JPH0670117B2 - Method for producing phthalocyanine addition condensation resin - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a phthalocyanine addition condensation resin.

Prior art and its problems Metal phthalocyanine has attracted attention as a material for light absorption, conduction, photoconduction, energy exchange, electrodes, catalysts, etc. because metal ions are present in a large π-electron conjugated system, and various studies have been conducted. It is being appreciated.

The present inventors have proposed various polymers having phthalocyanine in the main chain or side chain (Makromol. Chem. 30 1480).
1981, pp. 180 2073 1979, etc.) and found that it can be used as a material having a high function.

Further, JP-A-60-184083 discloses phthalocyanine as a monomer which can be polymerized or crosslinked by an electron beam, an ultraviolet ray or the like.

By the way, the polymer metal complex is used for deodorant fiber and the like by utilizing the fact that it catalytically removes malodorous substances, and when a phthalocyanine compound and its polymer compound are used for these, these are excellent. It has been found by the present inventors that the deodorizing effect is exerted [Freglens Journal No. 72 (1985)].

From this, it is thought that if not only polymerization but also a resin compound such as a polymer can be obtained by using a novel polymerizable phthalocyanine compound, a highly functional material having a wider range of applications will be realized. Be done.

II Object of the Invention An object of the present invention is to provide a method for producing a phthalocyanine addition condensation resin using a novel phthalocyanine monomer, which can realize a highly functional material applicable to a resin processed material having a deodorant ability. .

III DISCLOSURE OF THE INVENTION Such an object is achieved by the present invention described below.

That is, the present invention uses a monomer represented by the following formula (I), which is subjected to addition condensation with phenols, ureas or melamines to form a phthalocyanine ring in the main chain.
A method for producing a phthalocyanine addition condensation resin, which comprises obtaining a phthalocyanine addition condensation resin containing 50 wt% or less.

Formula (I) PcCONH-R) n (In the above formula (I), Pc represents a phthalocyanine residue, R represents H or -LOH (wherein L represents a lower alkylene group), and n represents. It is an integer of 1 or more. } IV Specific Structure of the Invention Hereinafter, the specific structure of the present invention will be described in detail.

The phthalocyanine addition condensation resin in the present invention is obtained by addition-condensing a monomer represented by the following formula (I) and a compound capable of addition condensation with this monomer.

Formula PcCONH-R) n (I) In the above formula (I), R represents H or -LOH.

Here, L represents an alkylene group, but the alkylene group may be linear or branched. And it is preferable that the number of carbon atoms is 1 to 5, especially 1.

And, n is an integer of 1 or more, and may be an arbitrary integer of generally 1 to 8, but is usually 2, 4 or 8, and particularly 2
Or 4.

On the other hand, Pc represents a monovalent or higher-valent residue of phthalocyanine, and the group represented by -CONH-R is bonded to the benzene ring forming the phthalocyanine ring.

In this case, the above group is bonded to an arbitrary position of the benzene ring of phthalocyanine, but is usually bonded to 3-position to 4-position.

Therefore, the bonding position of the above groups is 3,3 ′ when n = 2.
−, 3,4′−, 3,3 ″ −, 3,4 ″ −, 4,4′−.

When n = 4, 3,3 ', 3 ", 3-is the main, and when n = 8, 3,4,3', 4 ', 3", 4 ", 3,4-is the main.

Further, the central atom of the phthalocyanine is not particularly limited, and in addition to Fe, Cu, Co, Ni, etc., V, Pb, Si, Ge, Sn, Al, Ru, Ti, Z
In addition to n, Mg, Mn, Lu, VO, etc., H ₂ is also possible.

However, among these, Fe, Ni, Co, Cu, Mg, Al, Mn, Sn or Lu is preferable.

In this case, 1 or 2 other ligands may be further coordinated above and below the phthalocyanine ring.

Although other substituents are not usually bonded to the phthalocyanine residue, a substituent such as a carboxy group, a sulfo group or an amino group may be bonded to the benzene ring of Pc, in particular.

The structural unit derived from the monomer represented by (I) is usually contained in the polymer main chain of the phthalocyanine addition condensation resin.

Phthalocyanine addition condensation resin obtained in the present invention is a monomer represented by the formula _{(I), PcCONH-R 2} ) n ( as a monomer A) or PcCONH-L-OH) and n (monomer B) and an additional condensable It is a condensation polymer with a predetermined compound.

The polymerization rate of the phthalocyanine addition-condensation resin, the phthalocyanine content, etc. vary depending on the polymerization method, the type of the condensable compound used, etc., and can be changed according to the application, but usually the phthalocyanine content is the case of the monomers A and B. Both 50w
t% or less.

The phthalocyanine addition-condensation resin of the present invention may have improved thermal properties depending on the content of the phthalocyanine, although it may vary depending on the kind of the resin.

The molecular weight cannot be measured because the phthalocyanine addition condensation resin is insoluble and infusible. Most of the phthalocyanine addition-condensation resins exhibit a blue to green color, are very hard, and are completely insoluble in a solvent that dissolves phthalocyanine such as cold concentrated sulfuric acid.

The absorption spectrum of the phthalocyanine addition-condensation resin is almost the same as that of the above-mentioned phthalocyanine compound as a starting material, and different from the case where phthalocyanine is introduced into the polymer side chain by a polymer reaction. As a result, the method of synthesizing a polymer containing phthalocyanine can be introduced into the polymer chain by addition condensation in various forms from the introduction of phthalocyanine into the side chain by the conventional polymer reaction.

Moreover, when the phthalocyanine content is increased, a wide absorption band near 600 nm is obtained. This is absorption due to a state where phthalocyanine rings are stacked or assembled.
From the comparison with the absorption spectrum of the polymerization solution, it can be seen that the phthalocyanine ring is uniformly dispersed in the solution and aggregates when it is concentrated and immobilized by the polymerization.

For example, in urea resin, the infrared absorption spectrum is
Compared with the phthalocyanine compound of the above-mentioned starting material, the ν _OH of 3300 to 3400 cm ^-1 is generally decreased by the polymerization, and
Ν _CH around ^-1 increases. The absorption attributed to the amide at 1550 to 1660 cm ^-1 is broad and exhibits the same behavior as the urea resin.

The compound used for addition condensation with the monomer represented by the formula (I) may be any of a monomer, an oligomer and a prepolymer.

And phenol, o, m, p-cresol, phenol halide, methylphenol, ethylphenol, n-
Phenols such as butylphenol, tert-butylphenol, bisphenol, p-phenylphenol, xylene, resole, novolac; urea, monomethylol urea, monomethylol urea methyl ether, dimethylol urea, dimethylol urea dimethyl ether, trimethylol urea, trimethylol urea trimethyl. Urea such as ether, urone, methylene diurea, monomethylol methylene diurea, dimethylol methylene diurea, dimethylene triurea, monomethylol dimethylene triurea, dimethylol dimethylene triurea, dimethylol oxymethylene diurea, propylidene diurea and the like Urea such as ether derivative; melamine, monomethylol melamine, dimethylol melamine, trimethylol melamine, and these ethers Derivatives, 1 melamines melamine prepolymers such
Use more than one seed.

The prepolymer preferably has an average molecular weight of about 2000. You may use 2 or more types of these.

The phthalocyanine monomer may be used in a weight ratio of about 20 to 50 wt% with respect to these addition condensation monomers.

Such a phthalocyanine addition condensation resin is synthesized as follows.

First, the monomer represented by the above formula (I), PcCONH ₂ )
n and PcCONH-L-OH) n are synthesized.

PcCONH ₂ ) n is usually n = 2,4 around the phthalocyanine ring.
To 8 are amide derivatives having amide groups, and are synthesized from trimellitic anhydride or its derivative, urea, and metal chloride.

PcCONH-L-OH) n is synthesized as follows. An aqueous solution of an aldehyde (for example, HCHO, CH ₃ CHO, etc.) selected according to the desired phthalocyanine compound L is added to the above amide derivative, and reacted under a base catalyst such as sodium hydroxide at room temperature for several to several tens of hours. Let

After the reaction, it is dissolved in a large amount of water, filtered and concentrated, and crystals are obtained again with methanol, ethanol and the like.

The thus-synthesized phthalocyanine compound and a compound capable of addition condensation with the compound are subjected to an addition condensation reaction under an acid or basic catalyst or by heat to obtain a phthalocyanine addition condensation resin.

The reaction conditions vary depending on the addition-condensable compound used, but generally the reaction temperature is 100 to 150 ° C, and the reaction time is 2 to 36 ° C.
Good time.

Water or the like is used as the solvent of the reaction system.

And the monomer raw material is about 1 to 50%, especially 5 to 25%
Aqueous solution.

Moreover, hydrochloric acid, oxalic acid, or the like is used as the acidic catalyst.
On the other hand, ammonium chloride, hexamethylenetetramine, or the like is used as the basic catalyst.

The amount of catalyst is about 0.1 to 2% with respect to the monomer.

Further, when the phthalocyanine addition condensation resin is obtained, it is possible to form a thin film on a substrate such as glass or PET, and the obtained thin film resin exhibits a high absorbance at a film thickness of about 1 μm.

The phthalocyanine addition-condensation resin thus obtained can be used as a resin processing agent having a deodorizing ability, and can be used as, for example, a deodorizing fiber.

It can also be used as an optical recording layer, an electrophotographic carrier generating layer, a dye layer of an organic solar cell, and the like.

V Specific Action and Effect of the Invention In the present invention, the monomer represented by the formula (I) is used,
Since a phthalocyanine addition condensation resin is obtained by adding this monomer and a compound capable of addition condensation to this monomer, a phenol resin, a urea resin, and a melamine containing a phthalocyanine ring in the main chain, respectively, depending on the compound used. Resin or the like can be obtained.

Phthalocyanine can be introduced into the resin as the reaction product at a content of up to 50 wt%. And, these resins can be formed into a thin film and can be formed into a film having a thickness of about 1 μm.

The phthalocyanine addition-condensation resin thus obtained may be a highly functional material applicable to a resin processing agent having an odor eliminating property, an optical recording layer, an electrophotographic carrier generating layer, a dye layer of an organic solar cell, and the like. it can.

VI Specific Examples of the Invention Hereinafter, the present invention will be described in more detail by showing specific examples of the invention.

Example 1 PcCON with trimellitic anhydride, urea and CoCl ₂
H ₂ ) ₄ [central atom; Co (II)] was synthesized.

Similarly, the central atom is Ni (II), Mg (II), Al (II
I), Mn (II), Fe (III), Cu (II), Sn (II), Lu
(III) was also synthesized.

Next, PcCONH ₂ ) ₄ (Pc compound) synthesized in this way
Novolak, resole, dimethylol urea, polymethylol urea, methylol melamine, polymelamine (melamine-formaldehyde mixture refluxed for 1 hour) synthesized by reacting each of phenol, urea and melamine with formalin by a conventional method. The respective products were reacted to obtain the desired product.

In this case, water was used as the solvent, and the raw material (monomer) concentration was 5 to 25%. Acid catalyst or oxalic acid was used as the catalyst, and ammonium chloride or hexamethylenetetramine was used as the basic catalyst. The catalyst amount was 0.1 to 2% relative to the monomer, and the reaction was carried out at 100 to 150 ° C for 2 to 36 hours.

The ratios of the Pc compound and the prepolymer were as follows. The reaction products are also shown.

Example 2 A Co (II) phthalocyanine tetraamide derivative was synthesized in the same manner as in Example 1.

To 1.0 g of this derivative, add 10 m of 35% formalin aqueous solution,
An aqueous solution of NNaOH (1 m) was further added, the mixture was appropriately diluted with distilled water, and the mixture was reacted at room temperature for 24 hours. After the reaction, dissolve in a large amount of water, separate by filtration and concentrate, add methanol, and add PcCO
NH-CH ₂ OH) ₄ [central atom; Co (II)] 0.5 g was obtained.

Similarly, the central atom is Ni (II), Mg (II), Al (II
I), Mn (II), Fe (III), Cu (II), Sn (II), Lu
(III) was also synthesized.

Next, PcCONH-CH ₂ OH) ₄ (Pc synthesized as described above
When the compound) was reacted with each prepolymer of Example 1 in the same manner as in Example 1, a phenol resin, a urea resin, and a melamine resin were obtained in the same manner as in Example 1 depending on the prepolymer used.

The resin obtained as described above exhibited a blue to green color, was extremely hard, and was completely insoluble in a solvent that dissolves phthalocyanine such as cold concentrated sulfuric acid. As described above, since these resins are insoluble and infusible solids, the number average molecular weight could not be measured. Regarding the resinization of the resole, a brownish-red resin was obtained, which is thought to have decomposed the phthalocyanine during the thermal polymerization, but this is considered to be the color of the decomposed product due to the ether bond site of the benzyl ether formed during the resole polymerization. .

Also, the polymerizability is very high.

Regarding the urea resin, when the Pc content was up to 20 wt%, the thermal properties of the obtained resin were greatly improved, and it was possible to introduce it into the resin in an amount of 50 wt% or more.

Infrared absorption spectrum of urea resin is 3300 to 3400 cm ⁻¹ ν of phthalocyanine 20 wt% resin by polymerization.
_OH is decreasing and ν _CH near 2900 cm ^-1 is increasing. 1550
The absorption attributed to the amide at ~ 1660 cm ^-1 became broad and showed the same behavior as the urea resin.

From the result of visible spectrum measurement, when phthalocyanine wt% was increased, a wide absorption band around 600 nm was obtained due to the state where phthalocyanine rings were stacked or assembled.
From the comparison with the absorption spectrum of the polymerization solution, it was found that the phthalocyanine rings were uniformly dispersed in the solution and assembled when concentrated and immobilized by the polymerization.

Regarding resinification, it is possible to form a thin film on a glass substrate by 1μ
High absorbance was exhibited at a film thickness of about m.

Example When the deodorizing effect was examined using the phthalocyanine addition condensation resin obtained as described above, a good deodorizing effect was exhibited for malodorous substances such as human waste.

Claims (1)

[Claims] 1. A monomer represented by the following formula (I) is used,
This monomer is subjected to addition condensation with phenols, ureas or melamines to give a phthalocyanine ring in the main chain at 50 wt%.
A process for producing a phthalocyanine addition-condensation resin, which comprises obtaining a phthalocyanine addition-condensation resin containing: Formula (I) PcCONH-R) n (In the above formula (I), Pc represents a phthalocyanine residue, R represents H or -LOH (wherein L represents a lower alkylene group), and n represents. It is an integer of 1 or more. }