JP2014025029A - Stabilizer for a polyether sulfone resin, polyether sulfone resin composition including the stabilizer, and resin member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a stabilizer capable of improving the optical stability of a polyether sulfone resin and of yielding a transparent polyether sulfone resin, a polyether sulfone resin composition including the stabilizer, and a resin member obtained from the resin composition.SOLUTION: A stabilizer for a polyether sulfone resin expressed by the formula (1), a polyether sulfone resin composition including the stabilizer, and a resin member obtained from the resin composition are provided.

Description

  The present invention provides a polyethersulfone resin stabilizer represented by formula (1), and a polyethersulfone resin composition containing at least one of the stabilizers and at least one polyethersulfone resin, And a resin member obtained from the resin composition.

  Polyethersulfone resin is an amorphous and transparent resin, and has characteristics such as excellent hydrolysis resistance, chemical resistance, thermal decomposition resistance, mechanical strength, flame resistance, and environmental stress cracking resistance. In particular, polyethersulfone resins have superior hydrolysis resistance and mechanical strength compared to general-purpose engineering plastics, and are excellent in thermal deformation characteristics under high-temperature environments, so electrical / electronic parts, automotive parts, and medical equipment. It is used in various fields such as food containers.

  However, it is known that the polyethersulfone resin causes deterioration such as change in physical properties and appearance change (coloring) over time due to ultraviolet rays. In general, general-purpose resins such as polypropylene, acrylic resin, and polycarbonate are organic UV absorbers or deterioration inhibitors (salicylic acid compounds, benzophenone compounds, cyanoacrylate compounds, benzotriazole compounds) against UV degradation. Compound) or a light stabilizer (hindered amine compound) has been added. However, for example, a film of a polyethersulfone resin is molded by melt extrusion using a T die or a coat hanger die under a high temperature condition such as 300 ° C. to 380 ° C. And light stabilizers have a low heat decomposability, and there is a problem that the function as a stabilizer is lowered by thermal decomposition. In addition, a method of applying a coating film to which an organic ultraviolet absorber or light stabilizer is added to the film is also conceivable. However, the number of processes increases and the transmittance decreases due to the coating film. It was an undesirable method.

For example, Patent Document 1 discloses that an inorganic ultraviolet absorber such as silica-CeO ₂ is added in order to avoid deterioration of the polyethersulfone resin due to ultraviolet rays. However, the inorganic ultraviolet absorber needs to have a particle size of, for example, 100 nm or less in order to maintain transparency in the visible region. However, if the particle size is small, generally the surface energy of the particles becomes high, the particles tend to aggregate, and the aggregates cause light scattering in the visible range, and the transparency of the polyethersulfone resin is low. There was a problem that was spoiled.

Japanese Patent Laid-Open No. 9-52964

  The present invention seeks to solve the problems associated with the prior art as described above. That is, light stability such as photodegradation resistance and light discoloration resistance can be improved with respect to the polyethersulfone resin, and the effect of improving the stability is expressed by addition of a small amount, and a transparent polyethersulfone resin composition is obtained. And a stabilizer for a polyethersulfone resin having excellent thermal decomposition resistance that does not decompose even at the molding temperature of the polyethersulfone resin, a polyethersulfone resin composition containing the stabilizer, and the resin composition It aims at providing the resin member obtained from a thing.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the metal complex represented by the formula (1) has a high heat decomposability and is extremely excellent in light stability with respect to the polyethersulfone resin. It has been found that it has an effect. Then, the said subject was led to the solution by using this metal complex as a stabilizer for polyether sulfone resins, and it came to the completion of this invention. That is, the present invention provides a polyethersulfone resin stabilizer as shown below, a polyethersulfone resin composition containing at least one of the stabilizers for the polyethersulfone resin, and the resin composition. The present invention relates to a resin member.

  Item 1. Formula (1):

Wherein Y ¹ , Y ² , Y ³ and Y ⁴ are each independently NH, NR ⁵ , an oxygen atom or a sulfur atom; belonging to Y ¹ , Y ² , Y ³ or Y ⁴ R ⁵ of NR ⁵ is an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 15 carbon atoms which may have a substituent; and among Y ¹ , Y ² , Y ³ and Y ⁴ When at least two are represented by NR ⁵ , each R ⁵ of NR ⁵ represents a substituent independent of each other;
Z ¹ and Z ² are each independently a nitrogen atom, CH or CR ⁶ ; R ⁶ of CR ⁶ attributed to Z ¹ or Z ² may have 1 substituent. An alkyl group having ˜8, an aryl group having 6 to 15 carbon atoms which may have a substituent, a heteroaryl group having 4 to 12 carbon atoms which may have a substituent, and a substituent. also represent an heteroaralkyl group or an aralkyl group having 7 to 15 carbon atoms having a carbon number of 5 to 12; in the case ^{where Z 1} and ^{Z 2} are both represented by CR ^6, independently each ^{R 6} of CR ⁶ are mutually The substituted substituents;
Each of R ¹ , R ² , R ³ and R ⁴ may be absent or present; each of the groups present among R ¹ , R ² , R ³ and R ⁴ is Any one to four of the four hydrogen atoms bonded to the four carbon atoms of the benzene ring to which the group can be bonded can be substituted; all R ¹ , R ² , R ³ and R ⁴ each independently has an optionally substituted alkyl group having 1 to 8 carbon atoms, a hydroxyl group, a carboxyl group, an alkoxy group having 1 to 4 carbon atoms, a halogeno group, and a substituent. An optionally substituted alkylaminosulfonyl group having 1 to 16 carbon atoms, a morpholinosulfonyl group which may have a substituent, a piperidinosulfonyl group which may have a substituent, and a substituent; Good pyrrolidinosulfonyl group, substituted Good thiomorpholinyl have a morpholino sulfonyl is a group or an optionally substituted piperazino sulfonyl group;
M represents a metal atom)
A stabilizer for a polyethersulfone resin represented by:

  Item 2. Item 2. The stabilizer for a polyethersulfone resin according to item 1, wherein the metal atom M in the formula (1) is a cobalt atom, a nickel atom or a copper atom.

  Item 3. 3. A polyethersulfone resin composition comprising at least one kind of the stabilizer for polyethersulfone resins according to item 1 or 2, and at least one polyethersulfone resin.

Item 4. Item 4. The polyethersulfone resin composition according to Item 3, wherein the polyethersulfone resin is a polyethersulfone resin composed of a repeating unit represented by the following formula (2).

  Item 5. Item 5. A resin member obtained from the polyethersulfone resin composition according to Item 3 or 4.

  The stabilizer for polyethersulfone resin of the present invention has an effect of improving light stability such as photodegradation resistance and light discoloration resistance over a long period of time with a small amount of addition to the polyethersulfone resin. Further, since the stabilizer is dissolved in the polyethersulfone resin, it has high transparency, and since it does not decompose even at the molding temperature of the polyethersulfone resin, it has high thermal decomposition resistance. Therefore, by using the stabilizer for polyethersulfone resin of the present invention, it is possible to provide a transparent and discolored polyethersulfone resin composition that can maintain excellent light stability over a long period of time. Can do.

Hereinafter, the present invention will be described in detail.
The present invention relates to a stabilizer for a polyethersulfone resin represented by the formula (1), a polyethersulfone resin composition containing at least one of the stabilizers, and a resin member obtained from the composition Is to provide.

In formula (1), Y ¹ , Y ² , Y ³ and Y ⁴ are each independently NH, NR ⁵ , an oxygen atom or a sulfur atom.

Examples of R ⁵ of the above NR ⁵ attributed to Y ¹ , Y ² , Y ³ or Y ⁴ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl. Group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, n-heptyl group, n-octyl group, etc. 8 alkyl groups; carbon number such as phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 3-chlorophenyl group, 4-bromophenyl group, 3,4-dichlorophenyl group, naphthyl group, etc. Examples include 6 to 15 aryl groups.

The alkyl group and aryl group as R ⁵ may have a substituent as in the above specific examples. When the alkyl group and the aryl group have a substituent, the carbon number of the alkyl group and the aryl group is the number of carbons of the group not including the substituent.
^{Incidentally, Y 1, Y 2, Y} 3, when ^Y least two of the ^four is represented by NR ^5, the ^{R 5} of NR ⁵ represent a substituent independent of each other, respectively.

Here, Y ¹ , Y ² , Y ³ and Y ⁴ in Formula (1) are particularly preferably an oxygen atom or a sulfur atom from the viewpoint of simplicity of the synthesis method.

Z ¹ and Z ² are each independently a nitrogen atom, CH or CR ⁶ .

Examples of R ⁶ of CR ⁶ attributed to Z ¹ or Z ² include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert. An alkyl group having 1 to 8 carbon atoms such as -butyl group, n-pentyl group, isopentyl group, neopentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, n-heptyl group, n-octyl group; Aryl groups having 6 to 15 carbon atoms such as 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 3-chlorophenyl group, 4-bromophenyl group, 3,4-dichlorophenyl group and naphthyl group 2-furyl group, 2-thienyl group, 5-chloro-2-thienyl group, 2-pyrrolyl group, 2-oxazolyl group, 5-methyl-2-oxyl; A heteroaryl group having 3 to 12 carbon atoms such as a sazolyl group and a 2-thiazolyl group; a heteroaralkyl group having 4 to 12 carbon atoms such as a 4-pyridylmethyl group, a 4-quinolylmethyl group and a 2-thienylmethyl group; Benzyl group, 3-aminobenzyl group, 4-aminobenzyl group, 3-methoxybenzyl group, 2-methoxyphenethyl group, 4- (n-pentyloxy) benzyl group, 2-allyloxyphenethyl group, 5-allyl-2 -Hydroxy-3-methoxybenzyl group, 4-phenylbenzyl group, 2-bromobenzyl group, 3-phenethyl group, 4-bromobenzyl group, 2-chlorobenzyl group, 3-chlorobenzyl group, 4-chlorobenzyl group, 6-bromo-2-hydroxybenzyl group, 5-bromo-3-nitro-2-hydroxyphenethyl group, 4- (n-butyl) L) benzyl group, 3-bromo-5-methoxy-4-hydroxybenzyl group, 4-benzyloxybenzyl group, 6-bromo-3-methoxy-2-hydroxybenzyl group, (1-bromo-2-naphthyl)- n-propyl group, 2-benzyloxybenzyl group, 3,5-bistrifluoromethylphenethyl group, 4-tert-butylbenzyl group, 5-bromo-2-fluorobenzyl group, 3-bromo-4-methoxybenzyl group, 5-bromo-2-methoxybenzyl group, 3-bromo-5-chloro-2-hydroxybenzyl group, 4-bromo-2-fluorobenzyl group, 2-bromo-4,5-dimethoxyphenethyl group, 3,4- Ethylenedioxybenzyl group, 3-bromo-4-fluorophenethyl group, 6-bromo-3,4-methylenedioxybenzyl group, 3-bromide -4-hydroxybenzyl group, 2-bromo-5-fluorophenethyl group, 4-cyanobenzyl group, 4-trifluorobenzyl group, 4- (4-chlorophenoxy) phenethyl group, 4- (N, N-diethylamino) Benzyl group, 3,4-diacetoxybenzyl group, 4- (N, N-diphenylamino) benzyl group, 4- [N- (4,4-dioxothiomorpholino)] benzyl group, 4- (N-pyrrolidino ) Benzyl group, 3- (2-hydroxyethoxy) benzyl group, 4- (2-hydroxyethoxy) phenethyl group, 4-hydroxy-3,5-dimethylbenzyl group, (6-hydroxy-2-naphthyl) -n- Examples thereof include aralkyl groups having 7 to 15 carbon atoms such as propyl group, 4-isopropylbenzyl group and 4-isobutylbenzyl group.

The alkyl group, aryl group, heteroaryl group, heteroaralkyl group and aralkyl group as R ⁶ may have a substituent as in the above specific examples. When these groups have a substituent, the carbon number of the group is the carbon number of a group that does not include a substituent.

Among those exemplified as R ⁶ of CR ⁶ attributed to Z ¹ or Z ² , an aralkyl group is particularly preferable from the viewpoint of simplicity of the synthesis method and reactivity.
Incidentally, a substituent case, ^{R 6} of CR ⁶ is that each independently of one another ^{that Z 1} and ^{Z 2} are both represented by CR ^6.

Furthermore, Z ¹ and Z ² in Formula (1) are particularly preferably nitrogen atoms from the viewpoint of simplicity of the synthesis method.

Each of R ¹ , R ² , R ³ and R ⁴ may not be present or may be present. Each of the groups present among R ¹ , R ² , R ³ and R ⁴ is any one to four of the four hydrogen atoms bonded to the four carbon atoms of the benzene ring to which the group may be bonded. , Preferably 1 or 2 can be substituted. All R ¹ , R ² , R ³ and R ^{4 present} are each independently of each other an optionally substituted alkyl group having 1 to 8 carbon atoms, hydroxyl group, carboxyl group, 1 to carbon atoms. 4 an alkoxy group, a halogeno group, an alkylaminosulfonyl group having 1 to 16 carbon atoms which may have a substituent, a morpholinosulfonyl group which may have a substituent, and a substituent. A piperidinosulfonyl group, an optionally substituted pyrrolidinosulfonyl group, an optionally substituted thiomorpholinosulfonyl group or an optionally substituted piperazinosulfonyl group. .

Examples of the alkyl group having 1 to 8 carbon atoms which may have the above-described substituents belonging to R ¹ , R ² , R ³ or R ⁴ include a methyl group, an ethyl group, and 2-methoxyethyl. Group, n-propyl group, isopropyl group, 3-chloro-n-propyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, 4-hydroxy-n-butyl group, n-pentyl group , Isopentyl group, neopentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, 6-phenyl-n-hexyl group, n-heptyl group, n-octyl group and the like. When the alkyl group has a substituent, the carbon number of the alkyl group is the carbon number of the alkyl group not including the substituent. The preferable carbon number of the alkyl group is 1 to 3. The substituent that the alkyl group may have is an alkoxy group having 1 to 3 carbon atoms such as a methoxy group, an ethoxy group, or an n-propoxy group; a halogeno group such as a chloro group, a bromo group, or a fluoro group; a hydroxyl group; Group, an aryl group having 6 to 12 carbon atoms such as a naphthyl group, and the like.

R ^1, attributed to ^R 2, ^{R 3} or ^{R 4,} the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, tert- butoxy group and the like.

Examples of the halogeno group belonging to R ¹ , R ² , R ³ or R ⁴ include a fluoro group, a chloro group, a bromo group, and an iodo group.

Examples of the alkylaminosulfonyl group having 1 to 16 carbon atoms which may have the above-described substituents belonging to R ¹ , R ² , R ³ or R ⁴ include, for example, an N-methylaminosulfonyl group, N -Ethylaminosulfonyl group, N-isopropylaminosulfonyl group, Nn-propylaminosulfonyl group, Nn-butylaminosulfonyl group, N, N-dimethylaminosulfonyl group, N, N-methylethylaminosulfonyl group, N, N-diethylaminosulfonyl group, N, N-ethylisopropylaminosulfonyl group, N, N-diisopropylaminosulfonyl group, N, N-di-n-propylaminosulfonyl group, N, N-di-n-butylamino Sulfonyl group, N, N-diisobutylaminosulfonyl group, N, N-di-2-ethylhexylaminosulfur Group and the like. The carbon number of the alkylaminosulfonyl group is the number of carbon atoms of the alkylaminosulfonyl group not containing a substituent when the group has a substituent. The alkylaminosulfonyl group preferably has 2 to 16 carbon atoms. Examples of the substituent that the alkylaminosulfonyl group may have are the same as the substituents that the alkyl group may have.

Examples of the morpholinosulfonyl group optionally having a substituent belonging to R ¹ , R ² , R ³ or R ⁴ include a morpholinosulfonyl group, a 2-methylmorpholinosulfonyl group, and a 3-methylmorpholinosulfonyl group. 2-ethylmorpholinosulfonyl group, 3-n-propylmorpholinosulfonyl group, 3-n-butylmorpholinosulfonyl group, 2,3-dimethylmorpholinosulfonyl group, 2,6-dimethylmorpholinosulfonyl group, 3-phenylmorpholinosulfonyl group Etc. The morpholinosulfonyl group may have a substituent having 1 to 5 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an isobutyl group, and an n-pentyl group. An aryl group having 6 to 12 carbon atoms such as a phenyl group and a naphthyl group.

Examples of the piperidinosulfonyl group optionally having a substituent belonging to R ¹ , R ² , R ³ or R ⁴ include a piperidinosulfonyl group, a 2-methylpiperidinosulfonyl group, 3-methylpiperidinosulfonyl group, 4-methylpiperidinosulfonyl group, 2-ethylpiperidinosulfonyl group, 4-n-propylpiperidinosulfonyl group, 3-n-butylpiperidinosulfonyl group, 2 , 4-dimethylpiperidinosulfonyl group, 2,6-dimethylpiperidinosulfonyl group, 4-phenylpiperidinosulfonyl group and the like. Examples of the substituent that the piperidinosulfonyl group may have are the same as the substituents that the morpholinosulfonyl group may have.

Examples of the pyrrolidinosulfonyl group optionally having a substituent belonging to R ¹ , R ² , R ³ or R ⁴ include a pyrrolidinosulfonyl group, a 2-methylpyrrolidinosulfonyl group, and 3-methyl. Pyrrolidinosulfonyl group, 2-ethylpyrrolidinosulfonyl group, 3-n-propylpyrrolidinosulfonyl group, 3-n-butylpyrrolidinosulfonyl group, 2,4-dimethylpyrrolidinosulfonyl group, 2,5-dimethylpyrrolidino A sulfonyl group, 3-phenylpyrrolidinosulfonyl group, etc. are mentioned. Examples of the substituent that the pyrrolidinosulfonyl group may have are the same as the substituents that the morpholinosulfonyl group may have.

Examples of the thiomorpholinosulfonyl group optionally having a substituent, which is assigned to R ¹ , R ² , R ³ or R ⁴ , include a thiomorpholinosulfonyl group, a 2-methylthiomorpholinosulfonyl group, 3- Methylthiomorpholinosulfonyl group, 2-ethylthiomorpholinosulfonyl group, 3-n-propylthiomorpholinosulfonyl group, 3-n-butylthiomorpholinosulfonyl group, 2,3-dimethylthiomorpholinosulfonyl group, 2,6-dimethylthiomorpholino A sulfonyl group, 3-phenylthiomorpholinosulfonyl group, etc. are mentioned. Examples of the substituent that the thiomorpholinosulfonyl group may have are the same as the substituents that the morpholinosulfonyl group may have.

Examples of the piperazinosulfonyl group optionally having a substituent belonging to R ¹ , R ² , R ³ or R ⁴ include a piperazinosulfonyl group, a 2-methylpiperazinosulfonyl group, 3-methylpiperazinosulfonyl group, 2-ethylpiperazinosulfonyl group, 3-n-propylpiperazinosulfonyl group, 3-n-butylpiperazinosulfonyl group, 2,5-dimethylpiperazinosulfonyl group 2,6-dimethylpiperazinosulfonyl group, 3-phenylpiperazinosulfonyl group, 2-pyrimidylpiperazinosulfonyl group and the like. Examples of the substituent that the piperazinosulfonyl group may have include a substituent that the morpholinosulfonyl group may have and a heteroaryl group having 4 to 12 carbon atoms such as a pyrimidyl group.

From the viewpoint of economy, that is, the availability of raw materials, the number of reaction steps, and the yield, R ¹ , R ² , R ³ and R ⁴ are each independently independent of each other or have a substituent. It is preferably an alkyl group having 1 to 8 carbon atoms, a halogeno group, or an alkoxy group having 1 to 4 carbon atoms, and may be absent, a halogeno group, or an alkoxy group having 1 to 4 carbon atoms. It is more preferable that it is not present.

R ¹ , R ² , R ³ and R ⁴ are each independently of each other an optionally substituted alkylaminosulfonyl group having 1 to 16 carbon atoms, an optionally substituted morpholinosulfonyl group, A piperidinosulfonyl group which may have a substituent, a pyrrolidinosulfonyl group which may have a substituent, a thiomorpholinosulfonyl group which may have a substituent or a substituent; The piperazinosulfonyl group is particularly advantageous in terms of solubility in a solvent, and among them, an alkylaminosulfonyl group having 1 to 16 carbon atoms which may have a substituent or a substituent. It is particularly advantageous when it is a morpholinosulfonyl group which may be present.

Y ¹ , Y ² , Y ³ and Y ⁴ , Z ¹ and Z ² , R ¹ , R ² , R ³ and R ⁴ are independent of each other, but the synthesis method is simple and the metal complex to be obtained From the viewpoint of quality (purity) control, it is preferable that Y ¹ = Y ² and Y ³ = Y ⁴ and Z ¹ = Z ² and R ¹ = R ² = R ³ = R ⁴ . From the viewpoint of solubility of the metal complex in various solvents, Y ¹ = Y ³ ≠ Y ² = Y ⁴ and Z ¹ = Z ² and R ¹ = R ³ = R ² = R ⁴ , or Y ¹ It is preferred that Y = Y ³ = Y ² = Y ⁴ and Z ¹ = Z ² and R ¹ = R ³ ≠ R ² = R ⁴ .

  Examples of the metal atom represented by M include a cobalt atom, a nickel atom, a zinc atom, and a copper atom. Among these, a cobalt atom, a nickel atom, and a copper atom are preferable from the viewpoint of thermal decomposition resistance, and a cobalt atom is more preferable.

Among the metal complexes as stabilizers for the polyethersulfone resin represented by the above formula (1), preferred specific examples are shown below;
In formula (1), Y ¹ , Y ² , Y ³ and Y ⁴ are each independently an oxygen atom or a sulfur atom;
Z ¹ and Z ² are each independently a nitrogen atom;
Each of R ¹ , R ² , R ³ and R ⁴ may be absent or present; each of the groups present among R ¹ , R ² , R ³ and R ⁴ is Any one to four of the four hydrogen atoms bonded to the four carbon atoms of the benzene ring to which the group can be bonded can be substituted; all R ¹ , R ² , R ³ and R ^{4 s} independently of each other may have a substituent, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogeno group, or an optionally substituted carbon number. 1 to 16 alkylaminosulfonyl groups, or an optionally substituted morpholinosulfonyl group;
M represents a cobalt atom, a nickel atom, or a copper atom.

  The metal complex represented by the formula (1) is obtained by reacting a ligand represented by the following formula (2) with a metal salt such as a metal halide, metal sulfate, metal acetate, or metal nitrate. Can be synthesized.

  Formula (2):

In the formula (2), Y ¹ , Y ² , Z ¹ , R ¹ , R ² are Y ¹ (and / or Y ³ ), Y ² (and / or Y ⁴ ), Z in the formula (1), respectively. ¹ (and / or Z ² ), R ¹ (and / or R ³ ), R ² (and / or R ⁴ ).

Examples of the ligand represented by the formula (2) include “JP-A-56-87575”, “Synthesis 1987, 368”, “Synthesis 1982, 590”, “Synthesis 1982, 1066-1067”, “J. Org. Chem. 2002, 67, 5753-5772 "," J. Org. Chem. 2002, 67, 5753-5772 "," J. Org. Chem. 1961, 26, 3434-3445 "," Gazz.Chim. Ital. 1996, 126, 329-337 ”,“ Gazz. Chim. Ital. 1994, 124, 301-308 ”, and“ Special Table 2007-535421 ”.
Hereinafter, a part of manufacturing method of the ligand represented by Formula (2) is demonstrated.

≪Ligand production method≫
I) In the following formula (3): in the formula (2), Y ¹ = Y ² = S, Z ¹ = N

For example, it can be synthesized according to the method described in JP-A-56-87575. That is, 2-aminobenzothiazole (when R ¹ and R ² are not present) or 2-amino-substituted benzothiazole (R ¹ and R ² may have a substituent alkyl group having 1 to 8 carbon atoms) , A hydroxyl group, a carboxyl group, an alkoxy group having 1 to 4 carbon atoms or a halogeno group) in the presence of an acid catalyst such as phenol, the mixture is heated to 150 to 185 [deg.] C. and reacted to produce 2,2'-iminobis Benzothiazole or 2,2′-iminobis (substituted benzothiazole) can be synthesized.

II) When the following formula (4): Y ¹ = S, Y ² = O, Z ¹ = N in the formula (2)

For example, it can be synthesized according to the method described in Synthesis 1987,368. That is, 2-aminophenol (when R ² is not present) or 2-amino-substituted phenol (wherein R ² may have a substituent, an alkyl group having 1 to 8 carbon atoms, a hydroxyl group, a carboxyl group, carbon (In the case of an alkoxy group or halogeno group of formulas 1 to 4) is dissolved in N, N′-dimethylformamide (DMF), an aqueous sodium hydroxide solution is added as a base, and the mixture is stirred at room temperature for 30 minutes, where S, S ′ - dimethyl-N-(2-benzothiazolyl) - carboxylic imide phosphorodithioate (when ^{R 1} is absent) or S, S'-dimethyl-N-[2-(substituted benzothiazolyl)] - carboxylic imide phosphorodithioate ^{(wherein R 1} is An optionally substituted alkyl group having 1 to 8 carbon atoms, hydroxyl group, carboxyl group, alkoxy group having 1 to 4 carbon atoms or halogeno 2- (2-benzothiazolylamino) benzoxazole or 2- [2- (substituted benzothiazolyl) amino] -substituted benzoxazole is synthesized by dropping a DMF solution in the case of a group) and refluxing in a nitrogen atmosphere. be able to.

  Said S, S′-dimethyl-N- (2-benzothiazolyl) carbonimidodithioate or S, S′-dimethyl-N- [2- (substituted benzothiazolyl)] carbonimidodithioate is described, for example, in Synthesis 1982,590. Can be synthesized according to the methods described.

That is, 2-aminobenzothiazole (when R ¹ is not present) or 2-amino-substituted benzothiazole (wherein R ¹ may have a substituent, an alkyl group having 1 to 8 carbon atoms, a hydroxyl group, a carboxyl group) In the case of an alkoxy group having 1 to 4 carbon atoms or a halogeno group), an aqueous sodium hydroxide solution is added dropwise to this solution in a water bath or ice bath, carbon disulfide is then added dropwise, and water is added. An aqueous sodium oxide solution is added dropwise, and then methyl iodide is added dropwise to form S, S′-dimethyl-N- (2-benzothiazolyl) carbonimide dithioate (when R ¹ is not present) or S, S′-dimethyl. -N-(2-substituted-benzothiazolyl) dicarbonimide phosphorodithioate ^{(R 1} is an alkyl group having 1 to 8 carbon atoms which may have a substituent, hydroxy Group, a carboxyl group, can be synthesized when an alkoxy group or a halogeno group having 1 to 4 carbon atoms).

III) In the case of Y ¹ = S, Y ² = NH, Z ¹ = N in the following formula (5):

For example, it can be synthesized according to the method described in Synthesis 1982, 1066-1067. That is, o-phenylenediamine (when R ² is not present) or o- (substituted phenylene) diamine (wherein R ² may have a substituent, an alkyl group having 1 to 8 carbon atoms, a hydroxyl group, a carboxyl group, C 1-4 alkoxy or halogeno group) is dissolved in DMF, where S, S′-dimethyl-N- (2-benzothiazolyl) -carbonimidodithioate (if R ¹ is not present) or S, S′-dimethyl-N- [2- (substituted benzothiazolyl)]-carbonimidodithioate (wherein R ¹ may have a substituent, an alkyl group having 1 to 8 carbon atoms, a hydroxyl group, a carboxyl group, After dropwise addition of a DMF solution of an alkoxy group having 1 to 4 carbon atoms or a halogeno group), the mixture is refluxed for 10 to 16 hours to give 2- (2-benzothia Riruamino) benzimidazole or 2- [2- (substituted-benzothiazolyl amino)] can be synthesized substituted benzimidazol.

IV) In the following formula (6): In the formula (2), Y ¹ = S, Y ² = NH, Z ¹ = CH

For example, J.A. Org. Chem. It can synthesize | combine according to the method described in 2002,67,5753-5772. That is, o-phenylenediamine (when R ² is not present) or o- (substituted phenylene) diamine (wherein R ² may have a substituent, an alkyl group having 1 to 8 carbon atoms, a hydroxyl group, a carboxyl group, An alkoxy group having 1 to 4 carbon atoms or a halogeno group) and ethyl-2-benzothiazolylacetate (when R ¹ is not present) or ethyl-2- (substituted benzothiazolyl) acetate (where R ¹ is a substituent). (In the case of an alkyl group having 1 to 8 carbon atoms, a hydroxyl group, a carboxyl group, an alkoxy group having 1 to 4 carbon atoms or a halogeno group which may have) by refluxing at 160 ° C. for 6 hours in a nitrogen atmosphere ( 2-benzothiazolyl) (2-benzimidazolyl) methane or [2- (substituted benzothiazolyl)] [2- (substituted benzimi Dazolyl)] methane can be synthesized.

Examples of the ethyl-2-benzothiazolyl acetate or ethyl-2- (substituted benzothiazolyl) acetate include those described in J. Org. Org. Chem. It can synthesize | combine according to the method described in 2002,67,5753-5772.
That is, by mixing ethyl cyanoacetate with 2-amino-thiophenol or 2-amino-substituted thiophenol and reacting at 120 ° C. for 2 hours under a nitrogen atmosphere, ethyl-2-benzothiazolyl acetate or Ethyl-2- (substituted benzothiazolyl) acetate can be synthesized.

V) In the following formula (7): In the formula (2), Y ¹ = Y ² = O, Z ¹ = CH

For example, it can be synthesized according to the method described in US3250780. That is, 2-aminophenol (when R ¹ and R ² are not present) or 2-amino-substituted phenol (an alkyl group having 1 to 8 carbon atoms that R ¹ and R ² may have a substituent, hydroxyl Group, carboxyl group, alkoxy group having 1 to 4 carbon atoms or halogeno group) and malonic acid are mixed, and this mixed solution is added to polyphosphoric acid under stirring while maintaining the temperature at 70 ° C. Next, the reaction solution is heated to 175 ° C. and reacted to synthesize bis (2-benzoxazolyl) methane or bis [2- (substituted benzoxazolyl)] methane.

VI) The following formula (8): In the formula (2), Y ¹ = Y ² = S, Z ¹ = CH

For example, J.A. Org. Chem. It can be synthesized according to the method described in 1961, 26, 3434-3445. That is, 2-aminothiophenol (when R ¹ and R ² are not present) or 2-amino-substituted thiophenol (wherein R ¹ and R ² may have a substituent, an alkyl group having 1 to 8 carbon atoms) , Hydroxyl group, carboxyl group, alkoxy group having 1 to 4 carbon atoms or halogeno group) and malonic acid are mixed, and this mixed solution is added to polyphosphoric acid under stirring while keeping the temperature at 70 ° C. Next, bis (2-benzothiazolyl) methane or bis [2- (substituted benzothiazolyl)] methane can be synthesized by reacting this reaction solution at 125-150 ° C. for 2 hours.

VII) In the case of Y ¹ = NR ⁵ , Y ² = NR ⁵ , Z ¹ = CH in the following formula (9): Formula (2)

For example, Gazz. Chim. Ital. It can be synthesized according to the method described in 1996, 126, 329-337. That is, (N-substituted-) o-phenylenediamine (when R ¹ and R ² are not present) or (N-substituted-) [o- (substituted phenylene)] diamine (R ¹ and R ² have a substituent) In the case of an alkyl group having 1 to 8 carbon atoms, a hydroxyl group, a carboxyl group, an alkoxy group having 1 to 4 carbon atoms or a halogeno group) and diethyl malonate, By refluxing at 155 ° C. for 11 hours, bis [2- (N-substituted) benzimidazolyl] methane or bis [2- (N-substituted) (substituted benzimidazolyl)] methane can be synthesized.

VIII) In the following formula (10): in the formula (2), Z ¹ = CR ⁶

For example, Gazz. Chim. Ital. 1994, 124, 301-308. As described above, R ⁶ of CR ⁶ attributed to Z ¹ or Z ² in formula (1) is particularly preferably an aralkyl group. Here, the case where this aralkyl group is, for example, a 4-pyridylmethyl group is taken up, and the synthesis method will be described below. Even when it is a substituent other than the 4-pyridylmethyl group, it can be synthesized according to the same synthesis method by selecting a corresponding substrate (aldehyde body corresponding to the substituent).

(2-benzothiazolyl) (2-benzimidazolyl) methane or [2- (substituted benzothiazolyl)] [2- (substituted benzimidazolyl)] methane obtained in IV) or bis (2-benzoxazolyl) obtained in V) ) Methane or bis [2- (substituted benzoxazolyl)] methane, or bis (2-benzothiazolyl) methane or bis [2- (substituted benzothiazolyl)] methane obtained from VI), or VII) Bis [2- (N-substituted) benzimidazolyl] methane or bis [2- (N-substituted) (substituted benzimidazolyl)] methane;
By mixing acetic acid and sodium acetate, adding 4-pyridinecarboxaldehyde to react here, and reducing with palladium carbon or the like,

From the compound obtained in IV), the corresponding 4- [β, β- (2-benzothiazolyl) (2-benzimidazolyl) ethyl] pyridine or 4- [β, β- {2- (substituted benzothiazolyl)} {2 -(Substituted benzimidazolyl)} ethyl] pyridine,
From the compound obtained in V), the corresponding 4- [β, β-bis (2-benzoxazolyl) ethyl] pyridine or 4- [β, β-bis {2- (substituted benzooxazolyl) } Ethyl] pyridine,
From the compound obtained in VI), the corresponding 4- [β, β-bis (2-benzothiazolyl) ethyl] pyridine or 4- [β, β-bis {2- (substituted benzothiazolyl)} ethyl] pyridine is
VII) from the corresponding 4- [β, β-bis {2- (N-substituted) benzimidazolyl} ethyl] pyridine or 4- [β, β-bis {2- (N-substituted) (Substituted benzimidazolyl) ethyl] pyridine can be synthesized.

IX) In Formula (2), each of at least one substituent of R ¹ and R ² may have a substituent, an alkylaminosulfonyl group having 1 to 16 carbon atoms, and may have a substituent. A morpholinosulfonyl group, an optionally substituted piperidinosulfonyl group, an optionally substituted pyrrolidinosulfonyl group, an optionally substituted thiomorpholinosulfonyl group or a substituent; In the case of piperazinosulfonyl group which may have

For example, according to the method described in JP-T-2007-535421, each of the ligands obtained by the methods I) to VIII) (in the formula (2), R ¹ and R ² are not present, or If present, it is limited to those in which any one to three of the four hydrogen atoms bonded to the four carbon atoms of the benzene ring to which the group can be bonded are substituted). An optionally substituted alkylaminosulfonyl group having 1 to 16 carbon atoms, a morpholinosulfonyl group which may have a substituent, a piperidinosulfonyl group which may have a substituent, and a substituent; A pyrrolidinosulfonyl group which may have a substituent, a thiomorpholinosulfonyl group which may have a substituent or a piperazinosulfonyl group which may have a substituent can be introduced.

Here, taking 2,2′-iminobisbenzothiazole or 2,2′-iminobis (substituted benzothiazole) obtained in I) as an example, the synthesis method will be described below.
2,2′-Iminobisbenzothiazole or 2,2′-iminobis (substituted benzothiazole) obtained in I) is added to chlorosulfonic acid and the mixture is stirred overnight. Further, thionyl chloride is added and stirred at 50 ° C. for 1 hour. After cooling to room temperature, the mixture is poured onto ice and suction filtered. The corresponding 2,2′-iminobis (substituted benzothiazole) can be synthesized by stirring the solid collected by filtration with the primary or secondary amine together with the remaining ice.

<< Method for Producing Metal Complex Represented by Formula (1) >>
For example, Polyhedron 2006, 25, 2363-2374 Org. Chem. In accordance with the method described in 2002,67,5753-5772, the ligand obtained based on the manufacturing method of said I)-IX), metal halide, metal sulfate, metal acetate, metal nitrate The corresponding metal complex can be synthesized by reacting with a metal salt such as. That is, a ligand obtained on the basis of the above production methods I) to IX) and a metal acetate corresponding to M in formula (1) are mixed with methanol, ethanol, water, N, N-dimethylformamide. It can be synthesized by reacting in a solvent such as (DMF).

<< Polyethersulfone resin composition containing at least one of the stabilizers for polyethersulfone resin represented by formula (1) >>
The polyethersulfone resin composition in the present invention contains at least one polyethersulfone resin stabilizer represented by the formula (1), and further contains at least one polyethersulfone resin. And Furthermore, you may contain at least 1 type of solvent as needed.

  The amount of each of the stabilizers for polyethersulfone resin of the present invention is not particularly limited as long as the effect of stabilizing the polyethersulfone resin can be obtained, but with respect to 100 parts by weight of the polyethersulfone resin material. It is 0.001-15 weight part, Preferably it is 0.01-10 weight part, More preferably, it is 0.03-5 weight part. If it is less than 0.001 part by weight, a sufficient stabilizing effect may not be obtained, and even if added in an amount of 15 parts by weight or more, a stabilizing effect commensurate with the amount added cannot be obtained and it is not economical.

  From the viewpoint of the stabilizing effect of the polyethersulfone resin, the stabilizer for the polyethersulfone resin represented by the formula (1) in the present invention is preferably contained in a dissolved state at a molecular level.

The method for mixing the stabilizer for the polyethersulfone resin of the present invention with a polyethersulfone resin and, if necessary, a solvent is not particularly limited and can be mixed by a known method.
For example, when the stabilizer for the polyethersulfone resin is used after being dissolved in a solvent, the mixing procedure is not particularly limited, and the components may be mixed in any order.

  Adopting a method in which the stabilizer for polyethersulfone resin is kneaded into a polyethersulfone resin (resin component which does not contain a solvent itself) having fluidity by melting it by heating without using a solvent. May be. In this case, it is preferable to use a known melt kneader. For example, a synthetic resin composition as a molding material can be obtained by melt-kneading using a short screw extruder, extruding into a stride shape, and cutting into a pellet shape. The temperature at the time of melt kneading can be appropriately set in consideration of both the decomposition temperature of the stabilizer for the polyethersulfone resin to be used and the melting point or glass transition point of the polyethersulfone resin material to be used. The temperature at the time of melt kneading is usually in the same range as the molding temperature described later, and even at such a temperature, the stabilizer of the present invention can be used effectively with almost no decomposition. The pressure at the time of kneading can be appropriately set according to the physical properties of the polyethersulfone resin material to be used.

  The polyethersulfone resin used in the present invention is not particularly limited as long as it has an aromatic group in the main chain and has an oxy group and a sulfonyl group as a linking group for the aromatic group. And polyethersulfone resins described in JP-A-200977138 and JP-A-2009-138149.

That is, as a method for producing the polyethersulfone resin used in the present invention, a dihalodiphenyl compound and a dihydric phenol compound are polycondensed in an organic solvent in the presence of an alkali metal compound, Examples thereof include a method in which an alkali metal disalt and a dihalodiphenyl compound are polycondensed.
Hereinafter, a method for producing a PES resin will be briefly described.

  The organic solvent is preferably a polar solvent, for example, a sulfoxide solvent such as dimethyl sulfoxide, an amide solvent such as N, N-dimethylformamide or N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N- Pyrrolidone solvents such as vinyl-2-pyrrolidone, piperidone solvents such as N-methyl-2-piperidone, imidazolidinone solvents such as 1,3-dimethyl-2-imidazolidinone, hexamethylphosphoamide, γ- Examples include butyrolactone, sulfolane, diphenyl ether, dimethyl sulfoxide, and diphenyl sulfone. A mixed solvent of two or more of these can also be used.

  Examples of the alkali metal compound include alkali metal carbonates, alkali metal hydroxides, alkali metal hydrides, alkali metal alkoxides, and the like. In particular, anhydrous alkali metal carbonates such as potassium carbonate and sodium carbonate are preferred.

  Examples of the dihalodiphenyl compound include dihalodiphenyl compounds having a sulfonyl group, for example, dihalodiphenyl sulfones such as 4,4′-dichlorodiphenyl sulfone and 4,4′-difluorodiphenyl sulfone, 1,4-bis (4 -Chlorphenylsulfonyl) benzene, bis (halogenophenylsulfonyl) benzenes such as 1,4-bis (4-fluorophenylsulfonyl) benzene, 4,4′-bis (4-chlorophenylsulfonyl) biphenyl, 4,4 ′ -Bis (halogenophenylsulfonyl) biphenyls such as bis (4-fluorophenylsulfonyl) biphenyl, and the like. These dihalodiphenyl compounds may be used in combination of two or more. Among these, 4,4'-dichlorodiphenyl sulfone or 4,4'-difluorodiphenyl sulfone is more preferable, and 4,4'-dichlorodiphenyl sulfone is particularly preferable because it is easily available.

  Examples of the dihydric phenol compound include hydroquinone, catechol, resorcin, 4,4′-biphenol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) methane, Bis (4-hydroxyphenyl) alkanes such as 2,2-bis (4-hydroxyphenyl) ethane, dihydroxydiphenyl sulfones such as 4,4′-dihydroxydiphenylsulfone, dihydroxydiphenyl ethers such as 4,4′-dihydroxydiphenyl ether Or a part of hydrogen atoms bonded to these benzene rings is a lower alkyl group such as a methyl group, an ethyl group or a propyl group, a lower alkoxy group such as a methoxy group, an ethoxy group or a propyloxy group, or Chlorine atom, bromine atom, fluorine atom And those which are substituted with halogen atoms. In particular, hydroquinone, 4,4′-biphenol, 2,2-bis (4-hydroxyphenylpropane), 4,4′-dihydroxydiphenyl ether, or 4,4′-dihydroxydiphenyl sulfone is preferable from the viewpoint of availability. 4,4′-dihydroxydiphenyl sulfone is particularly preferred. Two or more of the above dihydric phenol compounds may be mixed and used.

  It is preferable that the dihydric phenol compound and the dihalodiphenylsulfone compound are polycondensed using an approximately equimolar amount. In addition, in order to adjust the molecular weight of the polyethersulfone resin, the polycondensation was carried out so that the amount of the dihydric phenol compound used was slightly more or less than the equimolar amount relative to the amount of the dihalodiphenylsulfone compound used. It may be a thing.

  The polycondensation reaction temperature for the production of the polyethersulfone resin is preferably in the range of 140 to 340 ° C. If the reaction temperature is too high, the resulting polyethersulfone resin may be highly colored. On the other hand, if the reaction temperature is too low, the polymerization rate may decrease, and it may be difficult to obtain a polyethersulfone resin having an appropriate molecular weight within a practical reaction time.

  Thus, a suitable polyethersulfone resin applicable to the present invention can be obtained, but a commercially available polyethersulfone resin may be used. Examples of such commercially available PES resins include Sumika Excel (trade name) PES3600P, 4100P, 4800P, 5200P, and 5003P manufactured by Sumitomo Chemical Co., Ltd. and trade names UDELP-1700 of AMOCO.

  The molecular weight of the polyethersulfone resin is such that when the polyethersulfone resin is dissolved in dimethylformamide (DMF) so as to have a concentration of 1 (W / V)%, the reduced viscosity (RV) of the resulting solution is 0. What is set to 3-0.8 is preferable.

  From the viewpoint of easy availability of raw materials and ease of synthesis, a polyethersulfone resin comprising a repeating unit represented by the following formula (2) is preferred.

  The polyether sulfone resin composition of the present invention can be appropriately used by combining one kind or two or more kinds without any particular restriction on conventionally known polyether sulfone resins.

  In the polyethersulfone resin composition of the present invention, in addition to the stabilizer for the polyethersulfone resin represented by the formula (1) described above, conventionally known additives are appropriately used within a range not impairing the effects of the present invention. It may be added. Such additives include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants and other antioxidants, UV absorbers, light stabilizers, heat stabilizers, curing agents, curing catalysts, crosslinking Agent, coupling agent, leveling agent, lubricant, antistatic agent, nucleating agent, flame retardant, filler, colorant, photocatalytic material, rust inhibitor, water repellent, conductive material, anti-blocking material, plasticizer, flow Examples include regulators, mold release agents, foaming agents, fluorescent whitening agents, flameproofing agents, and inorganic light shielding agents.

≪Resin member obtained from polyethersulfone resin composition≫
From the polyethersulfone resin composition as described above, a resin member can be obtained by a conventionally known molding and solidifying method.
Examples of the molding method include an injection molding method, an extrusion molding method, a vacuum molding method, a compression molding method, a laminate molding method, and a transfer molding method. The molding temperature is usually 300 to 390 ° C, particularly 320 to 380 ° C. Even at such a relatively high molding temperature, the stabilizer of the present invention can be used effectively with almost no decomposition.
Examples of the form of the resin member include a sheet, a plate, and a film, but are not particularly limited.

When the polyethersulfone resin composition of the present invention is formed into a resin member by forming a coating film, the resin member does not have a form in which the polyethersulfone resin composition is applied or laminated on the base material or the base material. Any form of laminates may be used.
The material of the base material is not particularly limited, and can be appropriately selected and used according to the application. For example, an inorganic base material such as glass, a metal plate, and ceramics, or an organic base material such as a synthetic resin. A base material is mentioned. The shape of the substrate may be a film or a board as desired, and is not particularly limited.

  The method for applying or laminating the polyethersulfone resin composition to the substrate is not particularly limited, and examples thereof include known methods such as a dip coating method and a spin coating method. Specifically, the stabilizer for polyethersulfone resin and the polyethersulfone resin of the present invention are dissolved in an organic solvent, and the obtained coating solution is applied or laminated on a substrate by a known method. The above-mentioned additives may be dissolved or dispersed in the coating liquid. Examples of the organic solvent include alcohols such as methanol, ethanol, IPA, butanol, tetrafluoropropanol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, diethylene glycol, and the like. Glycols, halogenated hydrocarbons such as chloroform and dichloromethane, ketones such as acetone, MEK, methyl isobutyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, 3-octanone, ethyl acetate, 2-hydroxy Ethyl propionate, 3-methyl-3-methoxypropionate-n-butyl, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, acetic acid-n-butyl, isobutyl acetate, formate n -Esters such as amyl, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, butyric acid n-butyl, ethyl pyruvate, γ-butyrolactone, ethyl lactate, diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, etc. Ethers, aromatics such as toluene, xylene, monochlorobenzene, dichlorobenzene, hydrocarbons such as n-pentane, cyclopentane, n-hexane, cyclohexane, n-heptane, cycloheptane, and 2-pyrrolidone Lactams such as N-methyl-2-pyrrolidone, ε-caprolactam, 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol dimethyl ester Ether, diethylene glycol monoethyl ether, diethylene glycol mono -n- butyl ether acetate, PGMEA, glycol ethers such as propylene glycol monomethyl ether acetate and other acetonitrile, sulfolane, dimethyl sulfoxide, DMF, or the like can be used.

In the lamination to the base material, a composition using other resins other than the polyethersulfone resin composition used in the present invention may be laminated, and the fluororesin is previously applied to the base material for peeling the laminate. Further, a peelable composition such as a silicone resin may be coated.
Thus, a resin member can be obtained from the resin composition by applying or laminating the polyethersulfone resin composition on the substrate, or by peeling off the laminate containing the polyethersulfone resin composition from the substrate, if desired. .

    Hereinafter, the present invention will be specifically described with reference to production examples, examples and comparative examples. However, the present invention is not limited to these examples.

Production Example 1
18.8 g (0.2 mol) of phenol was heated to 50 ° C. and melted, and 45.1 g (0.3 mol) of 2-aminobenzothiazole was added thereto, and then further heated to 180 ° C. and kept for 20 hours. did. Thereafter, the reaction solution was cooled to 80 ° C., 60 g of ethanol was added dropwise, and the temperature was further kept for 1 hour. Thereafter, the mixture was cooled to room temperature, the precipitate was filtered off, washed with ethanol and dried to obtain 32.1 g of white 2,2′-iminobisbenzothiazole (L1: see Table 1 below) as a ligand. It was. The yield was 75.5% based on 2-aminobenzothiazole.

Production Example 2
10 g (0.035 mol) of 2,2′-iminobisbenzothiazole obtained in Production Example 1 was added to 70.1 g (0.602 mol) of chlorosulfonic acid, and the mixture was stirred at room temperature for 18 hours. Further, 10 g (0.084 mol) of thionyl chloride was added and stirred at 50 ° C. for 1 hour. After cooling to room temperature, the mixture was poured onto 400 g of ice and suction filtered. The solid collected by filtration was immediately stirred with 13.1 g (0.101 mol) of diisobutylamine together with the remaining ice. After warming to room temperature, the mixture was made alkaline with about 1 mL of 50 wt% strength sodium hydroxide solution. The solid was filtered off with suction, washed with water, and dried to give pale yellow 2,2′-iminobis [6- (N, N-diisobutylaminosulfonyl) benzothiazole] (L2: see Table 1 below) 18.6 g Got. The yield was 80.0% with respect to 2,2′-iminobisbenzothiazole.

Production Example 3
In the same manner as in Production Example 2 except that 8.8 g (0.101 mol) of morpholine was used instead of 13.1 g (0.101 mol) of diisobutylamine in Production Example 2, 2,2′-iminobis (6 -Morpholinosulfonylbenzothiazole) (L3: see Table 1 below) 15.4 g was obtained. The yield was 75.5% based on 2,2′-iminobisbenzothiazole.

Production Example 4
In the same manner as in Production Example 1, except that 54.1 g (0.3 mol) of 2-amino-6-methoxybenzothiazole was used instead of 45.1 g (0.3 mol) of 2-aminobenzothiazole in Production Example 1. As a ligand, 41.7 g of white 2,2′-iminobis (6-methoxybenzothiazole) (L4: see Table 1 below) was obtained. The yield was 81.0% based on 2-amino-6-methoxybenzothiazole.

Production Example 5
In the same manner as in Production Example 1, except that 55.4 g (0.3 mol) of 2-amino-6-chlorobenzothiazole was used instead of 45.1 g (0.3 mol) of 2-aminobenzothiazole in Production Example 1. As a ligand, 37.2 g of white 2,2′-iminobis (6-chlorobenzothiazole) (L5: see Table 1 below) was obtained. The yield was 70.4% based on 2-amino-6-chlorobenzothiazole.

Production Example 6
Production Example 1 and Production Example 1 except that 53.5 g (0.3 mol) of 2-amino-5,6-dimethylbenzothiazole was used instead of 45.1 g (0.3 mol) of 2-aminobenzothiazole. Similarly, 42.1 g of white 2,2′-iminobis (5,6-dimethylbenzothiazole) (L6: see Table 1 below) was obtained as a ligand. The yield was 82.7% based on 2-amino-5,6-dimethylbenzothiazole.

Production Example 7
15.0 g (0.10 mol) of 2-aminobenzothiazole, 18.4 g (0.12 mol) of 2-chlorobenzoxazole and 100 g of 1,2-diethoxyethane were added, and 6.4 g of tetrabutylammonium bromide ( 0.02 mol) and 33.7 g (0.30 mol) of 50% aqueous potassium hydroxide solution were added, and then the temperature was raised to 60 ° C. and kept for 12 hours. Thereafter, the reaction solution was cooled to room temperature and neutralized by adding hydrochloric acid dropwise until pH = 7. The precipitate was filtered off, washed with water and methanol, and then dried to obtain 22.9 g of white 2- (2-benzothiazolylamino) benzoxazole (L7: see Table 1 below). The yield was 85.8% based on 2-aminobenzothiazole.

Production Example 8
In Production Example 7, instead of 15.0 g (0.10 mol) of 2-aminobenzothiazole, 18.0 g (0.10 mol) of 2-amino-6-methoxybenzothiazole and 18.4 g (0 of 2-chlorobenzoxazole) In the same manner as in Production Example 7, except that 18.8 g (0.10 mol) of 2,6-dichlorobenzoxazole was used instead of. 27.7 g of [2- (6-methylsulfonylbenzothiazolyl) amino] benzoxazole (L8: see Table 1 below) was obtained. The yield was 83.5% based on 2-amino-6- (methylsulfonyl) benzothiazole.

  Table 1 shows the structural formulas of the obtained ligands.

Production Example 9
3.40 g (0.012 mol) of the ligand (L1) obtained in Production Example 1 was dissolved in 24 g (70 ° C.) of warm DMF, and 1.50 g (0.006 mol) of cobalt acetate tetrahydrate was added thereto. ) Was added. The mixture was stirred at 70 ° C. for 1 hour, cooled to room temperature, and 20 g of methanol was added dropwise. The resulting precipitate was filtered off, washed with methanol and dried to obtain 3.41 g of an orange cobalt complex. The yield was 91.1% based on the ligand (L1).

Production Example 10
7.99 g (0.012 mol) of the ligand (L2) obtained in Production Example 2 was dissolved in 48 g (70 ° C.) of warm DMF, and 1.50 g (0.006 mol) of cobalt acetate tetrahydrate. ) Was added. The mixture was stirred at 70 ° C. for 1 hour, cooled to room temperature, and then 40 g of methanol was added dropwise. The resulting precipitate was filtered off, washed with methanol and dried to obtain 7.56 g of a yellow cobalt complex. The yield was 90.1% based on the ligand (L2).

Production Example 11
6.98 g (0.012 mol) of the ligand (L3) obtained in Production Example 3 was dissolved in 48 g (70 ° C.) of warm DMF, and 1.50 g (0.006 mol) of cobalt acetate tetrahydrate. ) Was added. The mixture was stirred at 70 ° C. for 1 hour, cooled to room temperature, and then 40 g of methanol was added dropwise. The generated precipitate was separated by filtration, washed with methanol, and dried to obtain 6.75 g of a yellow cobalt complex. The yield was 92.2% based on the ligand (L3).

Production Example 12
4.12 g (0.012 mol) of the ligand (L4) obtained in Production Example 4 was dissolved in 36 g (70 ° C.) of warm DMF, and 1.50 g (0.006 mol) of cobalt acetate tetrahydrate was added thereto. ) Was added. The mixture was stirred at 70 ° C. for 1 hour, cooled to room temperature, and 30 g of methanol was added dropwise. The generated precipitate was separated by filtration, washed with methanol, and dried to obtain 4.33 g of an orange cobalt complex. The yield was 97.0% based on the ligand (L4).

Production Example 13
4.23 g (0.012 mol) of the ligand (L5) obtained in Production Example 5 was dissolved in 36 g (70 ° C.) of warm DMF, and 1.50 g (0.006 mol) of cobalt acetate tetrahydrate. ) Was added. The mixture was stirred at 70 ° C. for 1 hour, cooled to room temperature, and 30 g of methanol was added dropwise. The generated precipitate was separated by filtration, washed with methanol, and dried to obtain 4.38 g of an orange cobalt complex. The yield was 95.9% based on the ligand (L5).

Production Example 14
4.07 g (0.012 mol) of the ligand (L6) obtained in Production Example 6 was dissolved in 36 g (70 ° C.) of warm DMF, and 1.50 g (0.006 mol) of cobalt acetate tetrahydrate was added thereto. ) Was added. The mixture was stirred at 70 ° C. for 1 hour, cooled to room temperature, and 30 g of methanol was added dropwise. The generated precipitate was separated by filtration, washed with methanol, and dried to obtain 4.26 g of an orange cobalt complex. The yield was 96.5% based on the ligand (L6).

Production Example 15
3.21 g (0.012 mol) of the ligand (L7) obtained in Production Example 7 was dissolved in 24 g (70 ° C.) of warm DMF, and 1.50 g (0.006 mol) of cobalt acetate tetrahydrate. ) Was added. The mixture was stirred at 70 ° C. for 1 hour, cooled to room temperature, and 20 g of methanol was added dropwise. The generated precipitate was separated by filtration, washed with methanol, and dried to obtain 3.05 g of an orange cobalt complex. The yield was 85.9% based on the ligand (L7).

Production Example 16
3.98 g (0.012 mol) of the ligand (L8) obtained in Production Example 8 was dissolved in 36 g (70 ° C.) of warm DMF, and 1.50 g (0.006 mol) of cobalt acetate tetrahydrate. ) Was added. The mixture was stirred at 70 ° C. for 1 hour, cooled to room temperature, and 30 g of methanol was added dropwise. The generated precipitate was separated by filtration, washed with methanol, and dried to obtain 3.87 g of an orange cobalt complex. The yield was 89.5% based on the ligand (L8).

Production Example 17
The same as Production Example 9 except that 1.20 g (0.006 mol) of copper acetate monohydrate was used instead of 1.50 g (0.006 mol) of cobalt acetate tetrahydrate in Production Example 9. As a result, 2.98 g of a grey-green copper complex was obtained. The yield was 78.9% based on the ligand (L1).

Production Example 18
Similar to Production Example 13 except that 1.49 g (0.006 mol) of nickel acetate tetrahydrate was used instead of 1.50 g (0.006 mol) of cobalt acetate tetrahydrate in Production Example 9. As a result, 2.82 g of a reddish purple nickel complex was obtained. The yield was 75.4% based on the ligand (L1).

<Stabilizing effect for polyethersulfone resin>
Example 1
100.0 parts by weight of a polyethersulfone resin (Sumitomo Chemical Co., Ltd., Sumika Excel PES 4100P reduced viscosity 0.41), 0.5 parts by weight of the cobalt complex obtained in Production Example 9, and 900.0 parts by weight of dichloromethane Mixed. The obtained polyethersulfone resin composition was applied onto a polyethylene terephthalate substrate using a bar coater (manufactured by Nippon Cedars Co., Ltd.), then preliminarily dried at room temperature in a nitrogen atmosphere for 5 minutes, and then at 60 ° C. For 5 minutes. Thereafter, the base material was removed to obtain a polyethersulfone resin thin film. The coating film thickness was 17 μm.
This polyethersulfone resin thin film was evaluated by the method described later.

(Example 2)
A polyethersulfone resin thin film was obtained in the same manner as in Example 1 except that 0.01 part by weight of cobalt complex was used instead of 0.5 part by weight of cobalt complex in Example 1.
This polyethersulfone resin thin film was evaluated by the method described later.

(Example 3)
A polyethersulfone resin thin film was obtained in the same manner as in Example 1 except that 0.03 part by weight of cobalt complex was used instead of 0.5 part by weight of cobalt complex in Example 1.
This polyethersulfone resin thin film was evaluated by the method described later.

Example 4
A polyethersulfone resin thin film was obtained in the same manner as in Example 1 except that 3.0 parts by weight of the cobalt complex was used instead of 0.5 parts by weight of the cobalt complex in Example 1.
This polyethersulfone resin thin film was evaluated by the method described later.

(Example 5)
A polyethersulfone resin thin film was obtained in the same manner as in Example 1 except that 0.5 part by weight of the cobalt complex obtained in Production Example 10 was used in place of 0.5 part by weight of the cobalt complex in Example 1.
This polyethersulfone resin thin film was evaluated by the method described later.

(Example 6)
A polyethersulfone resin thin film was obtained in the same manner as in Example 1 except that 0.5 part by weight of the cobalt complex obtained in Production Example 11 was used instead of 0.5 part by weight of the cobalt complex in Example 1.
This polyethersulfone resin thin film was evaluated by the method described later.

(Example 7)
A polyethersulfone resin thin film was obtained in the same manner as in Example 1 except that 0.5 part by weight of the cobalt complex obtained in Production Example 12 was used in place of 0.5 part by weight of the cobalt complex in Example 1.
This polyethersulfone resin thin film was evaluated by the method described later.

(Example 8)
A polyethersulfone resin thin film was obtained in the same manner as in Example 1 except that 0.5 part by weight of the cobalt complex obtained in Production Example 13 was used instead of 0.5 part by weight of the cobalt complex in Example 1.
This polyethersulfone resin thin film was evaluated by the method described later.

Example 9
A polyethersulfone resin thin film was obtained in the same manner as in Example 1 except that 0.5 part by weight of the cobalt complex obtained in Production Example 14 was used in place of 0.5 part by weight of the cobalt complex in Example 1.
This polyethersulfone resin thin film was evaluated by the method described later.

(Example 10)
A polyethersulfone resin thin film was obtained in the same manner as in Example 1 except that 0.5 part by weight of the cobalt complex obtained in Production Example 15 was used in place of 0.5 part by weight of the cobalt complex in Example 1.
This polyethersulfone resin thin film was evaluated by the method described later.

(Example 11)
A polyethersulfone resin thin film was obtained in the same manner as in Example 1 except that 0.5 part by weight of the cobalt complex obtained in Production Example 16 was used in place of 0.5 part by weight of the cobalt complex in Example 1.
This polyethersulfone resin thin film was evaluated by the method described later.

(Example 12)
A polyethersulfone resin thin film was obtained in the same manner as in Example 1 except that 0.5 parts by weight of the copper complex obtained in Production Example 17 was used instead of 0.5 parts by weight of the cobalt complex in Example 1.
This polyethersulfone resin thin film was evaluated by the method described later.

(Example 13)
A polyethersulfone resin thin film was obtained in the same manner as in Example 1, except that 0.5 parts by weight of the nickel complex obtained in Production Example 18 was used instead of 0.5 parts by weight of the cobalt complex in Example 1.
This polyethersulfone resin thin film was evaluated by the method described later.

(Comparative Example 1)
A polyethersulfone resin thin film was obtained in the same manner as in Example 1 except that no stabilizer was used in Example 1.
This polyethersulfone resin thin film was evaluated by the method described later.

(Comparative Example 2)
A polyether was obtained in the same manner as in Example 1 except that 0.5 part by weight of 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole was used instead of 0.5 part by weight of the cobalt complex in Example 1. A sulfone resin thin film was obtained. This polyethersulfone resin thin film was evaluated by the method described later.

(Comparative Example 3)
In Example 1, instead of 0.5 parts by weight of the cobalt complex, 0.5 part by weight of 2,5-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate was used. A polyethersulfone resin thin film was obtained in the same manner as in Example 1. This polyethersulfone resin thin film was evaluated by the method described later.

(Comparative Example 4)
A polyethersulfone resin thin film was prepared in the same manner as in Example 1 except that 0.5 parts by weight of 2,2,6,6-tetramethylpiperidyl methacrylate was used instead of 0.5 parts by weight of the cobalt complex in Example 1. Got. This polyethersulfone resin thin film was evaluated by the method described later.

(Comparative Example 5)
Instead of 0.5 parts by weight of the cobalt complex in Example 1, 2-[{3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl} methyl] -2-butylpropanedioic acid bis [1 , 2,2,6,6-pentamethyl-4-piperidinyl] A polyethersulfone resin thin film was obtained in the same manner as in Example 1 except that 0.5 part by weight was used. This polyethersulfone resin thin film was evaluated by the method described later.

(Comparative Example 6)
Instead of 0.5 parts by weight of the cobalt complex in Example 1, bis (4-hydroxy-3,5-di-tert-butylhydrocinnamic acid) ethylene (2,2,6,6-tetramethylpiperidine-1, 4-Diyl) A polyethersulfone resin thin film was obtained in the same manner as in Example 1 except that 0.5 part by weight was used. This polyethersulfone resin thin film was evaluated by the method described later.

(Comparative Example 7)
100.0 parts by weight of polyethersulfone resin (Sumitomo Chemical Co., Ltd., Sumika Excel PES, 4100P, reduced viscosity 0.41), 0.5 parts by weight of cerium oxide (manufactured by Kanto Chemical Co., Ltd.), and 900.0 parts by weight of dichloromethane The part was dispersed for 1 minute at 600 rpm using a planetary ball mill (trade name: premium line P-7, manufactured by Fritsch), then cooled for 10 minutes, and further subjected to dispersion treatment at 1100 rpm for 1 minute to obtain a cerium oxide dispersion. Obtained. As the dispersion medium, 50 g of 0.1 mmφ zirconia balls (trade name YTZ balls manufactured by Nikkato) were used. The obtained cerium oxide dispersion was applied onto a polyethylene terephthalate substrate using a bar coater (manufactured by Nippon Cedars Co., Ltd.), then pre-dried at room temperature in a nitrogen atmosphere for 5 minutes, and then at 60 ° C. for 5 minutes. Dried for minutes. Thereafter, the base material was removed to obtain a polyethersulfone resin thin film. This cerium oxide dispersion-polyethersulfone resin thin film was evaluated by the method described below.

[Heat-resistant decomposition (5% weight loss temperature)]
About the complex used in the examples (complexes obtained in Production Examples 9 to 18) and the commercially available deterioration inhibitors used in Comparative Examples 2 to 6, using TG / DTA6200 (manufactured by SII), A 5% weight loss temperature was measured under a temperature condition of 40 to 500 ° C. and 10 ° C./min.

[Photodegradation resistance (average molecular weight)]
Each obtained resin thin film was installed in a test furnace of a xenon weather meter manufactured by Suga Test Instruments Co., Ltd., and irradiated with light having an irradiance of 60 W / m ² for 100 hours. About the resin thin film before irradiation and after irradiation, a weight average molecular weight (Mw) is calculated | required as a polyethylene glycol conversion value by the gel permeation chromatography (GPC) which uses a dimethylsulfoxide as a solvent, and weight is obtained with the following formula | equation. The average molecular weight change rate (%) was calculated.

[transparency]
The turbidity (haze) of each obtained resin thin film was measured using a Nippon Denshoku Industries Co., Ltd. haze meter (NDH-2000).

[Light discoloration resistance (hue change)]
The hue change before and after the photodegradation resistance test of each obtained resin thin film was visually confirmed.

  According to the present invention, the polyethersulfone resin has a high decomposition temperature, has an effect of improving light stability such as photodegradation resistance and light discoloration resistance with a small addition amount, and is soluble in the polyethersulfone resin. A stabilizer for polyethersulfone resin having high transparency can be provided. Moreover, the transparent polyethersulfone resin composition which can maintain the outstanding light stability containing this stabilizer, and the resin member obtained from this resin composition can be provided.

Claims (5)

Formula (1):

Wherein Y ¹ , Y ² , Y ³ and Y ⁴ are each independently NH, NR ⁵ , an oxygen atom or a sulfur atom; belonging to Y ¹ , Y ² , Y ³ or Y ⁴ R ⁵ of NR ⁵ is an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 15 carbon atoms which may have a substituent; and among Y ¹ , Y ² , Y ³ and Y ⁴ When at least two are represented by NR ⁵ , each R ⁵ of NR ⁵ represents a substituent independent of each other;
Z ¹ and Z ² are each independently a nitrogen atom, CH or CR ⁶ ; R ⁶ of CR ⁶ attributed to Z ¹ or Z ² may have 1 substituent. An alkyl group having ˜8, an aryl group having 6 to 15 carbon atoms which may have a substituent, a heteroaryl group having 4 to 12 carbon atoms which may have a substituent, and a substituent. also represent an heteroaralkyl group or an aralkyl group having 7 to 15 carbon atoms having a carbon number of 5 to 12; in the case ^{where Z 1} and ^{Z 2} are both represented by CR ^6, independently each ^{R 6} of CR ⁶ are mutually The substituted substituents;
Each of R ¹ , R ² , R ³ and R ⁴ may be absent or present; each of the groups present among R ¹ , R ² , R ³ and R ⁴ is Any one to four of the four hydrogen atoms bonded to the four carbon atoms of the benzene ring to which the group can be bonded can be substituted; all R ¹ , R ² , R ³ and R ⁴ each independently has an optionally substituted alkyl group having 1 to 8 carbon atoms, a hydroxyl group, a carboxyl group, an alkoxy group having 1 to 4 carbon atoms, a halogeno group, and a substituent. An optionally substituted alkylaminosulfonyl group having 1 to 16 carbon atoms, a morpholinosulfonyl group which may have a substituent, a piperidinosulfonyl group which may have a substituent, and a substituent; Good pyrrolidinosulfonyl group, substituted Good thiomorpholinyl have a morpholino sulfonyl is a group or an optionally substituted piperazino sulfonyl group;
M represents a metal atom)
A stabilizer for a polyethersulfone resin represented by:   The stabilizer for polyethersulfone resins according to claim 1, wherein the metal atom M in the formula (1) is a cobalt atom, a nickel atom or a copper atom.   A polyethersulfone resin composition comprising at least one of the stabilizers for a polyethersulfone resin according to claim 1 or 2 and at least one polyethersulfone resin. The polyethersulfone resin composition of Claim 3 whose said polyethersulfone resin is a polyethersulfone resin which consists of a repeating unit shown by following formula (2).

  A resin member obtained from the polyethersulfone resin composition according to claim 3.