. The larger the numerical value, the better the misting, 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 Rheology Equipment Co., Ltd.) and the 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 this ink was measured by an infrared moisture meter. The smaller the numerical value, the better the emulsification rate, and the results are shown in Table 5.

[0060]

[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 10) is equivalent 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 terms of the level of printability among the present invention, a printing ink using a resin (Example 10) made of a radical copolymerization type component (b) is
It can be seen that, as compared with the printing ink using the resins (Examples 1 to 9) in which the component (b) is an addition reaction type resin, it is more excellent in misting and emulsification resistance.

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Claims (11)

(57) [Claims] 1. A polymer comprising (a) a rosin, (b) a polar group-containing petroleum resin, (c) a carboxylic acid and a hydrophobic polymerizable unsaturated compound, and reactive to the carboxylic acid in the polymer. A polyester resin composition obtained by reacting a resin partially reacted with a hydrophobic compound having: and (d) a polyol. 2. The component (a) comprises a rosin having two or more carboxyl groups in its molecule.
The polyester resin composition described. 3. The polyester resin composition according to claim 1, wherein the component (b) contains a petroleum resin having two or more polar groups in its molecule. 4. The component (c) has a weight average molecular weight of 2,000.
The polyester resin composition according to any one of claims 1 to 3, which is from 0 to 30,000. 5. The component (c) comprises, as a hydrophobic polymerizable unsaturated compound, an aliphatic unsaturated hydrocarbon monomer having 2 to 50 carbon atoms, an alicyclic unsaturated hydrocarbon monomer having 5 to 50 carbon atoms, and carbon. 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) as a hydrophobic compound having reactivity with carboxylic acids (i) an aliphatic monoalcohol having 6 to 50 carbon atoms, and (ii) an aliphatic dialcohol having 6 to 50 carbon atoms. Or (iii) at least one selected from the group consisting of (iii) aliphatic monoamine having 6 to 50 carbon atoms and (iv) aliphatic monoepoxy having 6 to 50 carbon atoms. The polyester resin composition described in 1. 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 40,000-40.
It is 10,000, The polyester resin composition in any one of Claims 1-7. 9. A polymer comprising (a) a rosin, (b) a polar group-containing petroleum resin, (c) a carboxylic acid and a hydrophobic polymerizable unsaturated compound, and reactive to the carboxylic acid in the polymer. A method for producing a polyester resin composition obtained by reacting a resin obtained by partially reacting with a hydrophobic compound having: and (d) a polyol. 10. A binder for a printing ink, which comprises the polyester resin composition according to claim 1. 11. A binder for a printing ink according to claim 10, a pigment, and a vegetable oil 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 ℃ or higher.