Thickener for UV (ultraviolet light) or EB (electron beam) curable inks

Abstract

To provide a thickener for UV (ultraviolet ray) or EB (electron beam)-curable ink that prevents the occurrence of a volatile component, has high solubility in acrylic monomers, and has high thickening properties, and a method for producing the same.SOLUTION: A thickener for UV- or EB-curable ink includes an aluminum chelate oligomer compound represented by general formula (1). (In the general formula (1), X is a β-keto ester represented by CH3-CO-CH2-CO-OR1, R1 is a C1-18 linear or branched alkyl group or alkenyl group. Y is a fatty acid represented by R2-COOH, R2 is a C1-18 linear, branched, or cyclic alkyl group, alkenyl group, cycloalkyl group, or cycloalkenyl group optionally substituted with a hydroxy group).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a thickener for UV (ultraviolet light) or EB (electron beam) curable inks, which does not generate volatile components, has high solubility in acrylic monomers, and has a high viscosity increasing property, and is composed of an aluminum chelate oligomer compound having a specific structure. [Background technology]

[0002] Metal organic compounds, such as aluminum organic compounds, have been used in printing ink production for many years. Metal organic compounds play an important role in ink production technology to control flowability, improve gloss, pigment dispersion, dryness, etc. The effect of gelling agents or thickeners used to control flowability is mainly explained by gloss, yield value, pigment wettability, and penetration power. Printing technology has made remarkable progress in recent years, and there is a demand for high-performance printing inks to achieve faster printing speeds and automated printing. When printing is made faster, problems such as misting and guide roller staining become an issue. In order to improve these defects, it is necessary to optimize the viscoelasticity of the printing ink by a moderate gelling reaction during the production of the gel varnish of the printing ink, and gelling agents have been improved. Furthermore, a recent trend is that conventional heat-curing inks are being replaced by UV (ultraviolet light) or EB (electron beam) curing inks, and the proportion of these inks is increasing due to environmental issues such as restrictions on the emission of solvents associated with heat curing (Non-Patent Document 1). Conventional thermosetting inks or paints generally use, as thickeners, metal organic compounds such as aluminum chelates containing alkoxy groups of monohydric alcohols, such as ethyl acetoacetate aluminum diisopropylate, aluminum soaps, and aluminum oligomers, such as cyclic aluminum oxide octylate. However, for example, aluminum alcoholates and aluminum chelates may generate alcohol, which is a volatile component, during ink production, which may be undesirable in terms of VOC (Volatile Organic Compounds) regulations, which have become an issue in recent years, and furthermore, compounds generated by transesterification with acrylic monomers may cause odor problems. Furthermore, the monovalent alkoxy groups in the chelates may have high reactivity, which may result in partial gel formation due to local reactions, and products with the desired quality may not be obtained. Furthermore, conventional metal soaps or aluminum chelate oligomers may have low solubility in acrylic monomers or resins used in UV (ultraviolet light) or EB (electron beam) curable inks, and may be added in a state of being diluted in a solvent in which they are dissolved in advance. If a solvent is used, the solvent may volatilize during resin curing, causing odor, and when curing at a low temperature of 100°C or less, organic solvents may remain in the resin, causing stickiness or insufficient curing (Patent Documents 1 and 2). Patent Document 3 also reports an aluminum chelate compound consisting of a β-ketoester and a dihydric or trihydric alcohol. However, dihydric or trihydric alcohols may also cause problems as they cause stickiness and unpleasant odors. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2001-181283 A [Patent Document 2] JP 2001-181284 A [Patent Document 3] International Publication No. WO2000 / 078703 [Non-patent literature]

[0004] [Non-Patent Document 1] Ryuji Okuda, Characteristics and Applications of UV Printing Inks, Network Polymer, Vol. 34, No. 5, 245-252 (2013) Summary of the Invention [Problem to be solved by the invention]

[0005] In order to solve these problems, a main object of the present invention is to provide a thickener for UV (ultraviolet light) or EB (electron beam) curable inks that does not generate volatile components, has high solubility in acrylic monomers, and has high viscosity increasing properties. [Means for solving the problem]

[0006] As a result of intensive research into solving the above problems, the inventors have found that the above problems can be solved by a thickener for UV (ultraviolet light) or EB (electron beam) curable inks, which is made of an aluminum chelate oligomer compound having a specific structure, and have thus completed the present invention.

[0007] That is, the present invention is as follows. (1) This is a thickener for UV (ultraviolet light) or EB (electron beam) curable inks, consisting of an aluminum chelate oligomer compound represented by the general formula (1). [ka] (In the above general formula (1), X is a β-ketoester represented by CH3-CO-CH2-CO-OR1, and R1 represents a linear or branched alkyl group or alkenyl group having 1 to 18 carbon atoms. Y is a fatty acid represented by R2-COOH, where R2 represents a linear, branched, or cyclic alkyl, alkenyl, cycloalkyl, or cycloalkenyl group having 1 to 18 carbon atoms, which may be substituted with a hydroxyl group. (2) In the above general formula (1), m:n=1:2 to 2:0, and m+n=2 to 20. (1) A thickener for UV (ultraviolet light) or EB (electron beam) curing inks. (3) Aluminum alkoxide, a β-ketoester represented by CH3-CO-CH2-CO-OR1 (R1 represents a linear or branched alkyl group or alkenyl group having 1 to 18 carbon atoms); A fatty acid represented by R2-COOH (R2 represents a linear, branched or cyclic alkyl, alkenyl, cycloalkyl or cycloalkenyl group having 1 to 18 carbon atoms, which may be substituted with a hydroxyl group), and water, This is a method for manufacturing thickeners for UV (ultraviolet) or EB (electron beam) curable inks. Effect of the Invention

[0008] According to the present invention, it is possible to provide a thickener for UV (ultraviolet light) or EB (electron beam) curable inks, which comprises an aluminum chelate oligomer compound having a specific structure, does not generate volatile components, has high solubility in acrylic monomers, and has high viscosity increasing properties. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Hereinafter, an embodiment of the present invention will be described. The aluminum chelate oligomer compound is represented by the general formula (1). [ka] (In the above general formula (1), X is a β-ketoester represented by CH3-CO-CH2-CO-OR1, and R1 represents a linear or branched alkyl group or alkenyl group having 1 to 18 carbon atoms. Y is a fatty acid represented by R2-COOH, where R2 represents a linear, branched, or cyclic alkyl, alkenyl, cycloalkyl, or cycloalkenyl group having 1 to 18 carbon atoms, which may be substituted with a hydroxyl group.

[0010] In the above general formula (1), m+n indicates the degree of polymerization of the aluminum chelate oligomer compound. The effects of the present invention can be obtained when m+n is in the range of 2 to 20, preferably 2 to 10, and more preferably 3 to 5. When m+n is less than 2, unreacted alkoxide remains and may become a source of odor. When m+n is 2 or more, there is no difference in the thickening property, but when m+n exceeds 20, production may take a long time.

[0011] In the above general formula (1), m:n indicates the ratio of the ligands of the aluminum chelate oligomer compound. The effect of the present invention can be obtained when m:n is in the range of 1:2 to 2:0, and preferably 2:3 to 2:0. n may be 0. That is, in one molecule of the aluminum chelate oligomer compound represented by the above general formula (1), the effect of the present invention can be obtained in a range in which the ligand represented by X is β-ketoester for 2 molecules of the ligand represented by Y, and preferably, the ligand represented by X is β-ketoester for 3 molecules of the ligand represented by Y. The ligand represented by Y may not be fatty acid. When m:n is less than 1:2, the viscosity may be reduced, the aluminum chelate oligomer compound may become solid, the solubility in acrylic monomer may be reduced, and handling may be difficult.

[0012] In the above general formula (1), X is a β-ketoester represented by CH3-CO-CH2-CO-OR1, and R1 represents a linear or branched alkyl group or alkenyl group having 1 to 18 carbon atoms. Specific examples of the β-ketoester include oleyl acetoacetate, myristoleyl acetoacetate, palmitoleyl acetoacetate, elaidyl acetoacetate, paxel acetoacetate, linoleyl acetoacetate, linoleyl acetoacetate, ethyl acetoacetate, hexyl acetoacetate, octyl acetoacetate, lauryl acetoacetate, myristyl acetoacetate, and stearyl acetoacetate. Oleyl acetoacetate is preferred.

[0013] In the above general formula (1), Y is a fatty acid represented by R2-COOH, where R2 is a linear, branched, or cyclic alkyl, alkenyl, cycloalkyl, or cycloalkenyl group having 1 to 18 carbon atoms, which may be substituted with a hydroxyl group. Specific examples of fatty acids include single-composition fatty acids such as 2-ethylhexanoic acid, acetic acid, butyric acid, crotonic acid, octanoic acid, lauric acid, stearic acid, and oleic acid, mixed fatty acids such as naphthenic acid and coconut oil fatty acid, and 12-hydroxystearic acid and ricinoleic acid having a hydroxyl group. Preferably, 2-ethylhexanoic acid is used.

[0014] The thickener for UV (ultraviolet ray) or EB (electron beam) curable ink, which is made of the specific aluminum chelate oligomer compound of the present invention, can be produced, for example, by the following method. Examples of aluminum alkoxides that are used as raw materials for aluminum chelate oligomer compounds include aluminum triisopropoxide, aluminum ethylate, aluminum sec-butylate, mono-sec-butoxyaluminum diisopropylate, etc. Aluminum triisopropoxide is preferred in terms of high reactivity, economy, and ready availability. Examples of aprotic solvents that dissolve aluminum alkoxides include hydrocarbon solvents such as xylene, toluene, hexane, and heptane; ester solvents such as ethyl acetate, butyl acetate, and di-2-ethylhexyl phthalate; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; and ether solvents such as tetrahydrofuran. A β-ketoester and a fatty acid are added to an aluminum alkoxide solution, heated under reflux, and a ligand substitution reaction is carried out. Water is then added to hydrolyze the alkoxy moiety and polycondensation occurs. If the total amount of water dropped is less than 0.8 moles per mole of aluminum alkoxide, hydrolysis may be insufficient, polymerization may be insufficient, and unreacted raw materials may remain. On the other hand, if the total amount of water exceeds 1.1 moles per mole of aluminum alkoxide, a polymer is produced, but aluminum hydroxide may be by-produced, and the product may become cloudy. It is preferable to dilute water with a water-soluble organic solvent and dropwise add it. Although not particularly limited, examples of the organic solvent include alcohols such as isopropanol, ethanol, and cyclohexanol, diethyl ether, and tetrahydrofuran, and any amount that can be mixed uniformly with water is necessary. Isopropanol is preferable from the viewpoints of high water solubility, easy removal due to its low boiling point, and economical efficiency. The organic solvent used to dissolve the raw alkoxide, and the alcohol produced by hydrolysis and the organic solvent used as a diluent for water are removed by distillation.

[0015] The thickener for UV (ultraviolet) or EB (electron beam) curable inks, which is made of the specific aluminum chelate oligomer compound of the present invention, obtained in this manner, does not generate volatile components when added in the production of UV / EB curable inks or paints, and has high solubility in acrylic monomers and high viscosity. The thickener for UV (ultraviolet) or EB (electron beam) curable inks, which is made of the specific aluminum chelate oligomer compound of the present invention, is a compound with excellent gelling ability that crosslinks and thickens resins for inks and paints. The thickener for UV (ultraviolet) or EB (electron beam) curable inks, which is made of the specific aluminum chelate oligomer compound of the present invention, can also be used as a gelling agent for inks or a crosslinking agent for paints, etc., according to the usual method.

[0016] For example, UV printing ink can be prepared by the following method, although it is not particularly limited. First, a resin (diallyl isophthalate resin, acrylic resin, etc.) and an acrylic monomer are stirred at 70 to 120°C for about 1 hour, and then an appropriate amount of a thickener for UV (ultraviolet light) or EB (electron beam) curable inks made of a specific aluminum chelate oligomer compound of the present invention is added, and the mixture is stirred at 70 to 120°C for 1 hour to obtain an ink varnish. A pigment (any organic or inorganic pigment), an initiator, etc. are added to this, and the mixture is milled and mixed in a bead mill, a three-roll mill, etc. to obtain a printing ink. Furthermore, to prepare a paint, a paint resin (such as an acrylic resin), a solvent, a pigment (any organic or inorganic pigment), other additives, and an appropriate amount of the thickener for UV (ultraviolet light) or EB (electron beam) curable inks comprising the specific aluminum chelate oligomer compound of the present invention can be added and mixed using a sand mill, a bead mill, a paint shaker, or the like. EXAMPLES

[0017] The effects of the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples, the solvents and reagents used were purchased from Sigma-Aldrich Japan LLC. The aluminum content was measured by chelate titration. The molecular weight was calculated by GPC (gel permeation chromatography). The column used was a combination of two ACQUITY (registered trademark) APC XT 45 columns manufactured by Waters and one ACQUITY APC XT 200 column, and the measurement was performed at 40°C using tetrahydrofuran as the solvent.

[0018] Production of oleyl acetoacetate A 1L four-neck flask was charged with 130.1g (1.00 mol) of ethyl acetoacetate, 268.5g (1.00 mol) of oleyl alcohol, and 100.0g of isopropanol. The mixture was heated to 83-90°C and refluxed with stirring for 3 hours. Then, the ethanol and isopropanol removal operations were carried out at normal pressure. When the distillation of ethanol and isopropanol ceased, the pressure in the system was reduced and the ethanol and isopropanol removal operations were carried out. The mixture was then cooled to room temperature, and 352.6g of a pale yellow transparent liquid was obtained.

[0019] Manufacturing Example 1 An aluminum chelate oligomer compound represented by the following general formula (2), in which, in the above general formula (1), X is oleyl acetoacetate, m=3, and n=0. [ka] A 500mL four-neck flask was charged with 81.7g (0.40 mol) of aluminum triisopropoxide and 80.8g of xylene, and heated to 50-70°C while stirring. 141.0g (0.40 mol) of oleyl acetoacetate was added over 30 minutes. The solution was heated to 60-82°C, and a mixed solution of 7.2g (0.40 mol) of water and 72.0g of isopropanol was added dropwise to the solution over 1 hour. After the dropwise addition was completed, the solution was heated to 85-90°C and refluxed for 20 minutes. Then, the operation of removing isopropanol was performed at normal pressure. When the distillation of isopropanol ceased, the solution was heated to 138-146°C, and the operation of removing xylene was performed. When the distillation of xylene ceased, the pressure inside the system was reduced, and the operation of removing xylene was performed. Then, the solution was cooled to room temperature, and 157.7g of a pale yellow transparent liquid was obtained. In order to confirm the formation of the compound, the aluminum content and the molecular weight were measured by GPC. Aluminum content: 6.7% by weight (theoretical value: 6.8% by weight) GPC molecular weight (Mn): 1210

[0020] Manufacturing Example 2 An aluminum chelate oligomer compound represented by the following general formula (3), in which, in the above general formula (1), X is oleyl acetoacetate, Y is 2-ethylhexanoic acid, m=3, and n=1. [ka] A 500mL four-neck flask was charged with 81.6g (0.40 mol) of aluminum triisopropoxide and 81.3g of xylene, and heated to 50-70°C while stirring. 94.0g (0.27 mol) of oleyl acetoacetate was added over 30 minutes. The solution was heated to 60-82°C, and a mixed solution of 7.2g (0.40 mol) of water, 19.2g (0.13 mol) of 2-ethylhexanoic acid, and 72.0g of isopropanol was added dropwise to the solution over 1 hour. After the dropwise addition was completed, the solution was heated to 85-90°C and refluxed for 20 minutes. Thereafter, the operation of removing isopropanol was performed at normal pressure. When the distillation of isopropanol ceased, the solution was heated to 138-146°C, and the operation of removing xylene was performed. When the distillation of xylene ceased, the pressure in the system was reduced, and the operation of removing xylene was performed. Thereafter, it was cooled to room temperature to obtain 129.9 g of a pale yellow transparent liquid. In order to confirm the formation of the compound, the aluminum content and the molecular weight were measured by GPC. Aluminum content: 8.0% by weight (theoretical value: 8.2% by weight) GPC molecular weight (Mn): 1224

[0021] Production Example 3 An aluminum chelate oligomer compound represented by the following general formula (4), in which in the above general formula (1), X is oleyl acetoacetate, Y is 2-ethylhexanoic acid, m=2, and n=3. [ka] A 500mL four-neck flask was charged with 81.8g (0.40 mol) of aluminum triisopropoxide and 81.2g of xylene, and heated to 50-70°C while stirring. 45.8g (0.13 mol) of oleyl acetoacetate was added over 30 minutes. The solution was heated to 60-82°C, and a mixed solution of 7.2g (0.40 mol) of water, 38.9g (0.27 mol) of 2-ethylhexanoic acid, and 72.0g of isopropanol was added dropwise to the solution over 1 hour. After the dropwise addition was completed, the solution was heated to 85-90°C and refluxed for 20 minutes. Thereafter, the operation of removing isopropanol was performed at normal pressure. When the distillation of isopropanol ceased, the solution was heated to 138-146°C, and the operation of removing xylene was performed. When the distillation of xylene ceased, the pressure in the system was reduced, and the operation of removing xylene was performed. After that, it was cooled to room temperature to obtain 106.7 g of a pale yellow liquid. In order to confirm the formation of the compound, the aluminum content and the molecular weight were measured by GPC. Aluminum content: 9.8% by weight (theoretical value 10.5% by weight) GPC molecular weight (Mn): 1229

[0022] Comparative Manufacturing Example 1 An aluminum compound represented by the following general formula (5): [ka] A 1L four-neck flask was charged with 81.7g (0.40 mol) of aluminum triisopropoxide and 80.8g of isopropanol, and heated to 50-70°C while stirring. 140.8g (0.4 mol) of oleyl acetoacetate was added over 30 minutes, and refluxed for 30 minutes. Isopropanol was distilled off, and the pressure in the system was further reduced to perform an operation to remove isopropanol. After that, it was cooled to room temperature, and 198.6g of a pale yellow transparent liquid was obtained.

[0023] Comparative Manufacturing Example 2 An aluminum compound represented by the following general formula (6): [ka] 81.7g (0.40 mol) of aluminum triisopropoxide and 80.0g of isopropanol were charged into a 1L four-neck flask and heated to 50-70°C with stirring. 422.4g (1.2 mol) of oleyl acetoacetate was added over 30 minutes and refluxed for 30 minutes. Isopropanol was distilled off, and the pressure in the system was further reduced to perform an operation to remove isopropanol. After that, it was cooled to room temperature to obtain 432.6g of a yellow transparent liquid.

[0024] Comparative Manufacturing Example 3 An aluminum compound represented by the following general formula (7): [ka] 81.7g (0.40 mol) of aluminum triisopropoxide and 80.1g of xylene were charged into a 1L four-neck flask and heated to 120-130°C while stirring. A mixed solution of 7.2g (0.4 mol) of water, 48.0g (0.4 mol) of 2-ethylhexanoic acid, and 64.8g of isopropanol was added dropwise to this solution over 2 hours while distilling off the by-product isopropanol. Then, the mixture was heated to 138-146°C and dexylene was performed. Then, the pressure inside the system was reduced to perform dexylene, and when the distillation of xylene ceased, the reaction solution was heated to 190°C and stirred under reduced pressure for 30 minutes. Then, the mixture was cooled to room temperature to obtain 74.5g of a pale yellow transparent solid.

[0025] Comparative Example 4 An aluminum compound represented by the following general formula (8): [ka] A 1L four-neck flask was charged with 81.7g (0.40 mol) of aluminum triisopropoxide and 80.8g of xylene, and heated to 80-90°C while stirring. 338.9g (1.2 mol) of oleic acid was added. After distilling off the by-product isopropanol at normal pressure, the mixture was heated to 136-143°C and refluxed for 30 minutes. Then, a dexylene operation was performed at normal pressure. When the distillation of xylene ceased, the pressure inside the system was reduced and a dexylene operation was performed. Then, the mixture was cooled to room temperature, and 348.5g of a pale yellow solid was obtained.

[0026] Comparative Example 5 An aluminum compound represented by the following general formula (9): [ka] 81.7g (0.40 mol) of aluminum triisopropoxide and 81.3g of toluene were charged into a 1L four-neck flask and dissolved with stirring. 52.1g (0.4 mol) of oleyl acetoacetate and 41.7g (0.4 mol) of neopentyl glycol were added and refluxed for 30 minutes. Then, isopropanol and toluene were removed. The mixture was cooled to room temperature to obtain 103.3g of a pale yellow solid.

[0027] Examples 1 to 21, Comparative Examples 1 to 42 33.0 parts by weight of diallyl isophthalate resin and 67.0 parts by weight of acrylic monomers (EO modified bisphenol A diacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, EO modified trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate) were heated and stirred at 50°C for 2 hours to prepare a test resin varnish. 4 parts by weight of the aluminum chelate oligomer compound produced in Production Examples 1 to 3 or the aluminum compound produced in Comparative Production Examples 1 to 5 were added to 100 parts by weight of this resin varnish. After heating and stirring at 70°C for 30 minutes, the viscosity was measured at 70°C using a cone plate type rotational viscometer (RE105R manufactured by Toki Sangyo Co., Ltd.). In addition, the generation of an unpleasant odor when heated and stirred at 70°C, the presence or absence of volatile matter (confirmation of the generation of air bubbles), and solubility in acrylic monomers were observed. The absence of an unpleasant odor was rated as ◯, the presence of an unpleasant odor was rated as ×, the absence of air bubbles was rated as ◯, the presence of air bubbles was rated as ×, the complete dissolution was rated as ◯, the presence of a slight residue or a suspension was △, and the presence of a residue or no dissolution at all was rated as ×. The observation evaluation results and the viscosity measurement results are shown in Tables 1 to 7.

[0028] [Table 1]

[0029] result In Examples 1 to 3, which used the thickener for UV (ultraviolet light) or EB (electron beam) curable inks made of a specific aluminum chelate oligomer compound of the present invention, no unpleasant odor was generated, no volatile matter was generated, the solubility in acrylic monomers was high, and the thickening ability was high. On the other hand, in Comparative Example 1, in which the aluminum compound of Comparative Production Example 1 was used, an unpleasant odor was generated, volatile matter was generated, and the thickener was not suitable for UV (ultraviolet light) or EB (electron beam) curable ink. In Comparative Example 2, in which the aluminum compound of Comparative Production Example 2 was used, the solubility in acrylic monomers was low, and the thickening was lower than in Examples 1 to 3. In Comparative Example 3, in which the aluminum compound of Comparative Production Example 3 was used, the solubility in acrylic monomers was low, and the thickening was lower than in Examples 1 to 3. In Comparative Example 4, in which the aluminum compound of Comparative Production Example 4 was used, the solubility in acrylic monomers was low, and the thickening was lower than in Examples 1 to 3. In Comparative Example 5, in which the aluminum compound of Comparative Production Example 5 was used, the thickening was lower than in Examples 1 to 3. In Comparative Example 6, in which no aluminum chelate oligomer compound or aluminum compound was used, no thickening occurred, and the viscosity was lower than in Examples 1 to 3.

[0030] [Table 2]

[0031] result In Examples 4 to 6, which used the thickener for UV (ultraviolet light) or EB (electron beam) curable inks made of a specific aluminum chelate oligomer compound of the present invention, no unpleasant odor was generated, no volatile matter was generated, the solubility in acrylic monomers was high, and the thickening ability was high. On the other hand, in Comparative Example 7, in which the aluminum compound of Comparative Production Example 1 was used, an unpleasant odor was generated, volatile matter was generated, and the thickener was not suitable for UV (ultraviolet light) or EB (electron beam) curable inks. In Comparative Example 8, in which the aluminum compound of Comparative Production Example 2 was used, the solubility in acrylic monomers was low, and the thickening was lower than in Examples 4 to 6. In Comparative Example 9, in which the aluminum compound of Comparative Production Example 3 was used, the solubility in acrylic monomers was low, and the thickening was lower than in Examples 4 to 6. In Comparative Example 10, in which the aluminum compound of Comparative Production Example 4 was used, the solubility in acrylic monomers was low, and the thickening was lower than in Examples 4 to 6. In Comparative Example 11, in which the aluminum compound of Comparative Production Example 5 was used, the thickening was lower than in Examples 4 to 6. In Comparative Example 12, in which no aluminum chelate oligomer compound or aluminum compound was used, no thickening occurred, and the viscosity was lower than in Examples 4 to 6.

[0032] [Table 3]

[0033] result In Examples 7 to 9, which used a thickener for UV (ultraviolet light) or EB (electron beam) curable inks made of a specific aluminum chelate oligomer compound of the present invention, no unpleasant odor was generated, no volatile matter was generated, the solubility in acrylic monomers was high, and the thickening ability was high. On the other hand, in Comparative Example 13, in which the aluminum compound of Comparative Production Example 1 was used, an unpleasant odor was generated, volatile matter was generated, and the thickener was not suitable for UV (ultraviolet light) or EB (electron beam) curable inks. In Comparative Example 14, in which the aluminum compound of Comparative Production Example 2 was used, the solubility in acrylic monomers was low, and the thickening was lower than in Examples 7 to 9. In Comparative Example 15, in which the aluminum compound of Comparative Production Example 3 was used, the solubility in acrylic monomers was low, and the thickening was lower than in Examples 7 to 9. In Comparative Example 16, in which the aluminum compound of Comparative Production Example 4 was used, the solubility in acrylic monomers was low, and the thickening was lower than in Examples 7 to 9. In Comparative Example 17, in which the aluminum compound of Comparative Production Example 5 was used, the thickening was lower than in Examples 7 to 9. In Comparative Example 18, in which no aluminum chelate oligomer compound or aluminum compound was used, no thickening occurred, and the viscosity was lower than in Examples 7 to 9.

[0034] [Table 4]

[0035] result In Examples 10 to 12, which used a thickener for UV (ultraviolet light) or EB (electron beam) curable inks made of a specific aluminum chelate oligomer compound of the present invention, no unpleasant odor was generated, no volatile matter was generated, the solubility in acrylic monomers was high, and the thickening ability was high. On the other hand, in Comparative Example 19, in which the aluminum compound of Comparative Production Example 1 was used, an unpleasant odor was generated, volatile matter was generated, and the thickener was not suitable for UV (ultraviolet light) or EB (electron beam) curable inks. In Comparative Example 20, in which the aluminum compound of Comparative Production Example 2 was used, the solubility in acrylic monomers was low, and the thickening was lower than in Examples 10 to 12. In Comparative Example 21, in which the aluminum compound of Comparative Production Example 3 was used, the solubility in acrylic monomers was low, and the thickening was lower than in Examples 10 to 12. In Comparative Example 22, in which the aluminum compound of Comparative Production Example 4 was used, the solubility in acrylic monomers was low, and the thickening was lower than in Examples 10 to 12. In Comparative Example 23, in which the aluminum compound of Comparative Production Example 5 was used, the thickening was lower than in Examples 10 to 12. In Comparative Example 24, in which no aluminum chelate oligomer compound or aluminum compound was used, no thickening occurred, and the viscosity was lower than in Examples 10 to 12.

[0036] [Table 5]

[0037] result In Examples 13 to 15, which used a thickener for UV (ultraviolet light) or EB (electron beam) curable inks made of a specific aluminum chelate oligomer compound of the present invention, no unpleasant odor was generated, no volatile matter was generated, the solubility in acrylic monomers was high, and the thickening ability was high. On the other hand, in Comparative Example 25, in which the aluminum compound of Comparative Production Example 1 was used, an unpleasant odor was generated, volatile matter was generated, and the thickener was not suitable for UV (ultraviolet light) or EB (electron beam) curable ink. In Comparative Example 26, in which the aluminum compound of Comparative Production Example 2 was used, the solubility in acrylic monomers was low, and the thickening was lower than in Examples 13 to 15. In Comparative Example 27, in which the aluminum compound of Comparative Production Example 3 was used, the solubility in acrylic monomers was low, and the thickening was lower than in Examples 13 to 15. In Comparative Example 28, in which the aluminum compound of Comparative Production Example 4 was used, the solubility in acrylic monomers was low, and the thickening was lower than in Examples 13 to 15. In Comparative Example 29, in which the aluminum compound of Comparative Production Example 5 was used, the thickening was lower than in Examples 13 to 15. In Comparative Example 30, in which no aluminum chelate oligomer compound or aluminum compound was used, no thickening occurred, and the viscosity was lower than in Examples 13 to 15.

[0038] [Table 6]

[0039] result In Examples 16 to 18, which used a thickener for UV (ultraviolet light) or EB (electron beam) curable inks made of a specific aluminum chelate oligomer compound of the present invention, no unpleasant odor was generated, no volatile matter was generated, the solubility in acrylic monomers was high, and the thickening ability was high. On the other hand, in Comparative Example 31, in which the aluminum compound of Comparative Production Example 1 was used, there was generation of an unpleasant odor and generation of volatile matter, and it was not suitable as a thickener for UV (ultraviolet light) or EB (electron beam) curable ink. In Comparative Example 32, in which the aluminum compound of Comparative Production Example 2 was used, the thickening property was lower than that of Examples 16 to 18. In Comparative Example 33, in which the aluminum compound of Comparative Production Example 3 was used, the solubility in acrylic monomers was low, and the thickening property was lower than that of Examples 16 to 18. In Comparative Example 34, in which the aluminum compound of Comparative Production Example 4 was used, the solubility in acrylic monomers was low, and the thickening property was lower than that of Examples 16 to 18. In Comparative Example 35, in which the aluminum compound of Comparative Production Example 5 was used, the thickening property was lower than that of Examples 16 to 18. In Comparative Example 36, in which no aluminum chelate oligomer compound or aluminum compound was used, there was no thickening, and the viscosity was lower than that of Examples 16 to 18.

[0040] [Table 7]

[0041] result In Examples 19 to 21, which used a thickener for UV (ultraviolet light) or EB (electron beam) curable inks made of a specific aluminum chelate oligomer compound of the present invention, no unpleasant odor was generated, no volatile matter was generated, the solubility in acrylic monomers was high, and the thickening ability was high. On the other hand, in Comparative Example 37, in which the aluminum compound of Comparative Production Example 1 was used, an unpleasant odor was generated, volatile matter was generated, and the thickener was not suitable for UV (ultraviolet light) or EB (electron beam) curable inks. In Comparative Example 38, in which the aluminum compound of Comparative Production Example 2 was used, the thickening was lower than that of Examples 19 to 21. In Comparative Example 39, in which the aluminum compound of Comparative Production Example 3 was used, the solubility in acrylic monomers was low, and the thickening was lower than that of Examples 19 to 21. In Comparative Example 40, in which the aluminum compound of Comparative Production Example 4 was used, the solubility in acrylic monomers was low, and the thickening was lower than that of Examples 19 to 21. In Comparative Example 41, in which the aluminum compound of Comparative Production Example 5 was used, the thickening was lower than that of Examples 19 to 21. In Comparative Example 42, in which no aluminum chelate oligomer compound or aluminum compound was used, no thickening occurred, and the viscosity was lower than that of Examples 19 to 21. [Industrial Applicability]

[0042] The thickener for UV (ultraviolet light) or EB (electron beam) curable ink, which is made of a specific aluminum chelate oligomer compound of the present invention, can be used as a thickener, crosslinking agent, or gelling agent for various inks, various paints, etc.

Claims

1. A thickener for UV (ultraviolet light) or EB (electron beam) curable ink, comprising an aluminum chelate oligomer compound represented by the general formula (1). 【Chemistry 1】 (In the above general formula (1), R １ represents a linear or branched alkyl or alkenyl group having 1 to 18 carbon atoms; R ２ represents a linear, branched or cyclic alkyl, alkenyl, cycloalkyl or cycloalkenyl group having 1 to 18 carbon atoms, which may be substituted with a hydroxyl group; m+n represents the degree of polymerization of the aluminum chelate oligomer compound, m being 2 to 20, and n may be 0.

2. 2. The thickener for UV (ultraviolet) or EB (electron beam) curable ink according to claim 1, wherein, in the above general formula (1), m:n=1:2 to 2:0, and m+n=2 to 20.

3. Aluminum alkoxide, CH ３ -CO-CH ２ -CO-OR １ (R １ represents a linear or branched alkyl group or an alkenyl group having 1 to 18 carbon atoms; R ２ -COOH(R ２ represents a linear, branched or cyclic alkyl, alkenyl, cycloalkyl or cycloalkenyl group having 1 to 18 carbon atoms, which may be substituted with a hydroxyl group; and water, A method for producing a thickener for UV (ultraviolet light) or EB (electron beam) curable ink.

Images