JP6829978B2 - Ink composition for active energy ray-curable offset printing - Google Patents

Description

The present invention relates to a rosin-modified alkyd resin and a method for producing the same, an ink composition for offset printing using the same, and a method for producing a printed matter using the same.

In recent years, environmental load reduction activities have been developed in various industries and industries, but the ultimate goal is common to global environmental conservation. In the printing ink industry, activities to promote the reduction of environmental load have been carried out from various viewpoints, and products that meet the purpose of such activities are to be given various certification marks. Examples of such a certification mark include an NL regulation mark, a vegetable mark, a GP mark, a Clionidae mark, and the like. Under these circumstances, the Printing Ink Industry Association recently established a new ink green mark (hereinafter referred to as IG mark) system. The IG mark is a system that mainly uses the ratio of the components derived from biomass among the components that make up the ink composition as an index, and ranks the environmentally friendly level of the ink composition in three stages according to the degree. .. In other words, it can be said that this system is characterized by encouraging the replacement of fossil resource-derived raw materials with biomass-derived raw materials for the purpose of reducing the environmental burden.

By the way, recently, in various printing fields, printing that instantly dries an ink composition existing on the surface of a printed matter by irradiating the printed matter immediately after printing with an active energy ray such as an ultraviolet ray or an electron beam has begun to spread. .. The ink composition used in this printing contains a photopolymerization initiator that generates radicals and cations by irradiation with active energy rays, and monomers and oligomers that polymerize by reacting with these radicals and cations. When the active energy rays are irradiated, the ink composition existing on the surface of the printed matter becomes a film-like cured product and becomes a dry state. Among such ink compositions, products that are cured by ultraviolet rays are called UV inks, and various products have been proposed in the field of offset printing in which high-speed printing is performed (see, for example, Patent Document 1). ..

As for UV ink, products that can be dried with less ultraviolet irradiation and energy-saving products that can be dried with light from light emitting diodes (LEDs) that consume less power are on sale, and the movement to reduce the environmental load is spreading. It is the same as other ink compositions. However, it is said that it is difficult to use a large amount of biomass-derived components in UV inks because a large amount of monomers and oligomers must be used as the components. Therefore, the above-mentioned IG mark certification criteria include biomass. The current situation is that the ratio of derived components is not included, and instead, environmentally friendly characteristics such as recycling suitability and energy saving measures are used as indicators.

Japanese Unexamined Patent Publication No. 2014-173070

Against the above background, it is socially useful to increase the proportion of biomass-derived components in UV inks, and it can be said that its significance is extremely great. However, the monomers and oligomers used in active energy ray-curable offset printing ink compositions such as UV inks have poor compatibility with biomass-derived materials used in general offset printing ink compositions. The current situation is that it is difficult to simply apply conventional materials.

The present invention has been made in view of the above circumstances, and a resin for an ink composition that can be used for preparing an active energy ray-curable ink composition and can increase the proportion of biomass-derived components. The purpose is to provide. Another object of the present invention is to provide an offset printing ink composition in which the proportion of biomass-derived components is increased, particularly an active energy ray-curable offset printing ink composition, by using such a resin. ..

As a result of diligent studies to solve the above problems, the present inventors have made a rosin-modified alkyd resin which is a polypolymer of an acid component containing a resin acid, a fatty acid and a polybasic acid and a polyhydric alcohol. Of these, those having a solubility parameter sp value of 9.0 to 11.0 (cal / cm ³ ) ^1/2 and an acid value of 1 to 50 mgKOH / g are monomers and oligomers that are raw materials for UV ink. In addition, since resin acids and fatty acids are components derived from biomass, it was found that the ratio of the components derived from the biomass can be increased by using them in UV ink. The present invention has been completed based on the above findings, and provides the following.

The present invention is a condensed polymer of an acid component containing a resin acid, a fatty acid and a polybasic acid, and a polyhydric alcohol, and has a solubility parameter sp value of 9.0 to 11.0 (cal / cal /) by the turbidity titration method. cm ^{3) 1/2,} an acid value of from 1~50mgKOH / g, the ratio of the mass of the fatty acid moiety to the total resin weight (wt%) Ru oil length 30 to 85 der rosin-modified alkyd It is an active energy ray-curable offset printing ink composition characterized by containing a resin.

It is preferable that the fatty acid contains a fatty acid having 8 to 16 carbon atoms.

The fatty acid is preferably a fatty acid of coconut oil or palm kernel oil.

The weight average molecular weight of the rosin-modified alkyd resin is preferably 1000 to 70,000.

Further, the present invention is a method for producing a printed matter, which comprises a step of printing using the active energy ray-curable offset ink composition.

According to the present invention, there is provided a resin for an ink composition that can be used for preparing an active energy ray-curable ink composition and can increase the proportion of biomass-derived components. Further, according to the present invention, by using such a resin, an offset printing ink composition having an increased proportion of biomass-derived components, particularly an active energy ray-curable offset printing ink composition, is provided.

Hereinafter, an embodiment of the method for producing a rosin-modified alkyd resin of the present invention, an embodiment of a rosin-modified alkyd resin, an embodiment of an ink composition for offset printing, and an embodiment of a method for producing a printed matter will be described. The present invention is not limited to the following embodiments and embodiments, and can be carried out with appropriate modifications within the scope of the present invention.

<First Embodiment of Method for Producing Rosin-Modified Alkyd Resin>
First, the first embodiment of the method for producing a rosin-modified alkyd resin of the present invention will be described. In the present embodiment, the method for producing a rosin-modified alkyd resin comprising a step of reacting an acid component containing a resin acid, a fatty acid and a polybasic acid with a polyhydric alcohol, wherein the obtained rosin-modified alkyd resin is prepared. It is characterized in that the above fatty acids are selected so that the solubility parameter sp value by the turbidity measurement method is 9.00 to 11.0 (cal / cm ³ ) ^1/2 .

Resin acid refers to abietic acid contained in rosins, isomers thereof, and derivatives thereof. Rosin is a non-volatile component of pine fat collected from Pinaceae plants, and contains abietic acid and its isomers as main components. Examples of abietic acid and its isomers include abietic acid, neo-avietic acid, palastolic acid, pimalic acid, isopimalic acid, dehydroabietic acid, etc., all of which have a carboxyl group and are polyhydric alcohols and esters described later. Can be formed. By introducing such a resin acid into the rosin-modified alkyd resin of the present invention, it is possible to improve the affinity for pigments and increase the proportion of biomass-derived components in the obtained rosin-modified alkyd resin.

The above-mentioned abietic acid and its isomer contain only one carboxyl group, but a plurality of carboxyl groups can be introduced by modifying this. For example, abietic acid is a trans-diene compound, but when it is heated, it can be isomerized to a cis-diene compound. By reacting the cis-diene compound thus obtained with a Diels-Alder reaction of a dienofil compound having a plurality of carboxyl groups such as maleic acid and 1,2-cyclohexene dicarboxylic acid, a plurality of carboxyl groups are formed in the avietic acid skeleton. Can be introduced. Further, a polymerized rosin is synthesized by polymerizing a plurality of molecules of abietic acid or an isomer thereof, and such a compound also has a plurality of carboxyl groups. The above-mentioned abietic acid and its isomer derivative refer to such a compound.

Since rosins contain a resin acid as a main component, rosins themselves can be used instead of the resin acid for synthesis. Although a plurality of types of rosins are known due to differences in the production method and subsequent chemical treatment, any rosin may be used in the present invention. Examples of such rosins include gum rosin, wood rosin, tall rosin, disproportionated rosin, hydrogenated rosin, polymerized rosin and the like. Further, the rosins may be modified by the Diels-Alder reaction as described above. From the viewpoint of storage stability, it is preferable to use rosins that chemically have or have few conjugated double bonds. Examples of such rosins include disproportionated rosins and hydrogenated rosins. However, although rosins having a conjugated double bond are also slightly inferior in terms of storage stability of the synthesized resin, they can be used without problems.

Fatty acids are obtained by hydrolyzing natural fats and oils such as vegetable oils and animal oils, and have one carboxyl group, so that they can form esters with polyhydric alcohols, which will be described later. By introducing such a fatty acid into the rosin-modified alkyd resin of the present invention, the proportion of biomass-derived components in the obtained rosin-modified alkyd resin can be increased. From this point of view, it is preferable to use an amount of fatty acid such that the oil length, which is the ratio (mass%) of the mass of the fatty acid portion to the mass of the entire resin, is about 30 to 85, and is about 50 to 85. It is more preferable to use a large amount of fatty acid.

As described above, in the method for producing a rosin-modified alkyd resin of the present invention, the sp value of the prepared rosin-modified alkyd resin by the turbidity measurement method is 9.00 to 11.0 (cal / cm ³ ) ^1/2 . One of the characteristics is to select fatty acids so as to become. This value is relatively high for this type of resin, and the prepared rosin-modified alkyd resin has such a high sp value, so that it has good compatibility with monomers and oligomers also having a high sp value. be able to.

Examples of the fatty acid include caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecic acid, palmitic acid, margaric acid, stearic acid, oleic acid, linoleic acid, arachidic acid, bechenic acid and the like. By the way, a fatty acid has a carboxyl group and can be said to be a compound having a relatively high sp value. Among these fatty acids, the smaller the number of carbon atoms, the higher the sp value tends to be. From such a viewpoint, in the present invention, fatty acids having 8 to 16 carbon atoms can be preferably used, and the fatty acids having 8 to 14 carbon atoms can be preferably used. Certain fatty acids can be used more preferably. By using one or a combination of two or more fatty acids having such a high sp value, the sp value of the prepared rosin-modified alkyd resin can also be increased. From this point of view, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadeconic acid, and palmitic acid are preferably exemplified. All of these fatty acids have a Feders sp value of 9.18 or higher. However, this does not mean that fatty acids having a lower sp value cannot be used, and even fatty acids having a lower sp value can be used without problems if combined with fatty acids having a higher sp value. In any case, these may be appropriately combined so that the solubility parameter sp value of the prepared rosin-modified alkyd resin by the dakuten measurement method is 9.00 to 11.0 (cal / cm ³ ) ^1/2. .. Further, the fatty acid may be an unsaturated fatty acid or a saturated fatty acid, but from the viewpoint of avoiding coloring due to alteration, those having an unsaturated bond contained in the molecule of 1 or less are preferably used. .. For fatty acids such as oleic acid, linoleic acid, and eleostearic acid, which have two or more unsaturated bonds, the double bond portion should be epoxidized and eliminated by oxidation treatment. Is desirable. Such modified fatty acids can also be used as fatty acids in the present invention. These fatty acids can be used alone or in combination of two or more.

As described above, a fatty acid having a smaller number of carbon atoms is preferable, and from such a viewpoint, it is preferable to use a fatty acid of coconut oil or palm kernel oil. Since these fatty acids are rich in fatty acids having 12 to 14 carbon atoms, they are preferably used to adjust the sp value of the rosin-modified alkyd resin so as to be high. However, since the sp value of the prepared rosin-modified alkyd resin should be 9.00 to 11.0 (cal / cm ³ ) ^1/2 , other fats and oils within a range in which such a range can be realized. A fatty acid derived from rosin may be used.

The polybasic acid is a compound having a plurality of carboxyl groups, and is a component for shrink-polymerizing with a polyhydric alcohol described later to increase the molecular weight. As the compound having a plurality of carboxyl groups, those used in the synthesis of alkyd resins can be used without limitation, and may have 2 or 3 or more carboxyl groups, or may be an acid anhydride thereof.

Examples of such compounds include phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, trimellitic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexendicarboxylic acid, 1,4-cyclohexendicarboxylic acid and hexahydroanhydride. Phthalic acid, 5-sodiosulfoisophthalic acid, fumaric acid, benzoic acid, tert-butylbenzoic acid, tetrahydrophthalic anhydride, phthalic anhydride, succinic acid, succinic anhydride, fumaric acid, sebacic acid, azelaic acid, tetrabrom anhydride Examples thereof include phthalic acid, methylhymic anhydride, tetrachlorophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, methylcyclohexendicarboxylic acid anhydride and the like. These can be used alone or in combination of two or more.

The polyhydric alcohol forms an ester with an acid component containing a resin acid, a fatty acid and a polybasic acid as described above, and increases the molecular weight of these components. As the polyhydric alcohol, those which have been used for synthesizing alkyd resins can be used without limitation, and examples thereof include compounds having 2 or 3 or more hydroxyl groups.

Examples of such compounds include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, and 1,3-butanediol. , Neopentyl glycol, spiroglycol, dioxane glycol, adamantandiol, 3-methyl-1,5-pentanediol, methyloctanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 2-methylpropanediol 1 , 3,3-Methylpentanediol 1,5, hexamethylene glycol, octylene glycol, 9-nonanediol, 2,4-diethyl-1,5-pentanediol, ethylene oxide-modified compounds of bifunctional phenols such as bisphenol A , A propylene oxide-modified compound of bifunctional phenol such as bisphenol A, ethylene oxide of bisphenol A, propylene oxide copolymer-modified compound, copolymer polyether polyol of ethylene oxide and propylene oxide, polycarbonate diol, adamantan diol, polyether diol , Polyol diol, polycaprolactone diol and the like. These can be used alone or in combination of two or more.

In order to adjust the molecular weight of the prepared rosin-modified alkyd resin, a monobasic acid other than a fatty acid may be added as an acid component. Examples of such a monobasic acid include benzoic acid, acetic acid, propionic acid, butyric acid and the like.

A rosin-modified alkyd resin is prepared by reacting the above-mentioned acid component containing a resin acid, a fatty acid and a polybasic acid with a polyhydric alcohol. As a reaction procedure, a small amount of a solvent such as xylene is added to the reaction vessel in which these raw materials are charged with an inert gas such as nitrogen gas flowing in, and the mixture is heated and azeotropically heated with condensed water to remove water. Examples thereof include a method of polycondensation. The reaction temperature can be about 170 to 250 ° C., and the reaction time can be about 5 to 25 hours, but is not particularly limited. The determination of the completion of the reaction can be made by monitoring the acid value of the reaction mixture according to the passage of the reaction time. That is, the reaction may be terminated when the decrease in the acid value of the reaction mixture due to the polycondensation stops. The polycondensation reaction can be carried out in a shorter time by distilling the water generated by the polycondensation out of the system or using a reaction catalyst. Examples of the reaction catalyst include tetrabutylzirconate, monobutyltin oxide (monobutyltin oxide), zirconium naphthate, tetrabutyl titanate and the like.

The weight average molecular weight of the rosin-modified alkyd resin obtained by the polycondensation reaction is preferably about 1000 to 70,000. Since the weight average molecular weight of the rosin-modified alkyd resin is determined by the balance between the acid component and the polyhydric alcohol, the initial synthesis should be performed on a small scale, and the reaction conditions and the type of raw materials should be determined before the large scale. It is desirable to move to synthesis.

The type and amount of fatty acid used as a raw material so that the solubility parameter sp value of the rosin-modified alkyd resin obtained by the polycondensation reaction by the turbidity titration method is 9.00 to 11.0 (cal / cm ³ ) ^1/2. It is necessary to select. Therefore, as in the case of the weight average molecular weight described above, it is desirable to perform the initial synthesis on a small scale, determine the reaction conditions, the type of raw material, etc., and then shift to the large scale synthesis. The solubility parameter sp value of the rosin-modified alkyd resin by the dakuten titration method is more preferably 9.3 to 10.0 (cal / cm ³ ) ^1/2 , and 9.5 to 10.0 (cal / cm ³ ) ^{1 / 2} is more preferable.

The acid value of the rosin-modified alkyd resin obtained by the polycondensation reaction is 1 to 50 mgKOH. When the acid value is 50 mgKOH or less, it is possible to suppress the occurrence of troubles such as abnormal emulsification in the offset printing ink composition to which this rosin-modified alkyd resin is applied. The acid value is preferably 1 to 25 mgKOH, more preferably 1 to 10 mgKOH. Since the acid value of the rosin-modified alkyd resin at the end of the reaction is determined by the balance between the amount of the acid component and the polyhydric alcohol, the first synthesis is carried out as in the case of the weight average molecular weight described above. It is desirable to carry out on a small scale, determine the reaction conditions and the types of raw materials, and then move to large-scale synthesis.

Here, the calculation of the solubility parameter sp value by the dakuten titration method will be described. This can be measured by dakuten titration, which is a simple actual measurement method. W. SUH, J.M. M. It is a value calculated according to the formula of CORBETT. Regarding the calculation of the sp value by this method, J. Apple. Polym. Sci. 1968, 12, 2359 can be referred to.
Formula sp value = (V _ml ^1/2 · δH + V _mh ^1/2 · δD) / (V _ml ^1/2 + V _mh ^1/2 )

In turbidity drip instillation, 0.5 g of a sample is dissolved in 10 mL of toluene or 10 mL of trimethylolpropantriacrylate (TMPTA), which is a good solvent, and n-hexane, which is a poor solvent with a low sp value, is added and titration at the turbidity point. Read the amount H (mL), and similarly read the quantification D (mL) at the turbidity point when ethanol, which is a high sp value poor solvent, is added to the toluene solution, and apply these to the following formulas, V _ml , V _mh , δH, and δD may be calculated and substituted into the above equation.

The molecular volume and sp value of each solvent used in the above dakuten titration are as follows.
Molecular volume of good solvent φ0 Toluene: 106.28 mL / mol
TMPTA: 279.55 mL / mol
Molecular volume of low sp value poor solvent φl n-hexane: 131.61 mL / mol
Molecular volume of high sp value poor solvent φh ethanol: 58.39 mL / mol
Sp value of each solvent Toluene: 9.14, TMPTA: 9.88
n-Hexane: 7.28, Ethanol: 12.58

V _ml = (φ0 ・ φl) / {(1-VH) ・ φl + VH ・ φ0}
V _mh = (φ0 ・ φh) / {(1-VD) ・ φh + VD ・ φ0}
VH = H / (M + H)
VD = D / (M + D)
δH = (δ0 ・ M) / (M + H) + (δl ・ H) / (M + H)
δD = (δ0 ・ M) / (M + D) + (δl ・ D) / (M + D)

δ0: Good solvent sp value δl: Low sp value Poor solvent sp value δh: High sp value Poor solvent sp value H: Low sp value Poor solvent titration (mL)
D: Titration of high sp value poor solvent (mL)
M: Amount of good solvent (mL)
VH: Volume fraction of low sp value poor solvent titration quantification (%)
VD: Volume fraction of high sp value poor solvent titration quantification (%)

<Second Embodiment of Method for Producing Rosin-Modified Alkyd Resin>
Next, a second embodiment of the method for producing a rosin-modified alkyd resin of the present invention will be described. In this embodiment, a transesterification step of preparing a reaction intermediate by transesterifying a vegetable oil and / or its fatty acid ester with a polyhydric alcohol and in the presence of any of the following (1) to (3). A method for producing a rosin-modified alkyd resin comprising a compression polymerization step of compressing and polymerizing the reaction intermediate, wherein the solubility parameter sp value of the obtained rosin-modified alkyd resin is 9.0 to 11. It is characterized in that the above vegetable oil is selected so as to be 0 (cal / cm ³ ) ^1/2 . In explaining the present embodiment, the description of the parts that overlap with the description of the first embodiment already described will be omitted as appropriate.
(1) Resin acid and polybasic acid (2) Resin acid derivative having a plurality of carboxyl groups (3) Resin acid derivative having a plurality of carboxyl groups and polybasic acid

The present embodiment includes two steps, a transesterification step and a subsequent polycondensation step. First, the transesterification step will be described.

[Transesterification process]
The transesterification step is a step of preparing a reaction intermediate by transesterifying a vegetable oil and / or its fatty acid ester with a polyhydric alcohol. In the first embodiment described above, an acid component containing a resin acid, a fatty acid and a polybasic acid and a polyhydric alcohol are deconstituted, but in the present embodiment, the fatty acid and the polyhydric alcohol among these raw materials are used. The major difference is that instead, a reaction intermediate obtained by transesterifying the fatty acid ester of the vegetable oil and / or the vegetable oil with the polyhydric alcohol is used. The method of transesterifying vegetable oil and / or its fatty acid ester with a polyhydric alcohol and then performing transesterification is often used in the synthesis of alkyd resins, and the ester exchange reaction performed here is transesterification. It is called.

Vegetable oil is an ester of fatty acid and glycerin, and in the production method of the present invention, it serves as a source of fatty acid and polyhydric alcohol (glycerin), and the total amount used is counted as a component derived from biomass. Vegetable oils include asa seed oil, flaxseed oil, eno oil, oyster oil, olive oil, cacao oil, capoc oil, kaya oil, mustard oil, kyonin oil, kiri oil, kukui oil, walnut oil, poppy oil, sesame oil, and saflower. Oil, daikon seed oil, soybean oil, sardine oil, camellia oil, corn oil, rapeseed oil, niger oil, nuka oil, palm oil, sunflower oil, sunflower oil, grape seed oil, gentle oil, pine seed oil, cotton seed oil, Examples include palm oil, peanut oil, and dehydrated castor oil. Further, an epoxidized vegetable oil in which the double bond is eliminated by the oxidation treatment can also be used as the vegetable oil in the present invention. Examples of such epoxidized vegetable oils include epoxidized soybean oil (ESO) and epoxidized linseed oil (ELO). These vegetable oils can be used alone or in combination of two or more.

Vegetable oil and / or vegetable oil fatty acid ester so that the solubility parameter sp value by the turbidity measurement method of the synthesized rosin-modified alkyd resin becomes a relatively high value of 9.00 to 11.0 (cal / cm ³ ) ^1/2. Must be selected. As described above, from this point of view, it is preferable to select vegetable oil or vegetable oil fatty acid ester having a fatty acid having a small number of carbon atoms, and coconut oil or palm kernel oil having abundant fatty acids having 12 to 14 carbon atoms is used. Is particularly preferred. Further, the fatty acid contained in the vegetable oil may be an unsaturated fatty acid or a saturated fatty acid, but from the viewpoint of avoiding coloring due to alteration, the number of unsaturated bonds contained in the molecule is 1 or less. Vegetable oils containing fatty acids are preferably used. The solubility parameter sp value of the synthesized rosin-modified alkyd resin by the dakuten measurement method is more preferably 9.3 to 10.0 (cal / cm ³ ) ^1/2 , and 9.5 to 10.0 (cal). / Cm ³ ) ^1/2 is more preferable.

The polyhydric alcohol reacts with a polybasic acid to contribute to a high molecular weight by polycondensation, and a fat chain is introduced by a transesterification reaction with a vegetable oil to improve solubility and affinity with a pigment. Examples of the polyhydric alcohol include compounds having 2 or 3 or more hydroxyl groups, such as ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, and polyethylene. Glycol, dipropylene glycol, 1,3-butanediol, neopentyl glycol, spiroglycol, dioxane glycol, adamantandiol, 3-methyl-1,5-pentanediol, methyloctanediol, 1,6-hexanediol, 1, 4-Cyclohexanedimethanol, 2-methylpropanediol 1,3,3-methylpentanediol 1,5, hexamethylene glycol, octylene glycol, 9-nonanediol, 2,4-diethyl-1,5-pentanediol, Ethylene oxide-modified compound of bifunctional phenol such as bisphenol A, propylene oxide-modified compound of bifunctional phenol such as bisphenol A, ethylene oxide of bisphenol A, propylene oxide copolymer modified compound, copolymerization of ethylene oxide and propylene oxide Polyether polyols, polycarbonate diols, adamantan diols, polyether diols, polyester diols, polycaprolactone diols, glycerin, trimethylolethane, trimethylolpropane, sorbitol, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tripentaerythritol, adamantan Examples thereof include triol and polycaprolactone triol. These polyhydric alcohols can be used alone or in combination of two or more.

By reacting the above vegetable oil and polyhydric alcohol, a transesterification reaction occurs, and a reaction intermediate is prepared. Examples of the reaction procedure include heating in a state in which an inert gas such as nitrogen gas is allowed to flow into the reaction kettle in which these raw materials are charged. The reaction temperature can be about 170 to 250 ° C., and the reaction time can be about 1 to 2 hours, but is not particularly limited.

The reaction mixture containing the reaction intermediate prepared through the transesterification step is subjected to the polycondensation step.

[Polycondensation step]
The polycondensation step involves the presence of (1) a resin acid and a polybasic acid, (2) a resin acid derivative having a plurality of carboxyl groups, or (3) a resin acid derivative having a plurality of carboxyl groups, and a polybasic acid. Below, it is a step of polycondensing the reaction intermediate obtained in the transesterification step. Each of the above (1) to (3) contains a compound containing a plurality of carboxyl groups in one molecule, that is, a polycarboxylic acid compound, and in this step, one or two or more of this compound and one molecule. The reaction intermediate containing the compound having a hydroxyl group of No. 1 is shrink-polymerized. Further, since the above (1) to (3) always contain a resin acid or a resin acid derivative, the resin acid is introduced into the polymer obtained as a result of polycondensation. As a result, a rosin-modified alkyd resin is synthesized.

The resin acid, the resin acid derivative having a plurality of carboxyl groups, and the polybasic acid are as described in the first embodiment of the method for producing a rosin-modified alkyd resin, and thus the description thereof will be omitted here. Similarly, a monobasic acid other than a fatty acid may be added as an acid component in order to adjust the molecular weight of the prepared rosin-modified alkyd resin.

As a procedure for the polycondensation reaction, any of the above (1) to (3) is put into the reaction mixture containing the above reaction intermediate, and xylene or the like is introduced in a state where an inert gas such as nitrogen gas is flowed into the reaction vessel. Examples thereof include a method in which a small amount of solvent is added, heating is performed, and the mixture is co-boiled with condensed water to remove water and carry out polypolymerization. The reaction temperature can be about 170 to 250 ° C., and the reaction time can be about 5 to 25 hours, but is not particularly limited. The determination of the completion of the reaction can be made by monitoring the acid value of the reaction mixture according to the passage of the reaction time. That is, the reaction may be terminated when the decrease in the acid value of the reaction mixture due to the polycondensation stops. The polycondensation reaction can be carried out in a shorter time by distilling the water generated by the polycondensation out of the system or using a reaction catalyst. Examples of the reaction catalyst include tetrabutylzirconate, monobutyltin oxide, zirconium naphthate, tetrabutyl titanate and the like.

The weight average molecular weight of the rosin-modified alkyd resin obtained by the polycondensation reaction is preferably about 1000 to 70,000. Since the weight average molecular weight of the rosin-modified alkyd resin is determined by the balance of vegetable oil, resin acid and / or its derivative, polybasic acid, and polyhydric alcohol, the initial synthesis is performed on a small scale, and the reaction conditions and raw materials are used. It is desirable to move to large-scale synthesis after deciding the type of.

As described above, the above ester is used so that the solubility parameter sp value of the rosin-modified alkyd resin obtained by the polycondensation reaction by the turbidity drip method is 9.00 to 11.0 (cal / cm ³ ) ^1/2. It is necessary to select the type and amount of vegetable oil and its fatty acid ester as raw materials in the exchange process. Therefore, as in the case of the weight average molecular weight described above, it is desirable to perform the initial synthesis on a small scale, determine the reaction conditions, the type of raw material, etc., and then shift to the large scale synthesis. The solubility parameter sp value of the rosin-modified alkyd resin by the dakuten titration method is more preferably 9.3 to 10.0 (cal / cm ³ ) ^1/2 , and 9.5 to 10.0 (cal / cm ³ ) ^{1 / 2} is more preferable.

The acid value of the rosin-modified alkyd resin obtained by the polycondensation reaction is 1 to 50 mgKOH. When the acid value is 50 mgKOH or less, it is possible to suppress the occurrence of troubles such as abnormal emulsification in the offset printing ink composition to which this rosin-modified alkyd resin is applied. The acid value is preferably 1 to 25 mgKOH, more preferably 1 to 10 mgKOH. The acid value of the rosin-modified alkyd resin at the end of the reaction is determined by the balance of the amounts of vegetable oil, resin acid and / or its derivative, polybasic acid, and polyhydric alcohol, and thus the weight described above. As in the case of average molecular weight, it is desirable to perform the initial synthesis on a small scale, determine the reaction conditions and the type of raw materials, and then move to the large scale synthesis.

<Third Embodiment of the Method for Producing a Rosin-Modified Alkyd Resin>
Next, a third embodiment of the method for producing a rosin-modified alkyd resin of the present invention will be described. In this embodiment, a transesterification step of preparing a reaction intermediate by transesterifying a vegetable oil and / or a fatty acid ester thereof with any of the following (1) to (3) and the above in the presence of a polyhydric alcohol. A method for producing a rosin-modified alkyd resin, which comprises a polycondensation step of polycondensing the reaction intermediate, and the solubility parameter sp value of the obtained rosin-modified alkyd resin by the turbidity measurement method is 9.0 to 11.0. (Cal / cm ³ ) The above vegetable oil is selected so as to be ^1/2 . In explaining the present embodiment, the description of the parts that overlap with the explanations of the first embodiment and the second embodiment already described will be omitted as appropriate.
(1) Resin acid and polybasic acid (2) Resin acid derivative having a plurality of carboxyl groups (3) Resin acid derivative having a plurality of carboxyl groups and polybasic acid

The present embodiment includes two steps, a transesterification step and a subsequent polycondensation step. First, the transesterification step will be described.

[Transesterification process]
The transesterification step involves plant oil and / or its fatty acid ester and (1) resinic acid and polybasic acid, (2) a resinic acid derivative having a plurality of carboxyl groups, or (3) a resin having a plurality of carboxyl groups. This is a step of preparing a reaction intermediate by transesterifying either an acid derivative or a polybasic acid. In the second embodiment described above, the vegetable oil and / or the fatty acid ester thereof was transesterified with the polyhydric alcohol and then transesterified, but in the present embodiment, the vegetable oil and / or the fatty acid ester thereof and the above (1). )-(3) The major difference is that the ester is transesterified with the polycarboxylic acid compound and then the polycarboxylic acid compound is transesterified. As described above, the method of transesterifying a vegetable oil and / or its fatty acid ester with a polycarboxylic acid compound and then performing transesterification is often used in the synthesis of an alkyd resin, and the ester performed here is used. The transesterification reaction is called acidlysis.

Since the vegetable oil and / or its fatty acid ester, resin acid, resin acid derivative, and polybasic acid have already been described, the description thereof is omitted here. Similarly, a monobasic acid may be added in addition to these acid components in order to adjust the molecular weight of the prepared rosin-modified alkyd resin.

In this step, a transesterification reaction occurs by reacting a vegetable oil and / or a fatty acid ester thereof, and any of the above (1) to (3), and a reaction intermediate is prepared. Examples of the reaction procedure include heating in a state in which an inert gas such as nitrogen gas is allowed to flow into the reaction kettle in which these raw materials are charged. The reaction temperature can be about 170 to 250 ° C., and the reaction time can be about 1 to 2 hours, but is not particularly limited.

The reaction mixture containing the reaction intermediate prepared through the transesterification reaction is subjected to a polycondensation step.

[Polycondensation step]
The polycondensation step is a step of polycondensing the reaction intermediate obtained in the transesterification step in the presence of a polyhydric alcohol. A polyhydric alcohol is a compound having a plurality of hydroxyl groups in one molecule, and in this step, this compound and the above reaction intermediate containing a compound having one or more carboxyl groups in one molecule are polycondensed. Let me. Since the compound contained in the reaction intermediate contains a resin acid or a resin acid derivative, the resin acid is introduced into the polymer obtained as a result of polycondensation. As a result, a rosin-modified alkyd resin is obtained.

Since the polyhydric alcohol is as described in the second embodiment of the method for producing a rosin-modified alkyd resin, the description thereof will be omitted here.

As a procedure for the polycondensation reaction, a polyhydric alcohol is added to the reaction mixture containing the above reaction intermediate, and a small amount of a solvent such as xylene is added to the reaction vessel with an inert gas such as nitrogen gas flowing in to heat the reaction mixture. , A method of polypolymerizing while removing water by co-boiling with condensed water can be mentioned. The reaction temperature can be about 170 to 250 ° C., and the reaction time can be about 5 to 25 hours, but is not particularly limited. The determination of the completion of the reaction can be made by monitoring the acid value of the reaction mixture according to the passage of the reaction time. That is, the reaction may be terminated when the decrease in the acid value of the reaction mixture due to the polycondensation stops. The polycondensation reaction can be carried out in a shorter time by distilling the water generated by the polycondensation out of the system or using a reaction catalyst. Examples of the reaction catalyst include tetrabutylzirconate, monobutyltin oxide (monobutyltin oxide), zirconium naphthate, tetrabutyl titanate and the like.

The raw material was subjected to the above transesterification step so that the solubility parameter sp value of the rosin-modified alkyd resin obtained by the polypolymerization reaction by the turbid drip method was 9.00 to 11.0 (cal / cm ³ ) ^1/2. It is necessary to select the type and amount of vegetable oil and its fatty acid ester. Therefore, it is desirable to perform the initial synthesis on a small scale, determine the reaction conditions and the types of raw materials, and then move to the large scale synthesis. The solubility parameter sp value of the rosin-modified alkyd resin by the dakuten titration method is more preferably 9.3 to 10.0 (cal / cm ³ ) ^1/2 , and 9.5 to 10.0 (cal / cm ³ ) ^{1 / 2} is more preferable.

The acid value of the rosin-modified alkyd resin obtained by the polycondensation reaction is 1 to 50 mgKOH. When the acid value is 50 mgKOH or less, it is possible to suppress the occurrence of troubles such as abnormal emulsification in the offset printing ink composition to which this rosin-modified alkyd resin is applied. The acid value is preferably 1 to 25 mgKOH, more preferably 1 to 10 mgKOH. The acid value of the rosin-modified alkyd resin at the end of the reaction is determined by the balance of the amounts of vegetable oil, resin acid and / or a derivative thereof, polybasic acid, and polyhydric alcohol. As with the values, it is desirable to perform the initial synthesis on a small scale, determine the reaction conditions and the type of raw materials, and then move to the large scale synthesis.

<Rosin-modified alkyd resin>
Next, an embodiment of the rosin-modified alkyd resin of the present invention will be described. The rosin-modified alkyd resin of the present invention is prepared by the above-mentioned method for producing a rosin-modified alkyd resin, and is one of the present inventions. The rosin-modified alkyd resin of the present invention is a condensed polymer of an acid component containing a resin acid, a fatty acid and a polybasic acid, and a polyhydric alcohol, and has a solubility parameter sp value of 9.0 to 11 by the turbidity titration method. It is 1.0 (cal / cm ³ ) ^1/2 and has an acid value of 1 to 50 mgKOH / g. In the following description, the description of parts that overlap with the description of each embodiment of the method for producing a rosin-modified alkyd resin that has already been described will be omitted as appropriate.

The rosin-modified alkyd resin of the present invention can be preferably used in the preparation of an ink composition for offset printing, and has good compatibility with monomers and oligomers used in the preparation of an active energy curable ink composition. It is preferably used in the preparation of active energy ray-curable type offset printing ink compositions. Since the rosin-modified alkyd resin of the present invention contains a large amount of biomass-derived raw materials, the content of biomass-derived components in the ink composition containing the raw materials can be increased. Further, since the rosin-modified alkyd resin of the present invention contains a resin acid skeleton in its polymer chain or side chain, it has excellent affinity for pigments, provides good pigment dispersibility, and has good gloss of the printed ink composition. Bring.

The rosin-modified alkyd resin of the present invention is a condensed polymer of an acid component containing a resin acid, a fatty acid and a polybasic acid and a polyhydric alcohol. Each of these components has already been described. The fatty acid and the polyhydric alcohol may be separately added to the reaction product in the future and reacted, or a vegetable oil which is an ester of the fatty acid and glycerin may be added to the reaction mixture and transesterified.

The solubility parameter sp value of the rosin-modified alkyd resin of the present invention by the dakuten titration method is 9.0 to 11.0 (cal / cm ³ ) ^1/2 . The active energy ray-curable ink composition contains monomers and oligomers as components, and these components have a relatively high sp value. Therefore, the rosin-modified alkyd resin of the present invention has a high sp value of 9.0 to 11.0 (cal / cm ³ ) ^1/2 , which is a high sp value for this kind of material. As a result, the rosin-modified alkyd resin of the present invention has high compatibility with monomers and oligomers, and is not limited to ordinary offset printing ink compositions, but also active energy ray-curable offset printing ink compositions. It can also be preferably used for objects. The solubility parameter sp value of the rosin-modified alkyd resin by the dakuten titration method is more preferably 9.3 to 10.0 (cal / cm ³ ) ^1/2 , and 9.5 to 10.0 (cal / cm ³ ) ^{1 / 2} is more preferable.

In order to have a high sp value as described above, the fatty acid constituting the rosin-modified alkyd resin preferably has a small number of carbon atoms, and the fatty acid preferably contains 8 to 16 carbon atoms. It is more preferably ~ 14. Since such low-chain length fatty acids are abundantly contained in coconut oil and palm kernel oil, the fatty acids constituting the rosin-modified alkyd resin of the present invention are preferably coconut oil or palm kernel oil fatty acids. Further, from the viewpoint of increasing the ratio of the components derived from biomass, the oil length, which is the ratio (mass%) of the mass of the fatty acid portion to the total mass of the rosin-modified alkyd resin, is preferably 30 to 85, preferably 50 to 85. Is more preferable.

The acid value of the rosin-modified alkyd resin of the present invention is 1 to 50 mgKOH / g. When the acid value is 50 mgKOH or less, it is possible to suppress the occurrence of troubles such as abnormal emulsification in the offset printing ink composition to which this rosin-modified alkyd resin is applied. The acid value is preferably 1 to 25 mgKOH, more preferably 1 to 10 mgKOH.

The weight average molecular weight of the rosin-modified alkyd resin of the present invention is preferably 1000 to 70,000. When the weight average molecular weight is 1000 or more, the dispersibility of the pigment is excellent and good viscoelasticity can be imparted to the ink composition, which is preferable. When the weight average molecular weight is 70,000 or less, the solubility is good. It is preferable because it is excellent in handling.

<Ink composition for offset printing>
An ink composition for offset printing, which comprises the above-mentioned rosin-modified alkyd resin, is also one of the present inventions. As described above, the rosin-modified alkyd resin of the present invention has a high biomass-derived component ratio as a raw material, and the biomass-derived component ratio of the offset printing ink composition containing the same can be increased. Therefore, this offset printing ink composition has a reduced environmental load, and is a product suitable for receiving various environment-related certifications such as IG mark certification.

Further, as already described, the rosin-modified alkyd resin of the present invention has excellent compatibility with the monomers and oligomers contained in the active energy ray-curable ink composition, and therefore, the active energy ray-curable type offset printing ink. It can be preferably used as a constituent component of the composition. Such an active energy ray-curable type offset printing ink composition is also one of the present inventions.

When the rosin-modified alkyd resin of the present invention is used as a component of an ink composition for offset printing, it may be dissolved in an oil component such as vegetable oil or mineral oil to form a varnish. When the rosin-modified alkyd resin of the present invention is used as a component of the active energy ray-curable offset printing ink composition, it is dissolved in a low-viscosity monomer such as trimethylolpropane triacrylate (TMPTA) or trimethylolpropane tetraacrylate. Let it be a varnish.

<Manufacturing method of printed matter>
One of the present inventions is also a method for producing a printed matter, which comprises a step of performing printing using the offset printing ink composition of the present invention. As described above, the offset printing ink composition of the present invention is characterized by having a high proportion of biomass-derived components and having a smaller environmental load than conventional products. By using such an offset printing ink composition, printing with a smaller environmental load can be performed, and a printed matter having a smaller environmental load can be obtained.

Hereinafter, the present invention will be described in more detail by showing examples, but the present invention is not limited to the following examples. In the following description, "parts" means parts by mass, and "%" means% by mass.

[Example 1]
800 parts of coconut oil and 36 parts of pentaerythritol were mixed in a reaction kettle equipped with a stirrer, a reflux condenser and a thermometer, and held at 250 ° C. for 1 hour to carry out a transesterification reaction. The mixture was cooled to 150 ° C., 160 parts of rosin, 50 parts of isophthalic acid, and xylene for reflux were added, and the mixture was gradually heated to 250 ° C. and held for 6 hours to dehydrate and carry out a polycondensation reaction. Further, in order to remove the solvent from xylene, the resin of Example 1 was obtained by carrying out a reaction under reduced pressure for 3 hours to distill off the solvent. The acid value of the resin of Example 1 was 13 mgKOH / g, the sp value by the dakuten titration method was 9.74, and the weight average molecular weight (Mw) measured by GPC was 7,000.

[Example 2]
800 parts of coconut oil and 36 parts of pentaerythritol were mixed in a reaction kettle equipped with a stirrer, a reflux condenser and a thermometer, and held at 250 ° C. for 1 hour to carry out a transesterification reaction. The mixture was cooled to 150 ° C., 160 parts of dehydroabietic acid, 50 parts of isophthalic acid, and xylene for reflux were added, and the mixture was gradually heated to 250 ° C. and held for 6 hours to dehydrate and carry out a polycondensation reaction. Further, in order to desolve xylene, the reaction was carried out under reduced pressure for 3 hours to distill off the solvent, thereby obtaining the resin of Example 2. The acid value of the resin of Example 2 was 13 mgKOH / g, the sp value by the dakuten titration method was 9.70, and the weight average molecular weight (Mw) measured by GPC was 7,000.

[Example 3]
800 parts of coconut oil and 50 parts of pentaerythritol were mixed in a reaction kettle equipped with a stirrer, a reflux condenser and a thermometer, and held at 250 ° C. for 1 hour to carry out a transesterification reaction. The polymer was cooled to 150 ° C., 160 parts of polymerized rosin, 50 parts of isophthalic acid, and xylene for reflux were added, and the mixture was gradually heated to 250 ° C. and held for 6 hours to carry out a polycondensation reaction while dehydrating. Further, in order to desolve xylene, the reaction was carried out under reduced pressure for 3 hours to distill off the solvent, thereby obtaining the resin of Example 3. The acid value of the resin of Example 3 was 12 mgKOH / g, the sp value by the dakuten titration method was 9.73, and the weight average molecular weight (Mw) measured by GPC was 14,000.

[Example 4]
800 parts of coconut oil, 20 parts of pentaerythritol, and 16 parts of glycerin were mixed in a reaction kettle equipped with a stirrer, a reflux condenser, and a thermometer, and held at 250 ° C. for 1 hour to carry out a transesterification reaction. The mixture was cooled to 150 ° C., 160 parts of rosin, 50 parts of isophthalic acid, and xylene for reflux were added, and the mixture was gradually heated to 250 ° C. and held for 6 hours to dehydrate and carry out a polycondensation reaction. Further, in order to desolve xylene, the reaction was carried out under reduced pressure for 3 hours to distill off the solvent, thereby obtaining the resin of Example 4. The acid value of the resin of Example 4 was 12 mgKOH / g, the sp value by the dakuten titration method was 9.74, and the weight average molecular weight (Mw) measured by GPC was 9000.

[Example 5]
800 parts of coconut oil and 36 parts of pentaerythritol were mixed in a reaction kettle equipped with a stirrer, a reflux condenser and a thermometer, and held at 250 ° C. for 1 hour to carry out a transesterification reaction. The mixture was cooled to 150 ° C., 160 parts of rosin, 50 parts of fumaric acid, and xylene for reflux were added, and the mixture was gradually heated to 250 ° C. and held for 6 hours to dehydrate and carry out a polycondensation reaction. Further, in order to desolve xylene, the reaction was carried out under reduced pressure for 3 hours to distill off the solvent, thereby obtaining the resin of Example 5. The acid value of the resin of Example 5 was 10 mgKOH / g, the sp value by the dakuten titration method was 9.73, and the weight average molecular weight (Mw) measured by GPC was 8,000.

[Example 6]
800 parts of coconut oil and 36 parts of pentaerythritol were mixed in a reaction kettle equipped with a stirrer, a reflux condenser and a thermometer, and held at 250 ° C. for 1 hour to carry out a transesterification reaction. After cooling to 150 ° C., 160 parts of rosin, 50 parts of 1,2-cyclohexene dicarboxylic acid, and xylene for reflux were added, and the mixture was gradually heated to 250 ° C. and held for 6 hours to dehydrate and carry out a polycondensation reaction. .. Further, in order to desolve xylene, the reaction was carried out under reduced pressure for 3 hours to distill off the solvent, thereby obtaining the resin of Example 6. The acid value of the resin of Example 6 was 11 mgKOH / g, the sp value by the dakuten titration method was 9.74, and the weight average molecular weight (Mw) measured by GPC was 8,000.

[Example 7]
800 parts of coconut oil and 36 parts of pentaerythritol were mixed in a reaction kettle equipped with a stirrer, a reflux condenser and a thermometer, and held at 250 ° C. for 1 hour to carry out a transesterification reaction. Cool to 150 ° C., add 160 parts of rosin, 50 parts of 1,2-cyclohexenedicarboxylic acid, and xylene for reflux, gradually heat to 250 ° C., hold for 6 hours, and perform polycondensation reaction while dehydrating. Therefore, 10 parts of benzoic acid was added, and a polycondensation reaction was carried out at 250 ° C. for 1 hour. Further, in order to remove the solvent from xylene, the reaction was carried out under reduced pressure for 3 hours to distill off the solvent, thereby obtaining the resin of Example 7. The acid value of the resin of Example 7 was 11 mgKOH / g, the sp value by the dakuten titration method was 9.73, and the weight average molecular weight (Mw) measured by GPC was 6,000.

[Example 8]
800 parts of coconut oil and 36 parts of pentaerythritol were mixed in a reaction kettle equipped with a stirrer, a reflux condenser and a thermometer, and held at 250 ° C. for 1 hour to carry out a transesterification reaction. Cool to 150 ° C., add 160 parts of rosin, 50 parts of 1,2-cyclohexenedicarboxylic acid, and xylene for reflux, gradually heat to 250 ° C., hold for 6 hours, and perform polycondensation reaction while dehydrating. Therefore, 10 parts of benzoic acid was added, and a polycondensation reaction was carried out at 250 ° C. for 1 hour. Further, in order to desolve xylene, the reaction was carried out under reduced pressure for 3 hours to distill off the solvent, thereby obtaining the resin of Example 8. The acid value of the resin of Example 8 was 11 mgKOH / g, the sp value by the dakuten titration method was 9.63, and the weight average molecular weight (Mw) measured by GPC was 8,000.

[Example 9]
800 parts of coconut oil and 36 parts of pentaerythritol were mixed in a reaction kettle equipped with a stirrer, a reflux condenser and a thermometer, and held at 250 ° C. for 1 hour to carry out a transesterification reaction. Cool to 150 ° C, add 160 parts of rosin, 50 parts of isophthalic acid, 10 parts of 1,2-cyclohexene dicarboxylic acid, and xylene for reflux, gradually heat to 250 ° C, hold for 12 hours and shrink while dehydrating. A polymerization reaction was carried out. Further, in order to remove the solvent from xylene, the reaction was carried out under reduced pressure for 3 hours to distill off the solvent, thereby obtaining the resin of Example 9. The acid value of the resin of Example 9 was 6 mgKOH / g, the sp value by the dakuten titration method was 9.73, and the weight average molecular weight (Mw) measured by GPC was 19 thousand.

[Example 10]
800 parts of coconut oil and 36 parts of pentaerythritol were mixed in a reaction kettle equipped with a stirrer, a reflux condenser and a thermometer, and held at 250 ° C. for 1 hour to carry out a transesterification reaction. Cool to 150 ° C., add 160 parts of rosin, 50 parts of fumaric acid, 10 parts of 1,2-cyclohexene dicarboxylic acid, and xylene for reflux, gradually heat to 250 ° C., hold for 12 hours, and shrink while dehydrating. A polymerization reaction was carried out. Further, in order to remove the solvent from xylene, the reaction was carried out under reduced pressure for 3 hours to distill off the solvent, thereby obtaining the resin of Example 10. The acid value of the resin of Example 10 was 5 mgKOH / g, the sp value by the dakuten titration method was 9.74, and the weight average molecular weight (Mw) measured by GPC was 21,000.

[Example 11]
800 parts of palm oil is mixed in a reaction vessel equipped with a stirrer, a reflux condenser, and a thermometer, and after raising the temperature to 150 ° C., 160 parts of rosin, 50 parts of 1,2-cyclohexenedicarboxylic acid, and xylene for reflux are added. Then, the polycondensation reaction was carried out while gradually heating to 250 ° C. and holding for 12 hours to dehydrate. Further, in order to desolve xylene, the reaction was carried out under reduced pressure for 3 hours to distill off the solvent, thereby obtaining the resin of Example 11. The acid value of the resin of Example 11 was 12 mgKOH / g, the sp value by the dakuten titration method was 9.74, and the weight average molecular weight (Mw) measured by GPC was 9000.

[Example 12]
800 parts of soybean oil is mixed in a reaction vessel equipped with a stirrer, a reflux condenser, and a thermometer, and after raising the temperature to 150 ° C., 160 parts of rosin, 50 parts of 1,2-cyclohexenedicarboxylic acid, and xylene for reflux are added. Then, the polycondensation reaction was carried out while gradually heating to 250 ° C. and holding for 12 hours to dehydrate. Further, in order to desolve xylene, the reaction was carried out under reduced pressure for 3 hours to distill off the solvent, thereby obtaining the resin of Example 12. The acid value of the resin of Example 12 was 10 mgKOH / g, the sp value by the dakuten titration method was 9.45, and the weight average molecular weight (Mw) measured by GPC was 8,000.

[Example 13]
800 parts of palm oil is mixed in a reaction vessel equipped with a stirrer, a reflux condenser, and a thermometer, and after raising the temperature to 150 ° C., 160 parts of disproportionate rosin, 50 parts of 1,2-cyclohexene dicarboxylic acid, and further for reflux. Xylene was added, and the mixture was gradually heated to 250 ° C., held for 12 hours, and dehydrated while undergoing a polycondensation reaction. Further, in order to desolve xylene, the reaction was carried out under reduced pressure for 3 hours to distill off the solvent, thereby obtaining the resin of Example 13. The acid value of the resin of Example 13 was 12 mgKOH / g, the sp value by the dakuten titration method was 9.76, and the weight average molecular weight (Mw) measured by GPC was 8,000.

[Example 14]
800 parts of palm oil is mixed in a reaction vessel equipped with a stirrer, a reflux condenser, and a thermometer, the temperature is raised to 150 ° C., 160 parts of rosin, 50 parts of fumaric acid, and xylene for reflux are added to 250 ° C. The polycondensation reaction was carried out while gradually heating and holding for 12 hours to dehydrate. Further, in order to desolve xylene, the reaction was carried out under reduced pressure for 3 hours to distill off the solvent, thereby obtaining the resin of Example 14. The acid value of the resin of Example 14 was 10 mgKOH / g, the sp value by the dakuten titration method was 9.74, and the weight average molecular weight (Mw) measured by GPC was 9000.

[Example 15]
Mix 800 parts of coconut oil in a reaction kettle equipped with a stirrer, a reflux condenser, and a thermometer, raise the temperature to 150 ° C., add 160 parts of rosin, 50 parts of fumaric acid, and xylene for reflux to 250 ° C. The polycondensation reaction was carried out while gradually heating and holding for 12 hours to dehydrate, and then 10 parts of benzoic acid was added and the polycondensation reaction was carried out at 250 ° C. for 1 hour. Further, in order to desolve xylene, the reaction was carried out under reduced pressure for 3 hours to distill off the solvent, thereby obtaining the resin of Example 15. The acid value of the resin of Example 15 was 11 mgKOH / g, the sp value by the dakuten titration method was 9.73, and the weight average molecular weight (Mw) measured by GPC was 8,000.

[Example 16]
Mix 800 parts of soybean oil in a reaction kettle equipped with a stirrer, a reflux condenser, and a thermometer, raise the temperature to 150 ° C., add 160 parts of rosin, 50 parts of fumaric acid, and xylene for reflux to 250 ° C. The polycondensation reaction was carried out while gradually heating and holding for 12 hours to dehydrate, and then 10 parts of benzoic acid was added and the polycondensation reaction was carried out at 250 ° C. for 1 hour. Further, in order to desolve xylene, the reaction was carried out under reduced pressure for 3 hours to distill off the solvent, thereby obtaining the resin of Example 16. The acid value of the resin of Example 16 was 11 mgKOH / g, the sp value by the dakuten titration method was 9.62, and the weight average molecular weight (Mw) measured by GPC was 7,000.

[Comparative Example 1]
800 parts of coconut oil and 36 parts of pentaerythritol were mixed in a reaction kettle equipped with a stirrer, a reflux condenser and a thermometer, and held at 250 ° C. for 1 hour to carry out a transesterification reaction. The mixture was cooled to 150 ° C., 160 parts of rosin and xylene for reflux were added, and the mixture was gradually heated to 250 ° C. and held for 12 hours to dehydrate and carry out a polycondensation reaction. Further, in order to remove the solvent from xylene, the reaction was carried out under reduced pressure for 3 hours to distill off the solvent, thereby obtaining the resin of Comparative Example 1. The acid value of the resin of Comparative Example 1 was 21 mgKOH / g, the sp value by the dakuten titration method was 8.84, and the weight average molecular weight (Mw) measured by GPC was 5,000.

[Comparative Example 2]
800 parts of soybean oil and 36 parts of pentaerythritol were mixed in a reaction kettle equipped with a stirrer, a reflux condenser and a thermometer, and held at 250 ° C. for 1 hour to carry out a transesterification reaction. The mixture was cooled to 150 ° C., 160 parts of rosin and xylene for reflux were added, and the mixture was gradually heated to 250 ° C. and held for 12 hours to dehydrate and carry out a polycondensation reaction. Further, in order to remove the solvent from xylene, the reaction was carried out under reduced pressure for 3 hours to distill off the solvent, thereby obtaining the resin of Comparative Example 2. The acid value of the resin of Comparative Example 2 was 18 mgKOH / g, the sp value by the dakuten titration method was 8.89, and the weight average molecular weight (Mw) measured by GPC was 7,000.

[Comparative Example 3]
Add 800 parts of palm oil, 160 parts of rosin, 36 parts of pentaerythritol, and xylene for reflux to a reaction kettle equipped with a stirrer, a reflux condenser, and a thermometer, gradually heat to 250 ° C., and hold for 12 hours. The polycondensation reaction was carried out while dehydrating. Further, in order to remove the solvent from xylene, the reaction was carried out under reduced pressure for 3 hours to distill off the solvent, thereby obtaining the resin of Comparative Example 3. The acid value of the resin of Comparative Example 3 was 17 mgKOH / g, the sp value by the dakuten titration method was 8.91, and the weight average molecular weight (Mw) measured by GPC was 8,000.

[Comparative Example 4]
Add 800 parts of soybean oil, 160 parts of rosin, 36 parts of pentaerythritol, and xylene for reflux to a reaction vessel equipped with a stirrer, a reflux condenser, and a thermometer, gradually heat to 250 ° C., and hold for 12 hours. The polycondensation reaction was carried out while dehydrating. Further, in order to remove the solvent from xylene, the reaction was carried out under reduced pressure for 3 hours to distill off the solvent, thereby obtaining the resin of Comparative Example 4. The acid value of the resin of Comparative Example 4 was 18 mgKOH / g, the sp value by the dakuten titration method was 8.85, and the weight average molecular weight (Mw) measured by GPC was 8,000.

[Compatibility test with monomer]
The compatibility of each of the resins of Examples 1 to 16 and Comparative Examples 1 to 4 with respect to various monomers used in the active energy ray-curable ink composition was tested. The test was carried out by mixing 80 parts of the resin, 19 parts of the monomer, and 1 part of butylhydroxytoluene (BHT) under heating at 80 ° C., stirring the mixture, cooling the mixture to 25 ° C., and visually observing the dissolved state. It was. Each resin was evaluated according to the following criteria, and the results are shown in Table 1. The unit of the sp value shown in Table 1 is (cal / cm ³ ) ^1/2 .
◯: Completely dissolved and the solution is clear Δ: The solution is slightly turbid ×: The solution is cloudy, solid is precipitated, or is insoluble

Each monomer shown in Table 1 is as follows. Soybean oil, which is an oil component used in ordinary offset printing ink compositions, and AF Solvent No. 7 (manufactured by JX Nikko Nisseki Co., Ltd.) were also added to the test.
DPHA: Dipentaerythritol Hexaacrylate TMPTA: Trimethylolpropane Triacrylate DI-TMPTA: Ditrimethylolpropane Tetraacrylate 3EO-TMPTA: Ethylene oxide 3 molar addition TMPTA
6EO-TMPTA: TMPTA with 6 moles of ethylene oxide
NPGDA: Neopentyl glycol diacrylate TPGDA: Tripropylene glycol diacrylate 3PO-TMPTA: 3 mol of propylene oxide added TMPTA
2PO-NPGDA: NPGDA with 2 moles of propylene oxide
AF-7: AF Solvent No. 7

As can be seen from Table 1, the rosin-modified alkyd resin of the present invention having an sp value of 9.0 to 11.0 has good compatibility with various monomers used in the active energy ray-curable ink composition. It can be seen that

[Preparation of varnish]
For each of the resins of Examples 1 to 16, 80 parts of the resin, 19 parts of DI-TMPTA, and 1 part of BHT were charged into a reaction kettle with a cooling tube, and varnishes 1 to 16 were prepared by heating and stirring at 100 ° C. for 1 hour, respectively. did. All varnishes were transparent and had good compatibility. The viscosity of each varnish was generally in the range of 1.9 to 5.4 Pa · s. The resins of Comparative Examples 1 to 4 had poor compatibility, and a varnish could not be prepared.

[Preparation of ink composition for active energy ray-curable offset printing]
Inks 1 to 16 were prepared using each of the varnishes 1 to 16 prepared in the above procedure. The preparation procedure is 70 parts of varnish, 15 parts of carbon black (manufactured by Mitsubishi Chemical Corporation, product name # 60), 7 parts of Irgacure 907 (manufactured by BASF), 4,4'-bis (diethylamino) benzophenone (EAB) 3 Mix the parts, knead the meat using a 3-roll mill with a roll temperature of 40 ° C. until the particle size becomes 5.0 μm or less, and add 5 parts of TMPTA as necessary to adjust the viscosity to around 40 Pa · s. To prepare an ink composition.

[Measurement of properties]
For each of the inks 1 to 16, the viscosity at 25 ° C. measured using a Laray viscometer and the slope measured at 25 ° C. according to JIS K5101 are listed in the “Viscosity” and “Slope” columns of Tables 2 and 3, respectively.

[Emulsification evaluation]
For each of the inks 1 to 16, the ink composition (1 g) was used in the presence of dampening water (KG-502 (manufactured by Komori Corporation) 1.5%) using a tabletop emulsifier (manufactured by Taiyo Kikai). ) Was kneaded with a rotating roller, and the emulsification rate (%) of the ink composition was measured after 0.5 minutes had elapsed. The results are shown in the "Emulsification rate" column of Tables 2 and 3.

[Evaluation of curability]
For each of the inks 1 to 16, a printing ink composition amount of 0.1 mL / 204 cm ² was spread on art paper (Mitsubishi Toku Art 110K) using an RI-2 type color spreader 2-split roll (manufactured by Ming Seisakusho). The test piece was used, and then the test piece was irradiated with ultraviolet rays using a 160 W / cm metal halide lamp (focal length 13 cm, condensing type, 1 lamp; manufactured by Heleus). At that time, it was evaluated by the curing rate at which it became tack-free by touch. The evaluation criteria were the following three stages, and the results are shown in the "Curability" column of Tables 2 and 3.
(Evaluation criteria)
◯: Curing rate is 100 m / min or more Δ: Curing rate is 60 m / min or more and less than 100 m / min ×: Curing rate is less than 60 m / min

[Evaluation of gloss]
The gloss value was measured using the test piece that became tack-free by the above evaluation of curability. In the measurement, a 60 ° reflected gloss was determined using a Murakami digital gloss meter (manufactured by Murakami Color Research Institute). The results are shown in the "Glossy" column of Tables 2 and 3.

[Evaluation of stains on printed paper]
Actual printing was performed on each of the inks 1 to 16 using a printing machine, and the stain on the printing paper surface at that time was evaluated. For printing, the printing machine is LITHRONE LS426, the dampening water is KG-502 (1.5%; manufactured by Komori Corporation), the printing paper is Mitsubishi Toku Art Paper (Kikuban), and the water dial is 5 from the standard water volume. The degree of stain on the printed paper when the points were lowered was evaluated. The evaluation criteria are as follows, and the results are shown in the "Printed paper surface stains" column in Tables 2 and 3.
◯: No stain on the printed paper surface ×: Stain on the printed paper surface was observed

As can be seen from Tables 2 and 3, the ink compositions prepared using the resins 1 to 16 according to the present invention exhibited practical properties, emulsifying properties, curing speed and gloss, as well as actual printing. There was no stain on the surface and it was good.

Claims (5)

It is a condensed polymer of an acid component containing a resin acid, a fatty acid and a polybasic acid, and a polyhydric alcohol, and has a solubility parameter sp value of 9.0 to 11.0 (cal / cm ³ ) ¹ by the turbidity titration method. ^{/ 2,} an acid value of from 1～50MgKOH / g, the oil length is the ratio of the mass of the fatty acid moiety to the entire resin mass (mass%) comprises der Ru rosin-modified alkyd resin 30 to 85 An active energy ray-curable offset printing ink composition comprising . The active energy ray-curable offset printing ink composition according to claim 1, which contains a fatty acid having 8 to 16 carbon atoms as the fatty acid. The active energy ray-curable offset printing ink composition according to claim 1 or 2, wherein the fatty acid is a fatty acid of coconut oil or palm kernel oil. The active energy ray-curable offset printing ink composition according to any one of claims 1 to 3, wherein the rosin-modified alkyd resin has a weight average molecular weight of 1000 to 70,000. A method for producing a printed matter, which comprises a step of printing using the active energy ray-curable offset printing ink composition according to any one of claims 1 to 4 .