JPH0517478A - New phthalocyanine derivative, its production and polymer substance containing the same derivative - Google Patents

Abstract

PURPOSE:To obtain the subject new compound having high deodorizing action on a bad smell, moldable together with a polymer substance to give a molded article having excellently deodorizing property. CONSTITUTION:A compound shown by formula I [Pc is phthalocyanine ring; M is H or metal; MPc is group shown by formula II; A is secondary or tertiary nitrogen or 2-18C alkylene which may be interrupted with O, cycloalkyl or phenyl; Y is NRR<7> (R and R<7> are H, 1-4C alkyl or NRR<7> is 5-to 6-membered saturated nitrogen-containing aromatic ring)] such as iron-phthalocyanine-tetra(N-6-aminohexyl)carboxamide. The compound shown by formula I, for example, is obtained by reacting a phthalocyanine-carboxamide shown by formula III with an amine shown by formula NH2-A-Y.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel phthalocyanine derivative, a process for producing the same, a deodorant composition containing the phthalocyanine derivative, and a deodorant polymer substance. The phthalocyanine derivative of the present invention has a high deodorizing property against bad odors, and is molded with various polymer substances to give a molded product having an excellent deodorizing property.

[0002]

2. Description of the Related Art Phthalocyanine (MPc) is an azaannulene compound closely related to porphyrin compounds contained in chloroplasts, and its derivative is used as a pigment. Further, in recent years, attention has also been paid to electronic, electrical, and optical functional molecules (compounds), and some of their derivatives have been used as metal complex catalysts in various reactions.

In particular, the oxidation catalytic action and catalase-like action of phthalocyanine are used for deodorizing various odorous components such as hydrogen sulfide, mercaptans and aldehydes. In order to exert such deodorizing effect, it is necessary to improve the efficiency of contact between phthalocyanine and the atmosphere containing odor.

Further, it is considered advantageous to support phthalocyanine on various polymer matrices because it is necessary to make a deodorant material into a product such as clothing, and deodorant fiber (Chemical 42, No. 5 (1987)). , Deodorant polyurethane foam
(Japanese Patent Laid-Open No. 63-54453), a poly (2-vinylpyridine-styrene) copolymer of a metal (iron) -phthalocyanine derivative, or a polymer in which polyurethane is covalently bonded (Masada Naomi et al., The Chemical Society of Japan No. 58). (Spring Annual Meeting Summary (1989))
Have been proposed.

[0005]

However, in these cases,
Since the phthalocyanine derivative used is a metal (eg, iron) -phthalocyanine-octa or tetracarboxylic acid, the polymer matrix composited with them or supporting them is limited to a neutral or basic one.

Therefore, although the conventional phthalocyanine-supported polymeric deodorant is effective against acidic odors such as hydrogen sulfide, it is slightly effective against basic odors such as ammonia and trimethylamine. There is only a neutralizing and deodorizing ability due to its own carboxyl group, and a sufficient effect is not obtained. Further, even if the same acidic odor is exhibited, deodorizing activity against hydrogen sulfide is considerably exhibited, but deodorizing activity against methyl mercaptan is considerably low.

Further, the deodorizing ability of the phthalocyanine derivative is good even in a humid environment, but is considerably lowered in a dry state of a normal atmospheric level.

An object of the present invention is to provide a novel phthalocyanine derivative which can be easily carried or retained on various polymer substances, particularly on a polymer substance having an acidic group, and a method for producing the same.

The phthalocyanine derivative of the present invention, due to its oxidation catalytic ability, has an acidic property such as hydrogen sulfide and mercaptans.
It makes it possible to deodorize (sulfur-based) odors. Furthermore, the present invention provides a deodorant composition having a practical deodorant ability even with respect to basic odors such as ammonia as a composite with a polymeric substance having an acidic group.

Another object of the present invention is to provide a composition having an excellent deodorizing activity even in a dry condition of a normal atmospheric level.

Still another object of the present invention is to provide a molded article such as a yarn or a urethane foam containing the novel phthalocyanine derivative or the deodorant composition.

[0012]

The present invention has the formula: MPc- (CONH-A-Y) n [I] [wherein Pc is a phthalocyanine ring; M is a hydrogen atom or a metal atom, and A is 1 to 3]. C2-18 alkylene optionally interrupted with secondary or tertiary nitrogen atoms, oxygen atoms, cyclohexyl groups or phenyl groups; Y is -N
RR '(R and R'represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or -NRR' represents a saturated nitrogen-containing aromatic ring having 5 to 6 rings) or an -OH group; 8
The present invention provides a phthalocyanine derivative represented by the formula and a method for producing the same.

(A) Novel Phthalocyanine Derivative The phthalocyanine derivative of the present invention has the formula [I]: MPc- (CONH-A-Y) n [wherein M, Pc, A, Y and n are the same as above]. ] Is shown. In the formula, MPc is the following formula in which a hydrogen atom or a metal atom M is bonded to the center of the phthalocyanine ring (Pc):

[Chemical 1] Means a phthalocyanine compound.

Various metals may be used as the metal M, but Fe, Cu, Ni, Co, Zn, V, Mn and the like are preferable, and Fe and Cu are particularly preferable.

The-(CONH-A-Y) n group represents a carboxamide group bonded to the benzene ring of phthalocyanine.

A represents alkylene having 2 to 18 carbon atoms, which may be interrupted by 1 to 3 secondary or tertiary nitrogen atom, oxygen atom, cyclohexyl group or phenyl group.

The alkylene may be branched, for example, ethylene, propylene, butylene, pentylene, hexylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, octadecylene, methylethylene, methyl. Examples include propylene, 2,2-dimethylethylene, ethylethylene and the like.

Such A is of the formula-(CH ₂ ) _m- [m is an integer of 2-18. ] Is represented. m is preferably 2 to 10, more preferably 3 to 6.

A may be a group in which the methylene group constituting the alkylene group of the above formula is interrupted at any position by a secondary or tertiary nitrogen atom, oxygen atom, cyclohexyl group or phenyl group. Good. Such A is 1
Those having 5 interrupting groups in the alkylene group are preferred. More preferably, it has 1 to 2 interrupting groups. This is represented by the formula:-(CH ₂ ) _p -X ^1- (CH ₂ ) _q -X ^2- (CH ₂ ) _r- [wherein p, q and r represent an integer of (p + q + r) = 2-18, X ¹ and X ² each represent a secondary or tertiary nitrogen atom, oxygen atom, cyclohexyl group or phenyl group. Further, ^one of X ¹ and X ² may be a single bond. ]] Is represented.

P, q and r are preferably (p + q
+ R) = 2-10, more preferably 2-6. Further, each of p, q and r is preferably 0 or an integer of 2 or more, and when q = 0, X ² is preferably a single bond.

X ¹ and X ² are the same or different and each is a secondary or tertiary nitrogen atom, oxygen atom, cyclohexyl group or phenyl group. Preferably, X ¹ = X ² or X ² is a single bond.

Y represents -NRR '(R and R'represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, a cyclohexyl group, a benzyl group or a phenyl group, respectively, or -NRR' is 5 to 6 ring. It represents a saturated nitrogen-containing aromatic ring) or an -OH group.

The alkyl group having 1 to 4 carbon atoms represented by R and R'is a linear or branched alkyl group,
Examples thereof include methyl, ethyl, propyl, isopropyl, butyl and isobutyl groups.

The 5-6 ring saturated nitrogen-containing aromatic ring is a pyrrolidino group or a piperidino group.

The group represented by -CONH-A-Y in the formula [I] is typically a group obtained from an aliphatic diamine, a group obtained from a polyamine, or a diamine having an oxygen atom. A group obtained from, a group obtained from a diamine having a cyclohexyl group or a phenyl group,
Examples thereof include groups obtained from amines having a terminal hydroxyl group.

The groups obtained from the aliphatic diamines include N- (2-aminoethyl) carbamoyl and N- (3
-Aminopropyl) carbamoyl, N- (2-aminopropyl) carbamoyl, N- (4-aminobutyl) carbamoyl, N- (5-aminopentyl) carbamoyl,
N- (6-aminohexyl) carbamoyl, N- (7-
Aminoheptyl) carbamoyl, N- (8-aminooctyl) carbamoyl, N- (9-aminononyl) carbamoyl, N- (10-aminodecyl) carbamoyl, N
-(11-aminoundecyl) carbamoyl, N- (1
2-aminododecyl) carbamoyl, N- (2-amino-2,2-dimethylethyl) carbamoyl, N- (5-
Amino-4,4-dimethylpentyl) carbamoyl, N
-(3-amino-2,2-dimethylpropyl) carbamoyl, N- (5-amino-4-methylpentyl) carbamoyl, N- (6-amino-3,5,5-trimethylhexyl) carbamoyl, N- ( 3-Methylaminopropyl) carbamoyl, N- (2-ethylaminoethyl) carbamoyl, N- (2-dimethylaminoethyl) carbamoyl, N- (2- (2hydroxyethyl) aminoethyl) carbamoyl, N- (4- (Diethylamino-1-
Methylbutyl) carbamoyl, N- (2-dimethylaminoethyl) carbamoyl, N- (2-diethylaminoethyl) carbamoyl, N- (2-isopropylaminoethyl) carbamoyl, N- (3-isopropylaminopropyl) carbamoyl, N- ( 2-diisopropylaminoethyl) carbamoyl, N- (3-dimethylaminopropyl) carbamoyl, N- (3-diethylaminopropyl) carbamoyl, N- (3-dibutylaminopropyl) carbamoyl, N- (2-cyclohexylaminoethyl) carbamoyl , N- (2-benzylaminoethyl) carbamoyl, N- (2-phenylaminoethyl)
Carbamoyl, N- (4-methylpiperazino) carbamoyl, N- (3-methylpiperazino) carbamoyl, homopiperazinylcarbonyl, N- (2-pyrrolidinoethyl) carbamoyl and the like can be mentioned.

Such a group has the following formula: -CONH- (CH ₂ ) _m -NRR '[m, R and R'are the same as defined above. ] Is represented. The preferred embodiments of m, R and R ′ are the same as described above.

[0028] Of the above examples, preferred are N- (2-aminoethyl) carbamoyl, N-
(3-aminopropyl) carbamoyl and N- (6-
Aminohexyl) carbamoyl may be mentioned.

The groups obtained from the polyamines include
N- (5-amino-3-azapentyl) carbamoyl,
N- (7-amino-4-azaheptyl) carbamoyl,
N- (7-amino-4-aza-4-methylheptyl) carbamoyl, N- (8-amino-3,6-diazaoctyl) carbamoyl, N- (11-amino-3,6,9-triazaundecyl) Carbamoyl, N- (9-amino-
3,7-Diazanonyl) carbamoyl, N- (12-amino-4,9-diazadodecyl) carbamoyl, N-
(2- (1-Piperazinyl) ethyl) carbamoyl, N
-(3- (4- (3-aminopropyl) piperazinyl)
Propyl) carbamoyl and the like.

Of these, those interrupted by 1 or 2 nitrogen atoms are those represented by the following formula: -CONH- (CH ₂ ) _p -N (-R '')-(CH ₂ ) _q- (N-R ''')-
(CH _{2) r} -NRR '[wherein, p, q, r, R and R' are as defined above. R ''
And R '''represents hydrogen, a methyl group or an ethyl group.
Further,-(N-R ''')-may be a single bond instead of this. ]] Is represented. Preferred embodiments such as p, q, r, R and R ′ are the same as above.

Of the R ″ and R ′ ″, preferred is hydrogen or a methyl group, and most preferred is hydrogen.

Among the above examples, the preferable one is N
-(5-Amino-3-azapentyl) carbamoyl and N- (8-amino-3,6-diazaoctyl) carbamoyl are mentioned.

The groups obtained from diamines having an oxygen atom include N- (8-amino-3,6-dioxaoctyl) carbamoyl and N- (13-amino-4,7,10).
-Trioxatridecyl) carbamoyl, N- (7-amino-4-oxaheptyl) carbamoyl, N- (ω-
Hydroxy-polyoxyethyleneoxyethyl) carbamoyl and the like can be mentioned.

Among them, those interrupted by 1 or 2 oxygen atoms are those represented by the following formula: -CONH- (CH ₂ ) _p -O- (CH ₂ ) _q -O- (CH ₂ ) _r -NRR '[ In the formula, p, q, r, R and R ′ are the same as above. Further, one of —O— may be a single bond. ]] Is represented. Preferred embodiments such as p, q, r, R and R ′ are the same as above.

Examples of the group obtained from the diamine having a cyclohexyl group or a phenyl group include N- (3- or 4-aminocyclohexyl) carbamoyl group and N-
(3- or 4-aminomethylcyclohexylmethyl)
Examples thereof include a carbamoyl group, an N- (3- or 4-aminomethylbenzyl) carbamoyl group and an N- (4- (4-aminocyclohexylmethyl) cyclohexyl) carbamoyl group.

Of these, those interrupted with a 1,3-phenylene group, a 1,4-phenylene group, a 1,3-cyclohexyl group or a 1,4-cyclohexyl group are preferred. Among them, those interrupted by a 1,3-phenylene group or a 1,3-cyclohexyl group are preferable. Especially 1,
Those interrupted with a 3-phenylene group are preferred.

The group interrupted by 1 to 2 groups has the following formula:

[Chemical 2] [In the formula, p, q, r, R and R ′ are the same as above. Ring A
And ring B represents a 1,3-phenylene group, a 1,4-phenylene group, a 1,3-cyclohexyl group or a 1,4-cyclohexyl group. Further, the ring B may be a single bond instead. ]] Is represented. Preferred embodiments such as p, q, r, R and R ′ are the same as above.

Next, the group obtained from amines having a terminal hydroxyl group corresponds to A shown in the above description of the group having a terminal amino group. This has the formula -CONH-A-OH [A is the same as above. ]] Is represented.

Specifically, N- (2-hydroxyethyl) carbamoyl, N- (6-hydroxy-4-azahexyl) carbamoyl, N- (3-hydroxypropyl) carbamoyl, N- (2-hydroxypropyl) carbamoyl. , N- (5-hydroxypentyl) carbamoyl group and the like.

Further, n is 1 to 8 and may be in the form of mono- or polycarboxylic acid. The position and number of carboxamide groups on each benzene ring are not particularly limited, and a mixture of isomers may be used. It may also be a mixture of compounds having different numbers of bound carboxamide groups. Those having n = 4 or 8 are easy to manufacture and are practically advantageous.

(B) Method for Producing Novel Phthalocyanine Derivative The phthalocyanine derivative is prepared by reacting a corresponding carboxylic acid and its active derivative (eg, ester, acid chloride, etc.) with H ₂
Although it can also be produced by a reaction with N-A-Y (formula [III]), it requires a long process, tends to cause a heterogeneous reaction, and has poor operability.

The above-mentioned phthalocyanine derivative of the formula [I] is represented by the formula: MPc- (CONH ₂ ) n [II] [wherein Pc, M and n are the same as those defined above] and the corresponding phthalocyanine carboxamide. NH ₂ —A—Y [III] [In the formula, A and Y are the same as the above] and can be easily produced by reacting with an amine compound. Compounds [II] and [III] may be reacted in equivalent amounts.

(B-1) Phthalocyaninecarboxamide derivative Specific examples of the phthalocyaninecarboxamide derivative of the formula [II] which is a raw material of the compound of the formula [I] of the present invention include metal-phthalocyanine-monocarboxamide and metal-phthalocyanine-diamine. Carboxamide, metal-phthalocyanine-tetracarboxamide, metal-phthalocyanine-octacarboxamide and the like can be mentioned. These metal phthalocyanine-carboxamide derivatives are compounds known per se and can be obtained by a known method or a method similar thereto (for example, H. Shirai, et al., Makromol. Chem., 1
78, 1889 ('77)).

That is, by a known method, a phthalic acid derivative, a trimellitic acid derivative, a pyromellitic acid derivative and the like and urea can be obtained by heating the corresponding metal salt in the presence of a catalyst. The obtained reaction product is washed with an organic solvent such as methanol and an acid aqueous solution (eg, dilute hydrochloric acid) and then with water, and the insoluble matter is collected by filtration to obtain a crude phthalocyanine-carboxamide. Although this product may be further purified, it can be immediately reacted with amines of the formula [III] to obtain the desired product of the formula [I].

(B-2) Amines As the amines of the formula [III] used in the present invention, amines corresponding to the above definitions of A and Y are used.

Specifically, aliphatic diamines (eg:
Ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, decamethylenediamine, 2,2-dimethylaminoethylamine, 2,2-diethylaminoethylamine, etc.), diamines containing cycloalkyl groups or phenyl groups (eg: 1,3- Bis (aminomethyl) cyclohexane, 4,4′-diaminodicyclohexylmethane, m-xylylenediamine, etc.), polyamines (eg, diethylenetriamine, triethylenetetramine, N, N-bis (aminopropyl) methylamine, etc.), hydroxy Examples thereof include alkylamines (eg, ethanolamine, ω-amino-polyethylene glycol, etc.).

(B-3) Conditions for producing phthalocyanine derivative The amount of these amines used is 1 to 1 per 1 mol equivalent of the carboxamide group of the starting phthalocyanine carboxamides.
The molar amount is 00 times, and more preferably 5 to 20 times.
The reaction temperature is about 140 ° C to about 200 ° C, preferably about 15 ° C.
The temperature is from 0 ° C to about 180 ° C. Although the reaction proceeds rapidly at this temperature, the heating is preferably performed for 0.5 to 5 hours, more preferably 1 to 3 hours in order to complete the reaction.

When the reaction is carried out with amines having a boiling point lower than the reaction temperature (eg ethylenediamine), the amines may be refluxed or under pressure (in a closed container).
It may also be carried out in a high boiling point solvent (eg, nitrobenzene, naphthalene, decalin, ethylene glycol mono- or di-lower alkyl ether, diethylene glycol mono- or di-lower alkyl ether, etc.) under reflux conditions.

After completion of the reaction, excess amines are removed by washing with water, methanol, ethanol or the like, and the residue is dissolved in an aqueous acid solution to make it basic (precipitation) or an acid (eg acetic acid, etc.). Organic acid or an inorganic acid such as hydrochloric acid and sulfuric acid), washed and purified by a known method such as recrystallization, and then collected by a known means such as filtration and centrifugation to obtain the desired product. May be.

(C) Poorly Water-Soluble Metal Hydroxide The water-insoluble metal hydroxide is preferably sparingly water-soluble near neutral. Specifically, 100 ml at 25 ° C
Is a sparingly water-soluble metal hydroxide having a solubility in water of 5 mg or less, preferably 1 mg or less, and more preferably 0.5 mg or less.

Examples of such metal hydroxides include Al,
Examples thereof include hydroxides of divalent or higher-valent metals such as Cu, Fe, Mn, Cr, and Ni, but hydroxides of Al and Cu are preferable, and those having a large specific surface area are particularly preferable.

(D) Deodorant composition containing a phthalocyanine derivative and a sparingly water-soluble metal hydroxide A phthalocyanine derivative and a sparingly water-soluble metal water can be obtained by simply mixing the phthalocyanine derivative and the sparingly water-soluble metal hydroxide. A deodorant composition containing an oxide is obtained.
The deodorant composition can also be obtained by mixing the phthalocyanine derivative during the production of the poorly water-soluble metal hydroxide.

The blending ratio of each component in this composition is
0.01 to 10% by weight of phthalocyanine derivative and 9
It is a poorly water-soluble metal hydroxide of 9.99 to 90% by weight.
Preferred are 0.1 to 5% by weight of phthalocyanine derivative and 99.9 to 95% by weight of sparingly water-soluble metal hydroxide.

(E) Phthalocyanine-carboxylic acid compound-containing deodorant composition Formula [I] which is the above-mentioned phthalocyanine derivative: MPc- (CONH-A-Y) n [M, Pc, A, Y and n are as described above] In addition to the compound represented by the formula [IV]: MPc- (COOH) n [wherein M, Pc and n are the same as those defined above], a phthalocyanine-carboxylic acid compound or a salt thereof can be added. You may use together. This phthalocyanine-carboxylic acid compound itself is known and can be obtained by a known method.
Among them, those with n = 4 or 8 are easy to manufacture,
It is practically advantageous.

Examples of the salt of compound [IV] include salts of alkali metals (sodium, potassium, etc.).

The compounding ratio at this time is such that the compound [I]: [IV] is in a weight ratio of 1:10 to 10: 1.

Such a mixed composition may have a more effective deodorizing activity even for basic odors.

Also, the phthalocyanine-carboxylic acid compound of the formula [IV] or a salt thereof may be used in combination with the deodorant composition containing the phthalocyanine derivative and the sparingly water-soluble metal hydroxide.

The compounding ratio at this time is the above compound [I].
It corresponds to the compounding ratio of [IV] and [IV], and this mixed composition may also have more effective deodorizing activity against basic odors.

(F) Novel Phthalocyanine Derivative or Deodorant Composition-Supporting Polymeric Substance Containing It The phthalocyanine derivative [I] of the present invention thus obtained and the deodorant composition containing it are It exhibits deodorizing activity by itself against acidic odors such as hydrogen sulfide and mercaptan, but has little effect on basic odors. Therefore, by supporting a polymeric substance having an acidic group effective for deodorizing a basic group or a molded article thereof,
A deodorant effective for both acidic and basic odors and excellent in moldability can be obtained.

The polymer substance and its molded product are
It is not particularly limited. Any of a polymeric substance having a basic group, a polymeric substance having a neutral group and a polymeric substance having an acidic group can be used. In particular, it is characterized in that it can be applied to a polymer substance having an acidic group, which has been difficult in the past. Generally, any material used as a molding material can be used without limitation to the molecular weight and the like.

Specific polymeric substances having an acidic group include polyacrylic acid, polyacrylonitrile and / or a copolymer of polyacrylamide and polyacrylic acid, alginic acid, polyglutamic acid (α or γ), sulfonated polystyrene, carboxy. Methyl cellulose,
Examples include carboxymethyl chitin and carboxymethyl chitosan.

Examples of the polymer substance having a neutral group include polyurethane (particularly, polyurethane foam as a molded body) and polyvinyl alcohol. In addition, examples of the polymeric substance having a basic group include chitosan.

In order to support the phthalocyanine derivative on the polymer substance or the molded article thereof, the phthalocyanine derivative may be simply adsorbed onto the polymer substance or may be chemically bonded thereto.

In order to support the phthalocyanine derivative of the present invention on these polymeric substances or molded products thereof, the phthalocyanine derivative is placed in an appropriate solvent (water alone, a mixture of water-miscible solvent and water or solvent alone). It can be carried out by dissolving or partially dissolving it, and adding a solution or dispersion of the polymer substance thereto or immersing the molded body.

The solvent used at this time is DM
F, DMSO, dimethylacetamide, N-methylpyrrolodone, pyridine and the like can be mentioned.

The amount of the phthalocyanine derivative supported or contained in the polymer substance and the deodorant composition containing the same are as follows:
It is in the range of 0.01 to 10% by weight, preferably 0.5 to 7% by weight, based on the whole including the polymer substance.

For example, when the polymer substance is alginic acid, the phthalocyanine derivative or its solution or dispersion may be added to a solution of alginic acid at an appropriate concentration and stirred. When the polymer substance is polyacrylonitrile / polyacrylic acid copolymer fiber, it is preferable to immerse the fiber in a solution of the phthalocyanine derivative in dilute acetic acid and appropriately stir it.

In the above-mentioned case, a colored fiber having an extremely high wash resistance (mainly derived from the coloring of the phthalocyanine derivative) can be obtained by simply immersing it, but in order to further improve the fastness, it is chemically bound. May be. For that purpose, as a suitable condensing agent in the above mixture, a condensing agent for forming an amide (or peptide) bond (eg, carbodiimides, carbonylimidazoles, and chloroformates and a deoxidizing agent (eg, triethylamine)) It is good to add a combination of. At that time, good results are often obtained by adding 4-dimethylaminopyridine, 4-pyrrolidinopyridine, DBN, DBU, pyridine, triethylamine or the like as a reaction accelerator.

In this case, the amount of the phthalocyanine derivative or the deodorant composition containing the phthalocyanine derivative is 0.1 to 10 based on the whole amount.
%, Preferably 0.5 to 7% by weight.

When the polymer substance is polyacrylic acid, it is treated with thionyl chloride or acetic anhydride by a method known per se to give an active group such as carbonyl chloride or acid anhydride in the polymer chain. May be generated in advance and reacted with a phthalocyanine derivative.
Also in this reaction, it is preferable to add the above reaction accelerator. In this case, the amount of the phthalocyanine derivative or the deodorant composition containing it is in the range of 0.5 to 5% by weight based on the whole.

Further, the carrier polymer substance and the phthalocyanine derivative may be bonded to each other by using a crosslinking agent. Examples of the cross-linking agent include formaldehyde (formalin), glutaraldehyde, epichlorohydrin, O, O′-diglycidyl ethylene glycol, hexamethylene diisocyanate, tolylene diisocyanate and the like.
The reaction can be carried out "one-pot" (for example, with formalin or glutaraldehyde) or stepwise (for example, with a crosslinking agent having a glycidyl group or an isocyanate group).

The polymer carrying the phthalocyanine derivative thus obtained is not only against acidic odors such as hydrogen sulfide and mercaptans which are odor controlling substances, but also against basic odors such as ammonia and triethylamine. Also has an excellent deodorizing ability, and exhibits an excellent deodorizing effect alone or in combination with other deodorizing agents.

Next, as the deodorant molding containing the phthalocyanine derivative and the poorly water-soluble metal hydroxide of the present invention, a phthalocyanine derivative-containing polyurethane foam-metal hydroxide composite is particularly preferable.

In order to produce such a molded article, diols or polyols, di- or polyisocyanates, chain extenders diamines, isocyanate condensation catalysts or foaming catalysts are reacted by a method known per se. When manufacturing polyurethane foam with
[I] A phthalocyanine derivative and a metal hydroxide are added and reacted.

The reaction proceeds satisfactorily only by mixing the above-mentioned reaction reagents at room temperature. However, in order to complete the reaction and cure the resin produced, the reaction is usually carried out at about 50-80 ° C in the latter stage of the reaction.
It is good to heat for a while.

The added metal hydroxide exists so that a part of the metal hydroxide is confined in the voids of the obtained resin, and the rest is bound to a functional group forming the structure of the resin by a coordinate bond. However, the addition amount during the reaction is not particularly limited as long as it does not inhibit the formation of polyurethane foam. After the reaction, the produced polyurethane foam is washed with water or a diluted alkali or dilute acid to remove excess reagents, residual catalysts, oligomers and the like as much as possible, and then dried appropriately to obtain the desired product.

The thus-obtained phthalocyanine derivative-containing urethane foam-metal hydroxide complex has a deodorizing ability under normal atmospheric conditions not only for hydrogen sulfide, which is an odor controlling substance, but also for mercaptans. Also, it can be used as a deodorizing material in combination with another deodorizing agent.

[0079]

The present invention will be described in more detail with reference to the following examples.

[Example 1] Iron-phthalocyanine-tetracarboxamide (2.0 g) and 1,6-hexamethylenediamine (4.0 g) were mixed well, and the mixture was mixed in an oil bath at 155 to 160 ° C to give 1.
The mixture was heated under reflux for 5 hours. The insoluble matter was collected by filtration while washing with water and then with methanol to obtain 2.02 g of a crude product. This product was added to a solution consisting of 7 ml of 1N hydrochloric acid and 200 ml of water and stirred. Then, the mixture was centrifuged to collect the supernatant, the precipitate was stirred with 100 ml of water, and then centrifuged again to collect the supernatant. Combine both supernatants and add approximately 19 ml of 1N aqueous potassium hydroxide solution to make it strongly alkaline,
The precipitate is collected by filtration, washed with methanol and dried to give 1.35 g.
Of iron-phthalocyanine-tetra (N-6-aminohexyl) carboxamide was obtained as a black powder.

100 mg of this product was added to 40 ml of 1N hydrochloric acid, dissolved by heating at 60 ° C., filtered, made alkaline with a 1N sodium hydroxide aqueous solution, and the formed precipitate was collected by washing with water and suspended in methanol. Collected by filtration
After washing with methanol and drying at 50 ° C for 8 hours,
1.53 mg of purified product was obtained as a black powder.

Elemental analysis value (as C ₆₀ H ₇₂ N ₁₆ O ₄ Fe · 4.5H ₂ O) Calculated value: C, 59.15; H, 6.70; N, 18.40 Actual value: C, 58.94; H, 6.40; N, 17.79 Ultraviolet absorption spectrum (λ _max (nm), (logε)): 690.0 (sh),
(4.07); 649.2, (4.13); 329.2, (4.37) Infrared absorption spectrum (cm ^-1 ): ca.3400, 2934, 2860, 16
51-1620, 1543, 1377,1325, 1156, 1102, 748, 611, 54
0, 480, 447, 412.

[Example 2] The reaction was carried out in the same manner as in Example 1, except that 4.0 g of m-xylylenediamine was used instead of 1,6-hexamethylenediamine. The reaction solution was treated in the same manner as in Example 1 to obtain 3.60 g of a crude product. This was first extracted with a solution of 12 ml of 1N hydrochloric acid added to 150 ml of water, and the supernatant was collected by centrifugation. The precipitate was extracted again with a solution of 4 ml of 1N hydrochloric acid added to 100 ml of water, and the supernatant was similarly collected. Combine both supernatants, 1N
It is made strongly alkaline with an aqueous solution of potassium hydroxide, the precipitate is collected by centrifugation, collected by filtration while being washed with methanol, and dried to obtain 2.35 g of iron-phthalocyanine-tetra (N-3).
-Aminomethylbenzyl) carboxamide was obtained as a dark green-black solid.

Ultraviolet absorption spectrum (λ _max (nm)): 698.8
(sh), 642.8, 564.4, 332.8, 320.4, 284.0.

Infrared absorption spectrum (cm ^-1 ): ca. 3340, 29
30, 2860, 1638, 1580, 1548, 1516, 1380, 1324, 130
0, 1156, 1106, 748, 700, 636, 620, 538, 499, 476,
443, 416, 406.

Example 3 The reaction was carried out in the same manner as in Example 1 except that 4.0 g of 3-aminopropanol was used instead of 1,6-hexamethylenediamine. The reaction mixture was treated in the same manner as in Example 1 to obtain 2.80 g of iron-phthalocyanine-tetra (N-3-aminopropyl) carboxamide as a green-black solid.

Example 4 As Example 1, except that 1,10-hexamethylenediamine was replaced by 1,10
The reaction was carried out with 9.28 g of decamethylenediamine. The reaction mixture was treated as in Example 1 to give 1.2 g of iron-
Phthalocyanine-tetra (N-10-aminodecyl) carboxamide was obtained as a green solid.

Example 5 As in Example 1, except that 1,6-hexamethylenediamine was replaced by 4,4 ′.
The reaction was carried out with 9.82 g of diaminodicyclohexylmethane. The reaction mixture was treated as in Example 1.1.
22 g of iron-phthalocyanine-tetra (N-4- (4-
Aminocyclohexylmethyl) cyclohexyl) carboxamide was obtained as a green-black solid.

[Example 6] The reaction was carried out in the same manner as in Example 1 except that 7.8 g of triethylenetetramine was used instead of 1,6-hexamethylenediamine. The reaction solution was treated in the same manner as in Example 1 to obtain 1.24 g of iron-phthalocyanine-tetra (N-8-amino-3,6-diazaoctyl) carboxamide as a purple-black solid.

[Example 7] 2.0 g of copper-phthalocyanine-tetracarboxamide and 6.3 of hexamethylenediamine
g was reacted in the same manner as in Example 1. The reaction solution was treated with water and the insoluble material was collected by filtration, washed with water and then with methanol, and dried to give 1.56 g of copper-phthalocyanine-tetra (N-6-aminohexyl) carboxamide as a purple black solid. Obtained.

[Example 8] The reaction was carried out in the same manner as in Example 7 except that 7.35 g of m-xylylenediamine was used instead of hexamethylenediamine. The product was treated with water, the insoluble matter was washed with water and then with methanol, and dried to obtain 2.56 g of copper-phthalocyanine-tetra (N-3).
-Aminomethylbenzyl) carboxamide was obtained as a purple-black solid.

Example 9 Trimellitic anhydride 3.2
g, phthalic anhydride 7.4 g, anhydrous ferric chloride 6.5 g, urea 40 g, and ammonium molybdate 1.64 g were mixed, 200 ml of nitrobenzene was added, and the mixture was heated under reflux in an oil bath at about 165 ° C. for 3 hours. . After allowing to cool, the nitrobenzene layer was decanted, the residue was washed with about 200 ml of methanol, and the insoluble matter was collected by filtration. 5% hydrochloric acid was added to the obtained insoluble matter.
After adding 50 ml and stirring overnight at room temperature, the mixture was collected by filtration, further washed with 5% hydrochloric acid (50 ml twice), washed with water, and dried to obtain 9.26 g of crude iron-phthalocyanine-monocarboxamide as a black solid. It was 2 g of the obtained product
Was heated to 4 g of hexamethylenediamine at about 165 ° C. for 2 hours, washed with water and then with methanol, and dried to 2.1.
7 g of dark green solid was obtained. This was stirred with 7 ml of 1N hydrochloric acid and 150 ml of water and centrifuged to collect the supernatant. To the precipitate, 4 ml of 1N hydrochloric acid and 100 ml of water were added again, and the mixture was stirred, centrifuged and the supernatant was collected. After repeating this operation once again, the supernatants were combined, filtered through a filter paper, made strong alkaline by adding about 20 ml of 1N potassium hydroxide aqueous solution, and the formed precipitate was collected by filtration until the washing liquid became almost neutral. After washing with water, washing with methanol and drying, 0.96 g of iron-phthalocyanine-mono (N-6-aminohexyl) carboxamide was obtained as a black powder.

Example 10 2 g of crude iron-phthalocyanine-monocarboxamide obtained as an intermediate in Example 9
And 4 g of m-xylylenediamine were mixed and heated at about 160 ° C. for 2 hours. The product was crushed in water-methanol, then filtered, washed with water and then with methanol, and dried to give 3.5.
5 g of green powder was obtained. The obtained product was treated with 1N hydrochloric acid (7 ml) and water (150 ml), then with 1N hydrochloric acid (5 ml) and water (100 ml) in the same manner as in Example 9, centrifuged, and the supernatant was collected and made alkaline with a 1N aqueous potassium hydroxide solution.
The formed precipitate was collected by filtration and dried to obtain 2.18 g of iron-phthalocyanine-mono (N-3-aminomethylbenzyl) carboxamide.

[Example 11] Trimellitic anhydride 9.
6g, phthalic anhydride 7.4g, urea 60g, anhydrous ferric chloride 9.75g, and ammonium molybdate 2.46g are mixed, and about 160 ° C in 300 ml of nitrobenzene.
The oil bath was heated for 3 hours. After allowing to cool, the nitrobenzene layer was removed by tilting, the residue was washed with methanol to loosen it, and the insoluble material was collected by filtration. 150 ml of 5% hydrochloric acid each,
After washing with 50 ml and 50 ml, followed by washing with water and drying, 18.41 g of crude iron-phthalocyanine-dicarboxamide was obtained as a black solid. 2 g of the obtained solid was heated and refluxed with 4 g of hexamethylenediamine in an oil bath at about 160 ° C. for 1.5 hours, the product was washed with water and then with methanol, insoluble matters were collected, and dried to obtain 2.02 g of a blue-green color. A solid was obtained.
Then, this solid was extracted with 7 ml of 1N hydrochloric acid and 200 ml of water, and then with 7 ml of 1N hydrochloric acid and 100 ml of water, and the extracts were combined, and the precipitate formed as an alkalinity with about 20 ml of 1N aqueous potassium hydroxide solution was collected by filtration, followed by water and methanol. After washing with water and drying, 1.35 g of iron-phthalocyanine-
Bis (N-6-aminohexyl) carboxamide was obtained as a black powder.

[Example 12] 2.0 g of crude iron-phthalocyanine-dicarboxamide obtained as an intermediate in Example 11 was heated with 4 g of m-xylylenediamine in an oil bath at about 160 ° C for 2 hours. After cooling, water and methanol were added to loosen the mixture, and the insoluble matter was collected to obtain 3.60 g of a green powder. This powder was then mixed with 12 ml of 1N hydrochloric acid and 150 m of water.
1, and then extracted with 4 ml of 1N hydrochloric acid and 100 ml of water.
The extracts were combined and made alkaline with a 1N aqueous potassium hydroxide solution, and the formed precipitate was collected by filtration. The obtained precipitate is water,
Then, it was washed with methanol and dried to obtain 2.35 g of iron-phthalocyanine-bis (N-3-aminomethylbenzyl) carboxamide as a black powder.

Example 13 1.0 g of the crude iron-phthalocyanine-dicarboxamide obtained in Example 11 together with 2.0 g of diethylenetriamine was added in an oil bath at about 160 ° C. to 1.0 g.
Heated for 5 hours. Then, the volatile components were distilled off from the reaction product under reduced pressure, and the residue was treated with 1N hydrochloric acid (4 ml) and water (50 ml).
The soluble matter was collected by treating with. A precipitate formed by making this soluble component alkaline with a 1N aqueous sodium hydroxide solution was collected by filtration, washed with water and dried to obtain 650 mg of iron-phthalocyanine-bis (N- (5-amino-3-azapentyl)) carboxamide. It was

[Example 14] Iron-phthalocyanine-tetra (N-6-aminohexyl) carboxamide 50 mg
Was dissolved in a mixed solution of 10 ml of acetic acid and 20 ml of water with slight heating. To this solution, 250 mg of chitosan was added and dissolved. To this, 88 μl of a 25% aqueous solution of glutaraldehyde was diluted with 3 ml of water, and the mixture was stirred overnight at room temperature and then at about 80 ° C. for 2 hours. After standing to cool, add 2
It was diluted with 00 ml of water and poured into 500 ml of 1N sodium hydroxide aqueous solution. Acetic acid was added to the obtained green solution to adjust the pH to 8 to 9, and a gel-like precipitate was deposited. This was filtered through a sieve, washed with water and then with methanol, and then lyophilized to obtain a dry gel of chitosan carrying 210 mg of iron-phthalocyanine-tetra (N-6-aminohexyl) carboxamide.

Example 15 1.0 g of sodium polyacrylate was heated with 20 g of acetic anhydride at about 110 ° C. for 2 hours. Then, the volatile matter was removed under reduced pressure, and 10 ml of pyridine was added to the residue. To this, a solution of 82 mg of iron-phthalocyanine-tetra (N-3-aminomethylbenzyl) carboxamide dissolved in 5 ml of pyridine was added,
Further, 50 mg of 4-dimethylaminopyridine was dissolved in a small amount of pyridine and added. After stirring for 20 minutes at room temperature,
Heated in an oil bath at about 90 ° C. for 1 hour. Pyridine was distilled off under reduced pressure, the obtained green granular material was transferred to a cellophane tube together with about 100 ml of water, and dialyzed in running water for 24 hours. Then, the obtained green viscous liquid (about 135 m
l) was poured into a solution prepared by dissolving 3.1 g of copper sulfate pentahydrate in 100 ml of water. The resulting gel-like material is filtered through a sieve,
After washing with water and freeze-drying, 760 mg of iron-phthalocyanine-
An immobilization product of tetra (N-3-aminobenzyl) carboxamide-supported polyacrylic acid with copper ions was obtained as a green-blue short fiber material.

Example 16 Sodium alginate 1.
0 g was suspended in 10 ml of toluene, 0.77 ml of thionyl chloride and 3 drops of pyridine were added, and the mixture was heated under reflux for 1 hour. The solvent layer was decanted off and the residue was washed with toluene, after which iron-phthalocyanine-mono
45 mg of (N-6-aminohexyl) carboxamide was suspended in 10 ml of pyridine, added, and further added with 50 mg of 4-dimethylaminopyridine and heated at 80 ° C. for 1.5 hours. The reaction mixture was evaporated to dryness under reduced pressure, and 100 ml of water was added to the residue.
Was added and dissolved, and the obtained viscous liquid was treated with an aqueous solution of copper sulfate in the same manner as in Example 15. The obtained precipitate was collected by filtration, washed with water and then freeze-dried to obtain 830 mg of an iron-phthalocyanine-mono (N-6-aminohexyl) carboxamide-supported alginic acid-immobilized product with a copper ion as a dark green-blue fibrous substance.

[Embodiment 17] In the same manner as in Embodiment 16,
However, instead of iron-phthalocyanine-mono (N-6-aminohexyl) carboxamide, iron-phthalocyanine-
The reaction was carried out using 80 mg of mono (N-5-amino-3-azapentyl) carboxamide. The obtained product was treated in the same manner as in Example 16 to give 1.04 g of an iron-phthalocyanine-mono (N-5-amino-3-azapentyl) carboxamide-supported alginic acid-immobilized product with copper ions as a dark blue fiber. I got it as a thing.

[Example 18] Iron-phthalocyanine-tetra (N-6-aminohexyl) carboxamide 11 mg
Was dissolved in 5 ml of acetic acid and 2.5 ml of water with slight heating, and water was added to make the total volume 20 ml. When 1.0 g (wet dry weight: 0.272 g) of wet polyacrylonitrile / polyacrylic acid copolymer fiber was immersed in this solution, the fiber was dyed a pale color and the supernatant became almost colorless.
The fibers are taken out, washed with water, dried under reduced pressure and then 277.2 mg.
Iron-phthalocyanine-tetra (N-6-aminohexyl) carboxamide-supported polyacrylonitrile / polyacrylic acid fiber was obtained.

Example 19 In the same manner as in Example 18, polyacrylonitrile / polyacrylic fibers were impregnated with iron-phthalocyanine-tetra (N-6-aminohexyl) carboxamide to give an almost colorless liquid, 1- (3). 50 mg of -dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 30 mg of 4-dimethylaminopyridine were added. After stirring overnight at room temperature, the same treatment as in Example 18 was carried out to obtain 274.2 mg of iron-phthalocyanine-tetra (N-6-aminohexyl) carbodiimide-supported polyacrylonitrile / polyacrylic acid fiber.

Example 20 In a paper cup having a capacity of about 500 ml, a polyether polyol represented by the following formula IV (ACTCOL 79-56; manufactured by Takeda Pharmaceutical Co., Ltd.): 20 g, copper-phthalocyanine-tetra (N-6-aminohexyl) carboxamide 163 mg, aluminum hydroxide (manufactured by Mizusawa Chemical Co., Ltd.) 125 mg, silicone oil,
0.2 g, triethylenediamine hydrate (hereinafter abbreviated as TED), 0.92 g and tin octanoate, 3 to 5 drops were charged and mixed. To this, 11.5 g of tolylene diisocyanate (hereinafter abbreviated as TDI) was added at room temperature and stirred vigorously. The mixture was allowed to stand at room temperature until foaming was completed, and then heated at 80 ° C. for 10 minutes to cure. The product was washed with water and then vacuum dried to obtain a deodorant urethane foam.

[Embodiment 21] In the same manner as in Embodiment 20,
However, instead of iron-phthalocyanine-tetracarboxylic acid, 163 mg of iron-phthalocyanine-tetra (N-3-hydroxypropyl) carboxamide was used for the reaction,
A deodorant urethane foam was obtained.

[Embodiment 22] In the same manner as in Embodiment 20,
However, instead of iron-phthalocyanine-tetracarboxylic acid, 163 mg of iron-phthalocyanine-tetra (N-3,6-diazahexyl) carboxamide was used for the reaction,
A deodorant urethane foam was obtained.

[Embodiment 23] In the same manner as in Embodiment 20,
However, instead of iron-phthalocyanine-tetracarboxylic acid, 163 mg of iron-phthalocyanine-tetra (N- (4- (4-aminocyclohexylmethyl) cyclohexyl) carboxamide was used for the reaction to obtain a deodorant urethane foam.

Example 24 2.0 g of iron-phthalocyanine-tetracarboxamide and 6.26 g of 1,6-hexamethylenediamine were mixed well, and the mixture was heated under reflux in an oil bath at 155 to 160 ° C. for 1 hour. 200 ml of water in the obtained green liquid
Was added and the formed precipitate was collected by filtration. After thoroughly washing the precipitate with water, the insoluble matter was collected by centrifugation, water was removed under reduced pressure, and the product was dried under reduced pressure to obtain iron-phthalocyanine-tetra (N
2.32 g of -6-aminohexyl) carboxamide was obtained as a dark green solid.

[Embodiment 25] In the same manner as in Embodiment 24,
However, instead of 1,6-hexamethylenediamine, m
-The reaction was carried out with 7.35 g of xylylenediamine. The reaction solution was treated in the same manner as in Example 24 to obtain 3.06 g of iron-phthalocyanine-tetra (N-3-aminomethylbenzyl) carboxamide as a green solid.

[0109]

INDUSTRIAL APPLICABILITY The novel phthalocyanine derivative of the present invention can be easily carried or held on various polymer substances. Therefore, the oxidative catalytic ability of the phthalocyanine derivative itself deodorizes acidic (sulfur-based) odors such as hydrogen sulfide and mercaptans, and also exhibits a practical deodorant ability against basic odors such as ammonia. . Further, the deodorant composition and the deodorant molded article of the present invention have excellent deodorant activity even in a wet state of a normal atmospheric atmosphere, and are significantly larger than conventional phthalocyanine derivative-containing deodorant urethane foams and the like. And to provide a deodorant molded article having improved deodorant activity.

Claims (7)

[Claims] 1. A formula: MPc- (CONH-A-Y) n [I] [wherein Pc is a phthalocyanine ring; M is a hydrogen atom or a metal atom, and A is 1 to 3 secondary or tertiary nitrogen atoms. atom,
An alkylene group having 2 to 18 carbon atoms which may be interrupted by an oxygen atom, a cyclohexyl group or a phenyl group;
NRR '(R and R'are hydrogen atoms or C1-4
Or a saturated nitrogen-containing aromatic ring in which -NRR 'has 5 to 6 rings. ) Or -OH group; n is 1 to
Means an integer of 8]. _2. A phthalocyanine-carboxamide represented by the formula: MPc- (CONH ₂ ) n [II] [wherein Pc, M and n are the same as above] and a formula: NH ₂ -A-Y [III ] The manufacturing method of the phthalocyanine derivative of Claim 1 which makes it react with amines represented by [In formula, A and Y are the same as the above]. 3. A deodorant composition containing the phthalocyanine derivative according to claim 1 and a sparingly water-soluble metal hydroxide. 4. A polymer substance carrying the phthalocyanine derivative according to claim 1. 5. A polymer substance containing the deodorant composition according to claim 3. 6. The polymer material is polyurethane.
Alternatively, the polymer substance according to item 5. 7. A molded product made of the polymer substance according to claim 4, 5 or 6.