JP4884623B2 - Aluminum chelate compounds and vehicle thickeners - Google Patents

Description

  The present invention relates to a novel aluminum chelate compound used as a vehicle thickener in the field of ink or paint.

  Conventionally, a metal that is an aluminum chelate containing an alkoxy group of a monohydric alcohol such as ethyl acetoacetate aluminum diisopropylate or an aluminum oligomer such as a cyclic aluminum oxide octylate as a gelling agent for a printing ink vehicle. Organic compounds are used.

  However, for example, an alkoxy group-containing aluminum chelate of a monohydric alcohol produces a monohydric alcohol that is a volatile component during ink production. Moreover, since the monovalent alkoxy group in the chelate has high reactivity, there is a problem that a partial gel is generated by a local reaction and a product having a desired quality cannot be obtained.

  On the other hand, the aluminum oligomer is a gelling agent that does not cause partial gelation, but the gelling ability is small, and a satisfactory thickening effect may not be obtained, which is not always optimal.

  Furthermore, in order to thicken the ink using an aluminum chelate or an aluminum oligomer having a conventional monovalent alkoxy group, it is generally necessary to perform the treatment at 100 ° C. or higher. Or it was not necessarily optimal for the use which adjusts a viscosity at the low temperature of 100 degrees C or less like EB (electron beam) curable ink.

  The problem to be solved by the present invention is that there is no generation of volatile components that are problematic in terms of environmental conservation during vehicle production in the ink and paint field, and there is a high gelling ability, offset printing and UV, To provide a novel aluminum chelate compound capable of producing a printing ink suitable for EB curable printing and a synthesis method thereof.

  In order to solve the above-mentioned problems, the present inventors have intensively studied. As a result, there is no generation of volatile components, and as a thickener for high-speed printing inks, particularly for offset printing inks and UV and EB curable printing inks, A novel aluminum chelate compound having good performance has been found and the present invention has been completed.

That is, the present invention relates to the general formula (1)
HO-X-OH (1)
Wherein, X is to display the neopentyl group. ]
Polyhydric alcohols having two free hydroxyl groups represented in the general formula (2)

[Wherein, R ¹ and R ² represent a linear or branched alkyl or alkenyl group having 1 to 18 carbon atoms. ]
It is related with the aluminum chelate compound obtained by making (beta) -ketoester and aluminum alkoxide shown by these react.

In addition, the present invention provides a general formula (1)
HO-X-OH (1)
Wherein, X is to display the neopentyl group. ]
Polyhydric alcohols having two free hydroxyl groups represented in the general formula (2)

[Wherein, R ¹ and R ² represent a linear or branched alkyl or alkenyl group having 1 to 18 carbon atoms. ]
Β-ketoester represented by the general formula ( 4 )

[Wherein R ³ represents a linear or branched alkyl or alkenyl group having 1 to 18 carbon atoms]
It is related with the aluminum chelate compound obtained by making the fatty acid and aluminum alkoxide shown by react.

  Furthermore, the present invention relates to a vehicle thickener comprising the above aluminum chelate compound.

  The aluminum chelate compound of the present invention is a compound suitable as a thickener for ink or paint vehicles. The reason why the aluminum chelate compound of the present invention has the effect of increasing the viscosity is considered to be mainly due to the gelation caused by crosslinking. Therefore, the thickener comprising the aluminum chelate compound of the present invention can be suitably used as a crosslinking agent and a gelling agent. Unlike the conventionally used ethyl acetoacetate aluminum diisopropylate, the thickener of the present invention may cause problems of local gelation with monohydric alcohol and environmental conservation problems in the normal ink and paint preparation process. In addition, a high thickening effect can be exhibited.

  The aluminum chelate compound of the present invention can be produced, for example, by the following method.

Aluminum alkoxide is an aprotic solvent for dissolving aluminum alkoxide, for example, hexane, heptane, toluene, xylene, or petroleum solvent, for example, No. 7, Solvent, AF Solvent No. 5, AF Solvent No. 7 Hydrocarbon solvents such as ethyl acetate, butyl acetate and di-2-ethylhexyl phthalate, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, tetrahydrofuran, propylene glycol monomethyl ether acetate, ether solvents such as butoxyethanol, N, N- dimethylformamide, 1,3-dimethyl-2-imidazolidine Gino emissions dissolved in an amide solvent such as, to the solution β- ketoester, polyhydric alcohol and fatty acid by the need It was added and heated to reflux, the replacement reaction of the ligand.

  Examples of the aluminum alkoxide used as a raw material for the aluminum chelate compound of the present invention include aluminum ethylate, aluminum isopropylate, aluminum sec-butyrate, mono-sec-butoxyaluminum diisopropylate, and the like. Aluminum isopropylate is preferred because it is easily available.

  The β-ketoester as a ligand is a compound represented by the general formula (2)

[Wherein, R ¹ and R ² represent a linear or branched alkyl or alkenyl group having 1 to 18 carbon atoms. ]
In a compound represented, when specifically exemplified, for example, methyl acetoacetate, ethyl acetoacetate, acetoacetate-isopropyl, acetoacetate t- butyl acetoacetate, isobutyl acetoacetate, n- butyl acetoacetate s ec - butyl, Examples thereof include 2-ethylhexyl acetoacetate, lauryl acetoacetate, oleyl acetoacetate, stearyl acetoacetate, and the like, but ethyl acetoacetate is preferred from the viewpoint of economy and availability.

The polyhydric alcohol used as a ligand is represented by the general formula (1)
HO-X-OH (1)
Wherein, X is to display the neopentyl group. ]
In a compound represented, a value o neopentyl glycol.

The fatty acid serving as a ligand is represented by the general formula ( 4 )

[Wherein R ³ represents a linear or branched alkyl or alkenyl group having 1 to 18 carbon atoms]
It is a compound shown by these. The fatty acid is added as a ligand to control the elasticity of the varnish, but may not be added if the desired elasticity can be obtained. As the fatty acid to be substituted, for example, a saturated or unsaturated fatty acid having a linear or branched chain having 1 to 18 carbon atoms is desirable. Specifically, acetic acid, butyric acid, hexanoic acid, 2-ethylhexanoic acid, octanoic acid, It may be a fatty acid having a single composition such as lauric acid, stearic acid and oleic acid, or a mixed fatty acid derived from a natural product such as coconut oil fatty acid or beef tallow fatty acid.

  The ligand substitution reaction is carried out at a reaction temperature of 80 ° C. to 200 ° C., more preferably 100 ° C. to 150 ° C. If it is less than 80 ° C., the progress of the reaction is slow, which leads to an inconvenient state, and if it exceeds 200 ° C., there may be a problem that the boiling point of the raw materials β-ketoester and polyhydric alcohol is exceeded. The target aluminum chelate compound can be obtained by distilling off the monohydric alcohol generated by the ligand substitution reaction. Alternatively, if there is no problem in mixing with ink or paint to be used thereafter, it can be handled as a solution as it is.

  Furthermore, when the substitution ratio of the ligand to aluminum is described in detail, when the aluminum compound of the present invention is used as a gelling agent for ink or a crosslinking agent for paint, the metal content (%) in the compound greatly affects the gelation ability. Therefore, it is necessary to select a ligand having an appropriate carbon number.

In order to obtain the crosslinking and thickening performance suitable for printing , the β -ketoester and fatty acid should be selected to have an appropriate molecular weight so that the aluminum content in the aluminum chelate compound is about 3 to 10%. It is necessary to use it.

  In order to obtain a compound suitable for this purpose, the ratio of β-ketoester groups to 0.5 mol of 2.5 mol of 1 mol of aluminum having a coordination number of 3 is 0 to 0 and the ratio of fatty acid groups to be added for elasticity adjustment is 0 to 0. 0.5, the polyhydric alcohol group involved in the crosslinking reaction is preferably in a ratio corresponding to the residue, and more preferably, the ratio of β-ketoester group to 1.0 mol of aluminum having a coordination number of 3 is 1.0. It is desirable that the ratio of the fatty acid group is 0 to 0.2 and the ratio of the polyhydric alcohol group is the balance.

Furthermore, considering the convenience in handling, in order to get what solution form has a carbon number of β- ketoester of R ¹ represented in one general formula (2) is 1 to 4, carbon atoms is R ² It is desirable that the carbon number of R ³ of the fatty acid represented by 2 to 18 and the general formula ( 4 ) is 4 to 18.

  Preferred structural formulas of the aluminum chelate compound of the present invention are exemplified below.

^Wherein, R 1, ^{R 2} and X are as defined above, X 'is to display the neopentyl group. ]

Among the aluminum chelate compound of the present invention, as a vehicle for a thickener in the ink or paint, as particularly preferred, in particular, it may be mentioned an ethyl acetoacetate aluminum neopentyl glycolate.

  The aluminum chelate compound of the present invention can be used as a vehicle thickener for inks or paints.

  For example, the ink may be prepared by the following method. First, after a resin (rosin-modified phenol resin or petroleum resin), drying oil (paulownia oil, linseed oil, soybean oil, etc.) and petroleum-based solvent are stirred at 200 ° C. for about 1 hour, the aluminum metal chelate derivative of the present invention is treated with 0.1%. Add 1-10% and stir at 180 ° C. for 1 hour to make an ink varnish. A pigment (arbitrary organic or inorganic pigment) and a petroleum solvent are added to this, and kneaded with a bead mill, a three-roll mill or the like to obtain a printing ink.

  In addition, paints can be prepared by coating resins (alkyd resins, acrylic resins, epoxy resins, silicone resins, etc.), solvents, pigments (any organic or inorganic pigments), other additives, and the aluminum metal chelate of the present invention. The derivative may be added in an amount of 0.1 to 10% and mixed with a sand mill, a bead mill or the like.

  In order to prepare a gel varnish for UV curable ink, photopolymerizable monomers (ethylene glycol diacrylate, trimethylolpropane methacrylate, pentaerythritol tetraacrylate, β-hydroxyalkyl methacrylate, etc.), pigments, photosensitizers, polymerization If the aluminum chelate compound of this invention is added 0.1 to 10% with respect to a photopolymerizable monomer as an inhibitor, a hardening accelerator, and other additives, and it stirs at 50-100 degreeC for about 1 hour, and is made to react. Good.

  A conventional aluminum chelate such as ethyl acetoacetate aluminum diisopropylate reacts with a carboxyl group or a hydroxyl group of a resin or oil and fat constituting a varnish to reach a gel structure. At this time, isopropyl alcohol which is a volatile component is generated. However, the aluminum chelate compound of the present invention generates a polyhydric alcohol after reaction with the resin and remains in the varnish, so that no volatile matter is generated. The produced polyhydric alcohol is considered to further increase the thickening effect of the varnish by hydrogen bonding with the resin.

(Example)
Hereinafter, the present invention will be described in more detail with reference to examples. In the examples, the aluminum content was measured by chelate titration method. In addition, this invention is not limited to the following Example.

Reference example 1
A glass reactor having a capacity of 300 ml was charged with 40.85 g (0.2 mol) of aluminum isopropylate and 48.85 g of toluene, and 26.03 g (0.2 mol) of ethyl acetoacetate and 1,2-butylene glycol 18.02g (0.2mol) was added, and it heated and refluxed for 1 hour.

  Isopropyl alcohol and toluene were distilled off from the reaction solution to obtain 48.85 g (yield 100%) of ethyl acetoacetate aluminum 1,3-butylene glycolate as a yellow solid. Further, this compound was soluble in solvents such as toluene, xylene, AF solvent 7 and the like.

In order to confirm the production | generation of the said compound, the aluminum content, the infrared absorption spectrum, and the < ¹ > H-NMR spectrum were measured.
Aluminum content 11.1% (theoretical value 11.0)
IR spectrum (cm ⁻¹ )
2979, 2929 (C—H stretching vibration of —CH ₂ — and —CH ₃ )
1615, 1523 (C = C and C = O stretching vibration)
1422, 1372 (C-H bending vibration)
1293 (C = O stretching vibration)
1175, 1103 (CO stretching vibration or C-H bending vibration)
784 (C = C conjugate system C—H bending vibration)
¹ H-NMR spectrum δ 1.0 to 1.1 ppm (H ratio 6, C H ₃ —CH—O—Al, C H ₃ CH ₂ —O—)
1.75~1.85ppm (-O- H ratio _{2, CH 3 -CH-C H} 2 -CH 2)
2.2 to 2.3 ppm (H ratio 3, C H ₃ —C—O—Al)
3.8~3.9ppm _(-O- H ratio _{5, CH 3 -C H -CH 2} -C H 2, CH 3 C H 2 -O-)
4.8~4.9ppm (H ratio _{1, CH 3 CH 2 -O-} C-C H = C-CH 3)
From the results of measurement of aluminum content, infrared absorption spectrum, and ¹ H-NMR spectrum, the ^one obtained here has ethyl acetoacetate aluminum 1,3-butylene glycolate having the structure of chemical formula ( 6 ) as an average structure. It is thought that.

Reference example 2
A glass reactor having a capacity of 300 ml was charged with 20.43 g (0.1 mol) of aluminum isopropylate and 46.66 g of toluene, and 35.26 g (0.1 mol) of oleyl acetoacetate was dissolved in this solution while stirring. 9.01 g (0.1 mol) of 1,3-butylene glycol was added and heated to reflux for 1 hour.

  Isopropyl alcohol and toluene were distilled off from the reaction solution to obtain 46.66 g (yield 100%) of oleyl acetoacetate aluminum-1,3-butylene glycolate as a yellow liquid. Further, this compound was soluble in solvents such as toluene, xylene, AF solvent 7 and the like.

In order to confirm the production | generation of the said compound, the aluminum content, the infrared absorption spectrum, and the < ¹ > H-NMR spectrum were measured.
Aluminum content 5.76% (theoretical value 5.78)
IR spectrum (cm ⁻¹ )
2924 (C—H stretching vibration of —CH ₂ — and —CH ₃ )
2854 (CH stretching vibration of —CH ₂ —)
1614, 1524 (C = C and C = O stretching vibration)
1463, 1422 (C-H bending vibration)
1294 (C = O stretching vibration)
1172, 1105 (CO stretching vibration or C-H bending vibration)
784 (C = C conjugate system C—H bending vibration)
¹ H-NMR spectrum δ 0.8 to 0.9 ppm (H ratio 3, oleyl group-terminated C H _3- )
1.2~1.3ppm (H ratio _{31, CH 3 (C H 2} ) 7 CH = CH (C H 2) 7 CH 2 -O-, C H 3 -CH-O-Al)
1.75~1.85ppm ((-O- H ratio _{2, CH 3 -CH-C H} 2 -CH 2)
2.0 to 2.1 ppm (H ratio 3, C H ₃ —C—O—Al)
3.85~3.95ppm (H ratio _{5, CH 3 -C H -CH 2} -C H 2 -O-, CH 3 (CH 2) 7 CH = CH (CH 2) 7 C H 2 -O-)
4.8 to 4.9 ppm (H ratio 1, —CH═CH (CH ₂ ) ₇ CH ₂ —O—C—C H = C—CH ₃ )
5.2 ~5.3ppm (H ratio _{2, CH 3 (CH 2)} 7 C H = C H (CH 2) 7 CH 2 -O-)
From the results of measurement of aluminum content, infrared absorption spectrum, and ¹ H-NMR spectrum, the product obtained here has an average structure of oleyl acetoacetate aluminum 1,3-butylene glycolate having the structure of chemical formula ( 7 ). It is thought that.

Reference example 3
A glass reactor having a capacity of 300 ml was charged with 40.85 g (0.2 mol) of aluminum isopropylate and 50.25 g of toluene, and 13.02 g (0.1 mol) of ethyl acetoacetate was dissolved in this solution while stirring. 14.42 g (0.1 mol) of 2-ethylhexanoic acid and 18.02 g (0.2 mol) of 1,3-butylene glycol were added and heated to reflux for 1 hour.

  Isopropyl alcohol and toluene were distilled off from the reaction solution to obtain 50.25 g (yield 100%) of ethyl acetoacetate aluminum-1,3-butyleneglycoxide octylate as a yellow solid. Further, this compound was soluble in solvents such as toluene, xylene, AF solvent 7 and the like.

In order to confirm the production | generation of the said compound, the aluminum content, the infrared absorption spectrum, and the < ¹ > H-NMR spectrum were measured.
Aluminum content 10.6% (theoretical value 10.7)
IR spectrum (cm ⁻¹ )
2962, 2933 (CH stretching vibration of —CH ₂ — and —CH ₃ )
2874 (CH stretching vibration of —CH ₂ —)
1615, 1526 (C = C and C = O stretching vibration)
1459, 1373 (C-H bending vibration)
1303 (C = O stretching vibration)
1176, 1105 (CO stretching vibration or C-H bending vibration)
784 (C = C conjugate system C—H bending vibration)
¹ H-NMR spectrum δ 0.75 to 0.85 ppm (H ratio 6, C H ₃ (CH ₂ ) ₂ CH ₂ (C H ₃ CH ₂ ) CHCOO—)
1.15~1.94ppm (H ratio _{8, CH 3 (C H 2} ) 2 C H 2 (CH 3 C H 2) CHCOO-)
1.25 to 1.35 ppm (H ratio 6, C H ₃ —CH—O—Al, C H ₃ CH ₂ —O—)
1.8~1.9ppm (-O- H ratio _{2, CH 3 -CH-C H} 2 -CH 2)
2.3 to 2.4 ppm (H ratio 4, C H ₃ —C—O—Al, CH ₃ (CH ₂ ) ₂ CH ₂ (CH ₃ CH ₂ ) C H COO—)
3.85~3.95ppm _(-O- H ratio _{5, CH 3 -C H -CH 2} -C H 2, CH 3 C H 2 -O-)
4.85~4.95ppm (H ratio _{1, CH 3 CH 2 -O-} C-C H = C-CH 3)
From the results of measurement of aluminum content, infrared absorption spectrum, and ¹ H-NMR spectrum, the ^one obtained here is an average structure of ethyl acetoacetate aluminum 1,3-butylene glycoloxide octylate having the structure of chemical formula ( 8 ). It is thought that.

Reference example 4
A glass reactor having a capacity of 300 ml was charged with 20.43 g (0.1 mol) of aluminum isopropylate and 48.26 g of toluene, and 35.26 g (0.1 mol) of oleyl acetoacetate was dissolved in this solution while stirring. Diethylene glycol 10.61 g (0.1 mol) was added and heated to reflux for 1 hour.

  Isopropyl alcohol and toluene were distilled off from the reaction solution to obtain 48.26 g (yield 100%) of oleyl acetoacetate aluminum diethylene glycolate as a yellow liquid. Further, this compound was soluble in solvents such as toluene, xylene, AF solvent 7 and the like.

In order to confirm the production | generation of the said compound, the aluminum content, the infrared absorption spectrum, and the < ¹ > H-NMR spectrum were measured.
Aluminum content 5.57% (theoretical value 5.59)
IR spectrum (cm ⁻¹ )
2923 (C—H stretching vibration of —CH ₂ — and —CH ₃ )
2853 (CH stretching vibration of —CH ₂ —)
1610, 1526 (C = C and C = O stretching vibration)
1465 (C-H bending vibration)
1295 (C = O stretching vibration)
1172, 1076 (CO stretching vibration or C-H bending vibration)
784 (C = C conjugate system C—H bending vibration)
¹ H-NMR spectrum δ 0.85 to 0.95 ppm (H ratio 3, oleyl group-terminated C H _3- )
1.2~1.3ppm (H ratio _{28, CH 3 (C H 2} ) 7 CH = CH (C H 2) 7 CH 2 -O-,
2.2 to 2.3 ppm (H ratio 3, C H ₃ —C—O—Al)
3.6~3.7ppm (H ratio _{10, -O-C H 2 -C} H 2 -O-C H 2 -C H 2 -O-, CH 3 (CH 2) 7 CH = CH (CH 2) ₇ C H ₂ —O—)
4.8 to 4.9 ppm (H ratio 1, —CH═CH (CH ₂ ) ₇ CH ₂ —O—C—C H = C—CH ₃ )
5.3~5.4ppm (H ratio _{2, CH 3 (CH 2)} 7 C H = C H (CH 2) 7 CH 2 -O-)
From the results of measurement of the aluminum content, infrared absorption spectrum, and ¹ H-NMR spectrum, it is considered that the product obtained here has oleyl acetoacetate aluminum diethylene glycolate having the structure of the chemical formula ( 9 ) as an average structure. .

Example 1
A glass reactor having a capacity of 300 ml was charged with 40.85 g (0.2 mol) of aluminum isopropylate and 51.65 g of toluene, and 26.03 g (0.2 mol) of ethyl acetoacetate and Neopentyl glycol 20.83 g (0.2 mol) was added, and the mixture was heated to reflux for 1 hour.

  Isopropyl alcohol and toluene were distilled off from the reaction solution to obtain 51.65 g (yield 100%) of ethyl acetoacetate aluminum neopentyl glycolate as a yellow solid. Further, this compound was soluble in solvents such as toluene, xylene, AF solvent 7 and the like.

In order to confirm the formation of the compound, the aluminum content and infrared absorption spectrum were measured.
Aluminum content 10.3% (theoretical value 10.4)
IR spectrum (cm ⁻¹ )
2923 (C—H stretching vibration of —CH ₂ — and —CH ₃ )
2856 (CH stretching vibration of —CH ₂ —)
1613, 1529 (C = C and C = O stretching vibration)
1420, 1371 (C-H bending vibration)
1304 (C = O stretching vibration)
1174, 1083 (CO stretching vibration or C-H bending vibration)
784 (C = C conjugate system C—H bending vibration)
From the results of measurement of the aluminum content and infrared absorption spectrum, the product obtained here is considered to have ethyl acetoacetate aluminum neopentyl glycolate having the structure of the chemical formula ( 10 ) as an average structure.

Reference Example 5
A glass reactor having a capacity of 300 ml was charged with 40.85 g (0.2 mol) of aluminum isopropylate and 48.71 g of toluene, and 26.03 g (0.2 mol) of ethyl acetoacetate and Trimethylolpropane (17.89 g, 0.13 mol) was added, and the mixture was heated to reflux for 1 hour.

  Isopropyl alcohol and toluene were distilled off from the reaction solution to obtain 48.71 g (yield 100%) of ethyl acetoacetate aluminum trimethylol propylate as a yellow solid. Further, this compound was soluble in solvents such as toluene, xylene, AF solvent 7 and the like.

In order to confirm the formation of the compound, the aluminum content and infrared absorption spectrum were measured.
Aluminum content 11.0% (theoretical value 11.1)
IR spectrum (cm ⁻¹ )
2922 (C—H stretching vibration of —CH ₂ — and —CH ₃ )
2854 (CH stretching vibration of —CH ₂ —)
1635, 1526 (C = C and C = O stretching vibration)
1423, 1370 (C-H bending vibration)
1289 (C = O stretching vibration)
1174, 1090 (CO stretching vibration or C-H bending vibration)
783 (C = C conjugate system C—H bending vibration)
From the results of measurement of the aluminum content and infrared absorption spectrum, the product obtained here is considered to have an ethyl acetoacetate aluminum trimethylol propylate average structure having the structure of formula ( 11 ).

Reference Example 6
A glass reactor having a capacity of 300 ml was charged with 40.85 g (0.2 mol) of aluminum isopropylate and 57.66 g of toluene and dissolved while stirring. To this solution, 26.03 g (0.2 mol) of ethyl acetoacetate and 26.84 g (0.2 mol) of trimethylolpropane were added and heated to reflux for 1 hour.

  Isopropyl alcohol and toluene were distilled off from the reaction solution to obtain 57.66 g (yield 100%) of ethyl acetoacetate aluminum trimethylol propylate as a yellow solid. Further, this compound was soluble in solvents such as toluene, xylene, AF solvent 7 and the like.

In order to confirm the formation of the compound, the aluminum content and infrared absorption spectrum were measured.
Aluminum content 9.33% (theoretical 9.36)
IR spectrum (cm ⁻¹ )
3600 (-OH stretching vibration)
2922 (C—H stretching vibration of —CH ₂ — and —CH ₃ )
2854 (CH stretching vibration of —CH ₂ —)
1635, 1526 (C = C and C = O stretching vibration)
1423, 1370 (C-H bending vibration)
1289 (C = O stretching vibration)
1174, 1090 (CO stretching vibration or C-H bending vibration)
783 (C = C conjugate system C—H bending vibration)

Example 2
Resin for testing by heating and stirring 40.0 parts by weight of rosin-modified phenolic resin, 30.0 parts by weight of linseed oil and 30.0 parts by weight of AF solvent 7 (solvent manufactured by Nippon Oil Co., Ltd.) for 1 hour. A varnish was prepared.

Aluminum content of 100 parts of this resin varnish diluted with 50% of the aluminum chelate compound synthesized in Example 1 and Reference Examples 1 to 5 , and ethyl acetoacetate aluminum diisopropylate as a comparative example with AF Solvent 7 respectively. Was added to 0.1%. The addition temperature was 90 ° C. Here, the state at the time of addition was observed. The results are shown in Table 1.

As is apparent from the results shown in Table 1, when the aluminum chelate compound of Example 1 of the present invention was used, no volatile matter was generated during the addition.

Example 3
AF Solvent No. 7 with 100 parts of resin varnish (resin varnish for test similar to Example 2 ), the aluminum chelate compound synthesized in Example 1 and Reference Examples 1 to 5 , and ethyl acetoacetate aluminum diisopropylate as a comparative example. Diluted to 50% with an aluminum content of 0.1%. The addition temperature was 90 ° C.

  These were heated at 180 ° C. for 3 hours for gelation reaction, and then the viscosity was measured at 25 ° C. using a Brookfield viscometer (manufactured by Tokyo Keiki Co., Ltd.). The results are shown in Table 2.

As is clear from the results shown in Table 2, the resin varnish using the aluminum chelate compound of Example 1 of the present invention has a high thickening effect.

Example 4
AF Solvent No. 7 with 100 parts of resin varnish (resin varnish for test similar to Example 2 ), the aluminum chelate compound synthesized in Example 1 and Reference Examples 1 to 5 , and ethyl acetoacetate aluminum diisopropylate as a comparative example. Diluted to 50% with an aluminum content of 0.1%. The addition temperature was 60 ° C, 90 ° C, 120 ° C, 150 ° C, 180 ° C. The presence or absence of a local gel of the resin varnish at each addition temperature was observed. The results are shown in Table 3. The case where the local gel was not generated was indicated by ○, and the case where the local gel was generated was indicated by ×.

As is clear from the results shown in Table 3, the resin varnish using the aluminum chelate compound of Example 1 of the present invention does not produce a local gel.

The aluminum chelate compound of the present invention can be used as a vehicle thickener for inks or paints, and can provide a high thickening effect without producing alcohol as a volatile component during vehicle production.

Claims (8)

General formula (1)
HO-X-OH (1)
Wherein, X is to display the neopentyl group. ]
Polyhydric alcohols having two free hydroxyl groups represented in the general formula (2)

[Wherein, R ¹ and R ² represent a linear or branched alkyl or alkenyl group having 1 to 18 carbon atoms. ]
An aluminum chelate compound obtained by reacting a β-ketoester represented by the formula (I) and an aluminum alkoxide. The average coordination molecular number of the β-ketoester represented by the general formula (2) and the polyhydric alcohol represented by the general formula (1) to aluminum is 0.5 mol of β-ketoester with respect to 1 mol of aluminum, respectively. The aluminum chelate compound according to claim 1, wherein ˜2.5 mol and the remainder is a polyhydric alcohol. The aluminum chelate compound has the general formula (3)

^[Wherein, R 1, ^{R 2} are as defined above, X 'is to display the neopentyl group. ]
The aluminum chelate compound according to claim 1, wherein the aluminum chelate compound is represented by the formula: General formula (1)
HO-X-OH (1)
Wherein, X is to display the neopentyl group. ]
Polyhydric alcohols having two free hydroxyl groups represented in the general formula (2)

[Wherein, R ¹ and R ² represent a linear or branched alkyl or alkenyl group having 1 to 18 carbon atoms. ]
Β-ketoester represented by the general formula ( 4 )

[Wherein R ³ represents a linear or branched alkyl or alkenyl group having 1 to 18 carbon atoms]
The aluminum chelate compound obtained by making the fatty acid and aluminum alkoxide shown by react. The β-ketoester represented by the general formula (2), the polyhydric alcohol represented by the general formula (1), and the fatty acid represented by the general formula ( 4 ) are coordinated to aluminum, and the average coordination molecular number The aluminum chelate according to claim 4, wherein the β-ketoester is 0.5 to 2.5 mol, the fatty acid is 0 to 2.0 mol, and the balance is a polyhydric alcohol with respect to 1 mol of aluminum. Compound. The aluminum chelate compound has the general formula ( 5 )

[Wherein R ¹ , R ² , R ³ and X are the same as defined above. ]
Aluminum chelate compounds according to claim 4 or 5, characterized in that in an aluminum chelate compound represented. General formula (1)
HO-X-OH (1)
Wherein, X is to display the neopentyl group. ]
Polyhydric alcohols having two free hydroxyl groups represented in the general formula (2)

[Wherein, R ¹ and R ² represent a linear or branched alkyl or alkenyl group having 1 to 18 carbon atoms. ]
A vehicle thickener comprising: an aluminum chelate compound obtained by reacting a β-ketoester represented by the formula (1) with an aluminum alkoxide. General formula (1)
HO-X-OH (1)
Wherein, X is to display the neopentyl group. ]
Polyhydric alcohols having two free hydroxyl groups represented in the general formula (2)

[Wherein, R ¹ and R ² represent a linear or branched alkyl or alkenyl group having 1 to 18 carbon atoms. ]
Β-ketoester represented by the general formula ( 4 )

[Wherein, R ³ represents a linear or branched alkyl group or alkenyl group having 1 to 18 carbon atoms. ]
A vehicle thickener comprising an aluminum chelate compound obtained by reacting a fatty acid represented by formula (1) with an aluminum alkoxide.