JP2015183056A - Dryer and oxidative-polymerizable composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a practical dryer not using metals having high health hazard properties such as cobalt or manganese; and an oxidative-polymerizable composition.SOLUTION: A dryer comprises at least one transition metal selected from the group consisting of iron, cerium and zirconium, or salt thereof, and a ligand composition or transition metal complex including a ligand represented by general formula (1) (excluding 2,2'-bipyridyl), or a ligand represented by general formula (2).

Description

  The present invention relates to a transition metal complex and an oxidatively polymerizable composition containing the same. According to the present invention, it is possible to dry an oxidation polymerization type ink or paint without using a metal with high health hazards (or strict regulations) such as cobalt or manganese.

  Film formation by oxidative polymerization of lacquer and dry vegetable oil has been known for a long time, and oxidative polymerization type inks and paints are still used industrially in the fields of printing and coating. In order to speed up the drying practically, a method of adding a metal carboxylate to an oxidative polymerization composition such as a resin or dry vegetable oil has been used for a long time. Specifically, metal salts of transition metals such as cobalt, manganese, lead, iron, or zinc and various carboxylic acids have been used. In particular, cobalt metal salts and manganese metal salts have excellent drying performance, and are therefore used as main drying accelerators (dryers).

However, the health hazards of some metal species cannot be ignored, and lead dryers were almost never used decades ago, except in the paint field. Cobalt was classified into Group 2B (suspected to be carcinogenic to humans) by the IARC (International Cancer Research Institute). For this reason, regulations are becoming stricter in each country. There are still no countries or regions where the use of cobalt dryers has been banned by law, but there are also major food manufacturers seeking to reduce the concentration in their product packaging. Manganese dryers, which are considered to be lower risk than cobalt, also have various laws and regulations in Japan, such as the Industrial Safety and Health Act, the Water Pollution Control Act, and the Water Supply Act. In this way, the non-use and reduction of cobalt and manganese are strongly demanded than before, but the effects of dryers such as iron, which are less harmful than both, are very low and are used practically alone. I couldn't.
In the field of printing inks, it is required to dry quickly after printing, but when printing, the opposite performance is required that it does not dry on the printing press. Furthermore, drying may be slow due to factors such as emulsification during printing and the pH of the paper being low, and troubles may occur in which the printed matter becomes defective, and a more difficult drying balance is required during printing and after printing. For these measures, a formulation in which a little more metal dryer is added and at the same time an antioxidant is often used. For example, hydroquinone-based antioxidants have a high effect of balancing the contradictory drying balance, but when hydrogen is applied to exert a reduction effect, it changes to a quinone structure with high health hazards and irritation. Both the dryer and the antioxidant are required to be reduced, and a fundamental review of the conventional formula is required.

  On the other hand, it has been known for some time that oxidation polymerization can be made faster by adding an amine compound to a metal dryer (Non-Patent Document 1), and there are a plurality of patent documents. For example, Patent Document 1 discloses a drying accelerator obtained by adding diethanolamine, diethylethanolamine, dibutylethanolamine, or n-butyldiethanolamine to a cobalt metal salt or a manganese metal salt. Also. Patent Document 2 discloses a printing ink dryer in which a specific amino alcohol is added to a fatty acid manganese salt. However, the drying accelerator described in Patent Document 2 uses a manganese salt, and is a burden on the environment.

JP 2001-49102 A WO2011 / 158694 JP 2004-323732 A JP 2005-154628 A

Ichikawa Ieyasu, “Science of Easy-to-understand Paper, Ink, and Printing”, 6th revised edition, Printing Bureau Chaokai, 1981, p. 237

In addition, drying accelerators using iron with low health hazards have been reported. For example, Patent Document 3 discloses an oxidatively polymerizable composition containing an oxidoreductase and a transition metal complex. However, the drying effect of the oxidatively polymerizable composition using the iron complex described in Patent Document 3 is not sufficient as compared with that using the manganese complex. Furthermore, Patent Document 4 discloses a curable resin composition using a porphyrin iron complex (tetraporphyrin iron or phthalocyanine iron). However, the porphyrin iron complex is colored and cannot be substantially used as a dryer. Further, the solubility was poor, and although dissolved in THF in the examples, THF was not practically usable as an ink solvent.
Accordingly, an object of the present invention is to provide a practical drying accelerator and an oxidatively polymerizable composition that do not use a metal with high health hazard such as cobalt or manganese.

As a result of diligent research on drying accelerators for printing inks that do not use metals with high health hazards such as cobalt or manganese, the present inventors have surprisingly found that a ligand having a specific structure and iron, cerium, etc. Further, it has been found that a drying accelerator having a performance equal to or higher than that of a conventional drying accelerator using cobalt or manganese can be obtained by complexing with zirconium or a salt thereof.
The present invention is based on these findings.

Therefore, the present invention
[1] At least one transition metal selected from the group consisting of iron, cerium, and zirconium, or a salt thereof; and general formula (1):
A ligand represented by the formula (excluding 2,2′-pipyridyl) or general formula (2):
A ligand composition or a transition metal complex containing a ligand represented by the general formula (1) and the general formula (2):
R ¹ is (i) a single bond, (ii) Formula (3):
(In the formula (3), X is a single bond, or an alkylene group having 1 to 4 carbon atoms, ^{R 5} is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group or a methoxy having from 1 to 4 carbon atoms A group comprising one or more pyridyl groups optionally substituted with a group), or (iii) Formula (4):
(In Formula (4), R ⁶ is one or more pyridyl groups optionally substituted with a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms or a methoxy group. R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or an aryl group; and R ⁴ is each a group represented by Independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group or an aryl group; a drying accelerator comprising the ligand composition or the metal complex;
[2] The group containing one or more pyridyl groups is a pyridyl group or formula (5):
A drying accelerator according to [1], which is a group represented by:
[3] The ligand is N, N, N ′, N′-tetrakis (2-pyridylmethyl) ethylenediamine, tris (2-pyridylmethyl) amine, bis (2-pyridylmethyl) amine, 2,4, A ligand selected from the group consisting of 6-tri (2-pyridyl) -1,3,5-triazine, 5,5′-dimethyl-2,2′-dipyridyl, and 2,2′-bipyridylyl , [1] or [2], or [4] a varnish containing a resin or drying oil, and an oxidatively polymerizable composition comprising the drying accelerator according to any one of [1] to [3] object,
About.

  According to the drying accelerator of the present invention, it is possible to dry a printing ink or paint using oxidative polymerization without using a metal such as cobalt or manganese, which is highly harmful to health. Further, the drying accelerator of the present invention has a shorter drying time by a C-type drying tester than the drying time by a glass plate. That is, it is difficult to dry on a printing machine, and is easy to dry on printed paper. Therefore, in actual use, an excellent drying balance can be obtained without adding an antioxidant, and the amount added can be reduced as compared with a conventional dryer.

[Drying accelerator]
The drying accelerator of the present invention includes a transition metal complex containing a ligand and a transition metal (iron, cerium, and / or zirconium) or a salt thereof.

  Printing inks and paints that utilize oxidative polymerization have a more robust coating by polymerizing the oxidatively polymerizable resin and drying oil (linseed oil, tung oil, soybean oil, etc.) in the composition through oxidative polymerization. Therefore, it is a dryer that practically increases the polymerization rate. The main factors affecting this oxidative polymerization include temperature, humidity, film thickness and the like. In the printing field, there are paper pH, pigment type (especially acidic carbon black), fountain solution and emulsification in addition to the aforementioned factors.

  The drying accelerator of the present invention may contain a ligand having a specific structure and a transition metal salt, or may contain a transition metal complex of a ligand having a specific structure and a transition metal.

<Ligand>
The ligand used in the drying accelerator of the present invention is:
General formula (1):
[Wherein R ¹ is (i) a single bond,
(Ii) Formula (3):
(In the formula (3), X is a single bond, or an alkylene group having 1 to 4 carbon atoms, ^{R 5} is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group or a methoxy having from 1 to 4 carbon atoms A group comprising one or more pyridyl groups optionally substituted with a group), or (iii) Formula (4):
(In Formula (4), R ⁶ is one or more pyridyl groups optionally substituted with a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms or a methoxy group. R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or an aryl group, and R ⁴ is each a group represented by Independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or an aryl group]
The ligand represented by these may be sufficient.

Moreover, the ligand used for the drying accelerator of the present invention is:
General formula (2):
[Wherein, R ¹ is (i) a single bond, (ii) a group represented by the above formula (3), or (iii) a group represented by the above formula (4), and each R ⁴ is independently selected. And a ligand represented by a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or an aryl group].

In the general formulas (1) and (2), R ⁴ means a group at three positions of ortho, meta, and para with respect to the nitrogen atom of the pyridyl group, and one group has the number of carbon atoms. It may be an alkyl group having 1 to 4 carbon atoms, a methoxy group or an aryl group, and two groups may be an alkyl group having 1 to 4 carbon atoms, a methoxy group or an aryl group, and 3 groups may have 1 to 1 carbon atoms. 4 may be an alkyl group, a methoxy group or an aryl group.

R ¹ is a single bond, a group represented by formula (3), or a group represented by formula (4), preferably a group containing a nitrogen atom, and most preferably in formula (3). It is a group represented.

<< Ligand of general formula (1) >>
(When R ¹ is a group represented by Formula (3))
When R ¹ is a group represented by the formula (3), X is a single bond or an alkylene group having 1 to 4 carbon atoms, and R ⁵ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or one It is a group containing the above pyridyl group. The pyridyl group may be optionally substituted with an alkyl group having 1 to 4 carbon atoms or a methoxy group.
Here, when X is a single bond, although not limited, R ⁵ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
When X is an alkylene group having 1 to 4 carbon atoms, R ⁵ may be a hydrogen atom or a group containing one or more pyridyl groups. In particular, when X is an alkylene group having 1 carbon atom (methylene group), it is not limited, but R ⁵ is preferably a group containing one or more pyridyl groups, more preferably a pyridyl group. Further, when X is an alkylene group having 2 carbon atoms (ethylene group), it is not limited, but R ⁵ is preferably a group containing one or more pyridyl groups, and the formula (5):
Is more preferable.

As a specific ligand when R ¹ is a group represented by the formula (3), (A) N, N, N ′, N′-tetrakis (2- Pyridylmethyl) ethylenediamine, (B) tris (2-pyridylmethyl) amine represented by the following formula (7), or (C) bis (2-pyridylmethyl) amine represented by the following formula (8) Can do.
(A)
(B)
(C)

Furthermore, as a derivative of tris (2-pyridylmethyl) amine, a compound represented by the following formula (9) in which the hydrogen atom of the pyridyl group is substituted by an alkyl group having 1 to 4 carbon atoms or a methoxy group can be exemplified. .

(When R ¹ is a group represented by Formula (4))
When R ¹ is a group represented by formula (4), R ⁶ is a group containing a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or one or more pyridyl groups. Although not limited, a pyridyl group or a group represented by the general formula (5) is preferable.
The pyridyl group may be optionally substituted with an alkyl group having 1 to 4 carbon atoms or a methoxy group.

As a specific ligand when R ¹ is a group represented by the formula (4), (D) 2,4,6-tri (2-pyridyl) -1 represented by the following formula (10) , 3,5-triazine.
(D)

(When R ¹ is a single bond)
When R ¹ is a single bond, it is not limited, but the ligand is preferably dipyridyl or a derivative thereof. In this case, R ² , R ³ , and R ⁴ may each independently be a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or an aryl group, preferably a hydrogen atom or carbon number 1 to 4 alkyl groups.
Specific examples of the ligand when R ¹ is a single bond include (E) 5,5′-dimethyl-2,2′-dipyridyl represented by the following formula (11).
(E)

<< Ligand of general formula (2) >>
(When R ¹ is a single bond)
When R ¹ is a single bond, the ligand is preferably dipyridyl or a derivative thereof, although not limited thereto. Specific examples of the ligand in the case where R ¹ is a single bond include (F) 2,2′-dipyridimyl represented by the following formula (12).
(F)

<Transition metal salt>
The transition metal salt that can be used in the drying accelerator of the present invention is not limited as long as it can form a complex with the ligand, and examples thereof include iron salts, cerium salts, and zirconium salts. However, an iron salt is preferable because of its high promoting effect.
The iron salt is not limited as long as it contains an iron atom capable of forming an iron complex with the ligand, but iron acetate, iron formate, iron lactate, iron chloride, iron octylate, or Mention may be made of iron naphthenate.
Examples of the cerium salt include cerium acetate, cerium formate, cerium lactate, cerium chloride, cerium octylate, and cerium naphthenate. Furthermore, examples of the zirconium salt include zircon acetate, zirconate formate, zircon lactate, zircon octylate, zircon octylate, and zirconate naphthenate.
Iron salts, cerium salts, zirconium salts, and the like that can be used in the present invention are transition metal salts that have higher safety to living bodies or the environment and less burden on the environment than cobalt or manganese.

<Transition metal complex>
The drying accelerator of the present invention may contain a transition metal complex. The transition metal complex that can be included in the drying accelerator of the present invention is a transition metal complex in which the ligand and at least one transition metal selected from the group consisting of iron, cerium, and zirconium are coordinated. is there. As the ligand of the transition metal complex, the ligand can be used without limitation. As a metal of the transition metal complex, iron, cerium, or zirconium can be used without limitation. A coordinate bond is a chemical bond in which bond electrons are provided to the molecular orbitals only from one of the two atoms that form the bond.

The method for obtaining the transition metal complex of the present invention is not limited and can be obtained by a usual method.
For example, it can be obtained by mixing the ligand and the transition metal salt. The mixing ratio of the ligand and the transition metal salt is not limited as long as the metal complex that can be used in the present invention is obtained, but the nitrogen in the ligand is one molecule of the transition metal salt. It is preferable that 3 to 4 atoms are coordinated. Therefore, in the case of a ligand containing two nitrogen atoms, the molar ratio of the ligand to 1 mol of the transition metal salt is preferably 0.18 to 18.0, more preferably 0.9 to 3.6. It is. In the case of a ligand containing 3 nitrogen atoms, the molar ratio of the ligand to 1 mol of the transition metal salt is preferably 0.12 to 12.0, more preferably 0.6 to 2.4. is there. In the case of a ligand containing 4 nitrogen atoms, the molar ratio of the ligand to 1 mol of the transition metal salt is preferably 0.09 to 9.0, more preferably 0.45 to 1.8. is there. In the case of a ligand containing 5 nitrogen atoms, the molar ratio of the ligand to 1 mol of the transition metal salt is preferably 0.07 to 7.0, more preferably 0.35 to 1.4. is there. In the case of a ligand containing 6 nitrogen atoms, the molar ratio of the ligand to 1 mol of the transition metal salt is preferably 0.06 to 6.0, more preferably 0.30 to 1.2. is there.

<< Drying accelerator containing metal complex >>
As one embodiment of the drying accelerator of the present invention, a drying accelerator containing the transition metal complex can be mentioned.

In the drying accelerator of the present invention, the transition metal complex may be used alone or in combination of two or more.
The drying accelerator of the present invention can contain a compound other than a transition metal complex as long as the function as a drying accelerator is not inhibited when added to an ink or paint. Specific examples of the compound added include a ligand and a diluent for a metal salt.
For example, examples of the diluent include alcohols, glycols, polyhydric alcohols, esters and ethers thereof.
In addition, the drying accelerator of this invention can also contain the drying inhibitor (antioxidant) for adjusting drying time.

<< Drying accelerator containing ligand and metal salt >>
As one embodiment of the drying accelerator of the present invention, a drying accelerator containing a ligand and a transition metal can be mentioned. The drying accelerator of the present invention may be a one-component drying accelerator in which the ligand and the metal salt are provided as one liquid (one agent). Further, a liquid containing a ligand (hereinafter sometimes referred to as a ligand-containing liquid) and a liquid containing a transition metal salt (hereinafter sometimes referred to as a transition metal-containing liquid) are two separate liquids. A two-component drying accelerator provided as (two agents) may be used. That is, the aspect which makes the 1st liquid and the 2nd liquid contain individually the ligand provided individually and the transition metal salt as a ligand composition may be sufficient.
In the case of a two-component drying accelerator, the ligand-containing liquid may be added to the ink or paint, and then the transition metal-containing liquid may be added to the ink or paint. Further, the transition metal-containing liquid may be added to the ink or the paint, and then the ligand-containing liquid may be added to the ink or the paint.

In the drying accelerator of the present invention, the ligand may be used alone or in combination of two or more. Moreover, although the said transition metal salt may be used by 1 type, you may use it in combination of 2 or more types.
The molar ratio of the ligand to the transition metal salt in the drying accelerator is not particularly limited as long as the effect of the present invention is obtained, but the nitrogen in the ligand with respect to one molecule of the transition metal salt. It is preferable that 3 to 4 atoms are coordinated. Therefore, the range of the molar ratio of the ligand to 1 mol of the transition metal salt is preferably the range described in the above “transition metal complex”.

  The addition amount of the drying accelerator or transition metal complex drying accelerator containing the ligand and metal salt of the present invention in the ink is limited as long as the drying time is shortened compared to the case where the drying accelerator is not used. Is not to be done. That is, it can be appropriately adjusted according to the type of ink to be added, the varnish composition, and the like. For example, it can be used as a drying accelerator (dryer) at 0.001 wt% to 5 wt%, preferably It is 0.005 weight%-2 weight%, More preferably, it is 0.01 weight%-1 weight%. Moreover, it is desirable to reduce the compounding quantity of a complex as much as possible in the range of a required drying time from a viewpoint of reduction to addition to an environment, and safety | security.

<< Ligand composition containing ligand and transition metal salt >>
The drying accelerator of the present invention may include a ligand composition including a ligand and a transition metal salt. A ligand composition is a composition containing the said ligand and the said transition metal salt, and can be used for the drying acceleration | stimulation of oxidation polymerization drying type printing ink and a coating material. The ligand composition can include one or more of the ligands. Further, the ligand composition may include one or more of the transition metal salts.
The ligand composition is usually provided by mixing a ligand and a transition metal salt. However, the ligand composition of the present invention includes a composition containing a ligand and a transition metal salt separately. For example, the ligand composition of the present invention is provided as a reagent containing a first liquid containing a ligand and a second liquid containing a transition metal salt, and includes a mode in which a user mixes.

[Oxidatively polymerizable composition]
The oxidative polymerizable composition containing the transition metal complex or the drying accelerator is not limited as long as it uses oxidative polymerization drying, and only replaces a conventional oxidative polymerization type ink or a drier in a paint. It's okay. The oxidatively polymerizable composition of the present invention contains a resin or a dry oil.

  As a resin contained in the oxidatively polymerizable composition of the present invention, a resin conventionally contained in an oxidatively polymerizable composition can be used without being changed. For example, rosin-modified phenol resin, rosin-modified maleic acid resin, unsaturated polyester, alkyd resin, and the like can be given. Also, when a resin that does not undergo oxidative polymerization is used in combination, it can be used with a conventional resin composition.

  When dry oil is contained in the conventional composition, it can be used without changing the composition. For example, dry oil such as akaritum fat, hemp seed oil, sesame oil, isano oil, sea urchin kernel oil, sesame oil, psyllium oil, pods oil, walnut oil, poppy oil, pomegranate seed oil, safflower oil, cinnamon oil , Soybean oil, tobacco seed oil, sweet potato kernel oil, Japanese drill oil, rubber seed oil, evening primrose seed oil, sunflower seed oil, grape seed oil, spinach seed oil, honey seed oil, or rumba nut oil . Moreover, even when semi-drying oil or non-drying oil is used in combination, it can be used without changing the composition.

(Coloring agent)
As the colorant that can be contained in the oxidative polymerization composition of the present invention, conventionally used colorants can be used without limitation. Examples of the colorant include pigments and dyes.
Examples of the pigment include organic pigments and / or inorganic pigments. Examples of the organic pigment include azo, phthalocyanine, anthraquinone, quinacridone, isoindoline, quinophthalone, and isoindoline pigments, and more specifically, disazo yellow or phthalocyanine blue. . Examples of inorganic pigments include titanium oxide, carbon black, calcium carbonate, barium sulfate, silica, dial, aluminum, or pearl. Examples of the dye include azo dyes, anthraquinone dyes, quinophthalone dyes, methine dyes, condensed polycyclic dyes, and reactive dyes.

(solvent)
When a solvent is used in the conventional composition, the conventional composition can be used without any particular limitation.

(Auxiliary agent)
When the conventional composition contains an adjuvant, it can be used as it is without any particular limitation. Examples of auxiliary agents include waxes, antiblocking agents, antioxidants, ultraviolet absorbers, leveling regulators, thixotropic regulators, and surfactants. Also, when a peroxide as an oxygen generator is used in combination, the conventional composition can be used without any particular limitation.

(Production method)
The production method of the oxidation polymerization composition of the present invention may be the same as the conventional method without any particular change.

"how to use"
The oxidation polymerization composition of the present invention can be used without particularly changing the conventional printing and coating methods. In addition, the drying accelerator is sometimes mixed immediately before use, but the drying accelerator of the present invention can be used in the same manner.

<Action>
Oxidative polymerization is said to be a radical reaction that begins with hydrogen abstraction from the carbon around the unsaturated bond and goes through the peroxidation state. These radicals are unstable and quickly disappear, but it is the dryer that stabilizes them and allows practical oxidative polymerization. It is said that the difference in the effect of the metal species of the fatty acid metal salt used as the dryer is caused by the difference in the electron orbit.
Improvement of drying property by addition of amine is caused by coordination of an electron donating N atom to a metal atom, and when the coordinated N atom is in a π-electron conjugated system, a further excellent effect is exhibited. This has been clarified (the effect cannot be obtained with a ligand having a structure in which the N atom cannot coordinate to the metal atom). That is, in the present invention, the ligands having the structures of the general formula (1) and the general formula (2) are superior in coordination with the metal atom as compared with the conventional ligands. When used, it is possible to improve the drying time.
In addition, by selecting ligands and metals that are highly effective and have low health hazards, even if the health hazards are not so high, the amount of addition is reduced as much as possible, and risks to health and the environment in the future. To meet market demands to minimize

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but these do not limit the scope of the present invention.

  In the following examples, the drying test method (method using a glass plate) and the drying test method (method using a C-type drying tester) were performed as follows.

<Method using glass plate>
The drying test using a glass plate was performed as follows according to JIS K5701-1-44.4.
It apply | coated to the glass plate so that the film thickness of a sample (ink) might be set to 75 micrometers. At a certain time interval, the state in which the sample was moved was examined by pressing a roll of paper for transfer onto the sample surface. The same operation was repeated at regular intervals until the ink was not transferred to the transfer paper. The time when the ink did not adhere was defined as the drying time. The temperature was 35 ° C. and the humidity was 35%.

<Method using C-type drying tester>
The drying test using a C-type drying tester was performed as follows according to JIS K5701-1-44.3.
Using the simple color developing machine described in JIS K5701-1 5.2.1b), the color developing sample is in accordance with “Developing with a simple color developing machine and a simple color developing device” in JIS K5701-1-5.3.2. Produced. Using an ink pipette, 0.05 cc of ink was developed on paper (Mitsubishi Special Art) with an RI tester. After the ink was uniformly extended on a 4-split roll, it was further dampened on the roll for 30 seconds and emulsified with water to develop a color developed sample.
The produced sample was immediately overlapped with the color paper surface of the color development sample, and wound around a rotating drum so that the paper was on the outside. The time when the tooth profile of the pressing gear hardly moved on the paper sheet was defined as the drying time.

《Creating a varnish》
The varnish having the composition of V1 shown in Table 1 was used. 44 parts by weight of rosin-modified phenolic resin (softening point 173 ° C., molecular weight 40,000, tolerance 5.0 g / g (AF5 sol / resin)), linseed oil 15 parts by weight, drill oil 10 parts by weight, petroleum solvent (AF5 sol: JX Nippon Mining) 31 parts by weight (Nisseki), 1.2 parts by weight of chelate (ALCH: manufactured by Kawaken Fine Chemical Co., Ltd.) and 0.05 parts by weight of antioxidant (BHT) were mixed to obtain a varnish. To 5 g of varnish, 0 solH (manufactured by JX Nippon Mining & Metals) was added until the varnish became cloudy, and the varnish tolerance was measured (Table 1).

<Create base ink>
The ink for the drying test was prepared with the composition shown in Table 2. 68 parts by weight of varnish, 3 parts by weight of alkyd resin (SYNKYD50: manufactured by Morimura Fine Chemical), 20 parts by weight of carbon black (M80A11: manufactured by Mitsubishi Chemical), 4 parts by weight of wax compound (MC850: manufactured by Morimura Fine Chemical), and petroleum-based solvent ( AF5sol: JX Nippon Mining & Co., Ltd. (5 parts by weight) was mixed to prepare an ink (Table 2).

Example 1
In this example, the effect of a drying accelerator using N, N, N ′, N′-tetrakis (2-pyridylmethyl) ethylenediamine (hereinafter referred to as TPEN) as a ligand was examined.
TPEN and iron acetate (metal salt) were weighed to a molar ratio of 1: 1. The mixture was dissolved in ethanol so that it might become 10 weight%, and the ethanol solution of the complex was created. When it was difficult to melt, it was heated to 40-60 ° C.
The TPEN and the ethanol solution of iron acetate were added to the ink (base black ink) as a drying accelerator, and a drying test using a glass plate and a drying test using a C-type dryer were performed. The results are shown in Table 3. The “drying accelerator concentration” shown in Table 3 indicates the weight% of a mixture of TPEN and iron acetate not containing ethanol.

Example 2
In this example, the amount of the mixture obtained from TPEN and iron acetate was examined. The procedure of Example 1 was repeated except that the addition amount of the mixture was changed from 0.1% by weight to 0.05% by weight. The results are shown in Table 3.

Example 3
In this example, the amount of the mixture obtained from TPEN and iron acetate was examined. The procedure of Example 1 was repeated except that the addition amount of the mixture was changed from 0.1% by weight to 0.03% by weight. The results are shown in Table 3.

Example 4
In this example, the amount of the mixture obtained from TPEN and iron acetate was examined. The procedure of Example 1 was repeated except that the addition amount of the mixture was changed from 0.1% by weight to 0.01% by weight. The results are shown in Table 3.

Example 5
In this example, the effect of a drying accelerator using tris (2-pyridylmethyl) amine (hereinafter referred to as TPMA) as a ligand was examined. The operation of Example 1 was repeated except that TPMA was used instead of TPEN. The results are shown in Table 3.

Example 6
In this example, the amount of the mixture obtained from TPMA and iron acetate was examined. The procedure of Example 2 was repeated except that TPMA was used instead of TPEN. The results are shown in Table 3.

Example 7
In this example, the amount of the mixture obtained from TPMA and iron acetate was examined. The procedure of Example 4 was repeated except that TPMA was used instead of TPEN. The results are shown in Table 3.

Example 8
In this example, the effect of a drying accelerator using bis (2-pyridylmethyl) amine (hereinafter referred to as BPMA) as a ligand was examined. The procedure of Example 1 was repeated except that TPMA was used in place of TPEN, and the addition amount of the mixture was changed from 0.1% by weight to 0.5% by weight. The results are shown in Table 3.

Example 9
In this example, the effect of a drying accelerator using 2,4,6-tri (2-pyridyl) -1,3,5-triazine (hereinafter referred to as TPT) as a ligand was examined. The procedure of Example 1 was repeated except that TPT was used instead of TPEN and that the addition amount of the mixture was changed from 0.1% by weight to 0.5% by weight. The results are shown in Table 3.

Example 10
In this example, the effect of a drying accelerator using 2,2′-bipyridyl (hereinafter referred to as 2bipyridyl) as a ligand was examined. The procedure of Example 1 was repeated except that 2 bipyridymil was used in place of TPEN, and the addition amount of the mixture was changed from 0.1% by weight to 0.5% by weight. The results are shown in Table 3.

<< Reference Example 1 >>
In this example, the ligand represented by the formula (13):
The effect of a drying accelerator using α, α ′, α ″ -tripyridyl (hereinafter referred to as “αtripyridyl”) represented by the following formula was examined. ΑTripyridyl was used in place of TPEN, and the amount of mixture added was 0. The procedure of Example 1 was repeated except that 1 wt% was changed to 0.5 wt%, and the results are shown in Table 3.
Note that α, α ′, α ″ -tripyridyl has a crossbone mark of UN GHS classification, and is therefore described as a reference example in the present specification.

<< Reference Example 2 >>
In this reference example, the ligand is represented by the formula (14):
The effect of a drying accelerator using 1,10-phenanthroline represented by the following (hereinafter referred to as FHEN) was examined. The procedure of Example 1 was repeated except that FHEN was used in place of TPEN and that the addition amount of the mixture was changed from 0.1% by weight to 0.5% by weight. The results are shown in Table 3.
In addition, 1,10-phenanthroline has a crossbone mark of the UN GHS classification, and is therefore described as a reference example in this specification.

<< Reference Example 3 >>
In this example, the ligand represented by the formula (15):
The effect of a drying accelerator using 4,7-diphenyl-1,10-phenanthroline (hereinafter referred to as DF) represented by The procedure of Example 1 was repeated except that DF was used in place of TPEN and the addition amount of the mixture was changed from 0.1% by weight to 0.5% by weight. The results are shown in Table 3.

<< Reference Example 4 >>
In this example, formula (16):
The effect of a drying accelerator using 2,2′-bipyridyl (hereinafter referred to as 2bipyridyl) represented by The procedure of Example 1 was repeated except that 2 bipyridyl was used in place of TPEN, and the addition amount of the mixture was changed to 0.1% by weight. The results are shown in Table 3.
In addition, 2,2′-bipyridymil has a crossbone mark of UN GHS classification, and is therefore described as a reference example in this specification.

Example 11
In this example, the effect of a drying accelerator using 5,5′-dimethyl-2,2′-dipyridyl (hereinafter referred to as DP) as a ligand was examined. The procedure of Example 1 was repeated except that DP was used in place of TPEN, and the addition amount of the mixture was changed from 0.1% by weight to 0.5% by weight. The results are shown in Table 3.

<< Comparative Example 1 >>
In this comparative example, the ligand is represented by the formula (17):
The effect of a drying accelerator using 4,4′-bipyridyl (hereinafter referred to as 4 bipyridyl) represented by The operation of Example 1 was repeated except that 4 bipyridyl was used in place of TPEN and the addition amount of the mixture was changed from 0.1 wt% to 0.5 wt%. The results are shown in Table 3.
In addition, 4,4'-bipyridyl has a crossbone mark of UN GHS classification.

<< Reference Example 5 >>
In this example, the ligand represented by the formula (18):
The effect of a drying accelerator using 2,2′-bipiperidine (hereinafter referred to as 2 bipiperidine) represented by The procedure of Example 1 was repeated except that 2 bipiperidine was used in place of TPEN and the addition amount of the mixture was changed from 0.1% by weight to 0.5% by weight. The results are shown in Table 3.

<< Comparative Example 2 >>
In this comparative example, as the ligand, the formula (19):
The effect of a drying accelerator using 4,4′-bipiperidine (hereinafter referred to as 4 bipiperidine) represented by The procedure of Example 1 was repeated except that 4 bipiperidine was used in place of TPEN, and the addition amount of the mixture was changed from 0.1% by weight to 0.5% by weight. The results are shown in Table 3.

Example 12
In this example, the effect of a drying accelerator using TPEN as a ligand and iron chloride as a metal salt was examined. The procedure of Example 1 was repeated except that iron chloride was used instead of iron acetate. The results are shown in Table 3.

Example 13
In this example, the effect of a drying accelerator using iron octylate as a metal salt was examined. The procedure of Example 1 was repeated except that iron octylate was used instead of iron acetate. The results are shown in Table 3.

<< Reference Example 6 >>
In this example, the ligand represented by the formula (20):
The effect of a drying accelerator using triethylenetetramine (hereinafter referred to as TAT) represented by The procedure of Example 1 was repeated except that TAT was used instead of TPEN, and the addition amount of the mixture was changed from 0.1% by weight to 0.7% by weight. The results are shown in Table 3.
Triethylenetetramine has a crossbone mark of the UN GHS classification.

Example 14
In this example, the procedure of Example 11 was repeated except that the molar ratio of DP to iron acetate was 2: 1. The results are shown in Table 3.

Example 15
In this example, the procedure of Example 11 was repeated except that the molar ratio of DP to iron acetate was 3: 1. The results are shown in Table 3.

Example 16
In this example, the procedure of Example 1 was repeated except that the molar ratio of TPEN to iron acetate was 1: 2. The results are shown in Table 3.

Example 17
In this example, the procedure of Example 1 was repeated except that the molar ratio of TPEN to iron acetate was 1: 3. The results are shown in Table 3.

Example 18
In this example, the procedure of Example 1 was repeated except that the molar ratio of TPEN to iron acetate was 1: 5. The results are shown in Table 3.

<< Comparative Example 3 >>
In this example, the effect of a drying accelerator using TPEN when no transition metal was added was examined. The procedure of Example 1 was repeated except that no iron acetate was added. The results are shown in Table 3.

<< Comparative Example 4 >>
In this example, the effect of a drying accelerator using DP when no transition metal was added was examined. The procedure of Example 11 was repeated except that no iron acetate was added. The results are shown in Table 3.

<< Comparative Example 5 >>
In this comparative example, the effect of using iron acetate without a ligand as a drying accelerator was examined. The procedure of Example 1 was repeated except that 0.5% by weight of iron acetate was used instead of the mixture of ligand and transition metal iron. The results are shown in Table 3.

<< Comparative Example 6 >>
In this comparative example, the effect as a drying accelerator of cobalt naphthenate conventionally used as a drying accelerator was examined. The procedure of Example 1 was repeated except that 0.2 wt% cobalt naphthenate was used in place of the mixture of ligand and transition metal iron. The results are shown in Table 3.

<< Comparative Example 7 >>
The operation of Comparative Example 6 was repeated, except that the amount of cobalt naphthenate added was changed to 0.1% by weight instead of 0.2% by weight. The results are shown in Table 3.

<< Comparative Example 8 >>
In this comparative example, the effect of manganese naphthenate, which has been conventionally used as a drying accelerator, as a drying accelerator was examined. The procedure of Example 1 was repeated except that 0.6% by weight of manganese naphthenate was used in place of the mixture of ligand and transition metal iron. The results are shown in Table 3.

<< Comparative Example 9 >>
The operation of Comparative Example 8 was repeated except that the addition amount of cobalt naphthenate was changed to 0.3% by weight instead of 0.6% by weight. The results are shown in Table 3.

Example 19
In this example, a case where no drill oil was used as a drying oil for varnish was examined. The procedure of Example 1 was repeated except that varnish (Table 1) of linseed oil 25% by weight was used in place of linseed oil 15% by weight and gill oil 10% by weight. The results are shown in Table 3.

<< Comparative Example 10 >>
In this comparative example, the effect of using the varnish of Example 15 and using iron acetate without a ligand as a drying accelerator was examined. The procedure of Example 19 was repeated except that 0.5% by weight of iron acetate was used instead of the mixture of ligand and transition metal iron. The results are shown in Table 3.

<< Comparative Example 11 >>
In this comparative example, the effect as a drying accelerator of cobalt naphthenate, which was conventionally used as a drying accelerator, was examined using the varnish of Example 15. The procedure of Example 19 was repeated except that 0.5% by weight of cobalt naphthenate was used in place of the mixture of ligand and transition metal iron. The results are shown in Table 3.

<< Comparative Example 12 >>
In this comparative example, the effect as a drying accelerator of manganese naphthenate, which has been conventionally used as a drying accelerator, was examined using the varnish of Example 15. The procedure of Example 19 was repeated except that 0.6% by weight of manganese naphthenate was used in place of the mixture of ligand and transition metal iron. The results are shown in Table 3.

TPEN (A): N, N, N ′, N′-tetrakis (2-pyridylmethyl) ethylenediamine,
TPMA (B): Tris (2-pyridylmethyl) amine BPMA (C): Bis (2-pyridylmethyl) amine TPT (D): 2,4,6-tri (2-pyridyl) -1,3,5- Triazine DP (E): 5,5′-dimethyl-2,2′-dipyridyl 2-bipyridyl (F): 2,2′-bipyridylyl αtripyridyl (G): α, α ′, α ″ -tripyridyl FHEN (H) : 1,10-phenanthroline DF (I): 4,7-diphenyl-1,10-phenanthroline 2 bipyridyl (J): 2,2′-bipyridyl 4 bipyridyl (K): 4,4′-bipyridyl 2 bipiperidine (L) ): 2,2′-bipiperidine 4 bipiperidine (M): 4,4′-bipiperidine TAT (N): triethylenetetramine

Inks using the drying accelerators of Examples 1 to 18 were compared with the ink using only iron acetate of Comparative Example 3 in the drying test using a glass plate and the drying test using a C-type dryer. In both tests, the drying time was shortened.
Moreover, compared with the cobalt naphthenate of Comparative Examples 6-9 and the manganese naphthenate which are conventional dryers, it was a drying time comparable.
Furthermore, in offset printing using fountain solution, it is important that the drying time on paper after emulsification by the C-type dryer does not become extremely slow compared to the glass plate drying time, as a measure of drying delay trouble due to emulsification during printing. is there. From this viewpoint, it is considered that many of the drying accelerators of the present invention are superior to conventional cobalt naphthenate and manganese naphthenate.
In addition, the drying accelerator of the present invention also showed an excellent drying time as compared with cobalt naphthenate and manganese naphthenate when a varnish containing no drill oil was used (Example 19). In general, when a dry oil is not included as a drying oil, the drying time tends to be long. From this point, the drying accelerator of the present invention has a remarkable effect.
In addition, it has been confirmed that there is no problem in storage stability after the addition of the accelerator of the present invention, and that offset printing using a fountain solution is performed, so that the problem of scumming or excessive emulsification is not exceeded.
By using the drying accelerator of the present invention at a minimum, it is possible to meet market demands to reduce health and environmental risks as much as possible.

  Table 4 shows the relationship between the compounds (ligands) used in Examples, Comparative Examples, and Reference Examples and the UN GHS classification mark (excluding physicochemical hazard marks) regarding health and environmental hazards. . As the ligand used in the present invention, an exclamation mark mark or an unmarked ligand is selected. Moreover, it is desirable to reduce the compounding quantity of a complex as much as possible in the range of a required drying time from a viewpoint of reduction to addition to an environment, and safety | security.

  The transition metal complex and the drying accelerator of the present invention can be used by replacing with an oxidatively polymerizable composition, such as an ink or paint, which has used a conventional fatty acid metal salt dryer, without any particular limitation.

Claims (4)

At least one transition metal selected from the group consisting of iron, cerium, and zirconium, or a salt thereof; and general formula (1):
A ligand represented by the formula (excluding 2,2′-pipyridyl) or general formula (2):
A ligand composition or a transition metal complex containing a ligand represented by:
In the general formula (1) and the general formula (2),
R ¹ is
(I) a single bond,
(Ii) Formula (3):
(In Formula (3), X is a single bond or a C1-C4 alkylene group,
R ⁵ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a group containing one or more pyridyl groups that may be optionally substituted with an alkyl group having 1 to 4 carbon atoms or a methoxy group. A group represented by: or (iii) Formula (4):
(In Formula (4), R ⁶ is one or more pyridyl groups optionally substituted with a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms or a methoxy group. Is a group represented by
R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or an aryl group;
Each R ⁴ is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group or an aryl group;
A drying accelerator comprising the ligand composition or the metal complex. The group containing one or more pyridyl groups is a pyridyl group or formula (5):
The drying accelerator of Claim 1 which is group represented by these.   The ligand is N, N, N ′, N′-tetrakis (2-pyridylmethyl) ethylenediamine, tris (2-pyridylmethyl) amine, bis (2-pyridylmethyl) amine, 2,4,6-tri A ligand selected from the group consisting of (2-pyridyl) -1,3,5-triazine, 5,5'-dimethyl-2,2'-dipyridyl, and 2,2'-bipyridymil. The drying accelerator according to 1 or 2.   The oxidatively polymerizable composition containing the varnish containing resin or drying oil, and the drying accelerator as described in any one of Claims 1-3.