JPS61152689A - Phthalocyanins - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (M is metal in group IIIB; X is halogen; Pc is phthalocyanin nucleus; R is alkyl, aryl, heterocyclic ring which may be substituted; Y is H, halogen; n is 5-16). EXAMPLE:Hexadeca-(OC2H5)16InBrPc. USE:Near infrared and infrared ray absorbent for optical recording media. PREPARATION:For example, the reaction of a compound of formula II with a compound of the formula: ROH such as ethanol is carried out at 140 deg.C for 2hr to give a compound of formula III. Then, the product is allowed to react with a compound of the formula: Li<+>(OC5H11)<-> at 150 deg.C for 2hr to form Li2 Pc(OR)16. Further, 1mol of the product is allowed to react with nmol MXY2 such as InCl3 in amyl alcohol at 130 deg.C for 1hr.

Description

BACKGROUND OF THE INVENTION Technical Field The present invention relates to phthalocyanine compounds, particularly phthalocyanine compounds having absorption in the near-infrared and infrared regions.

Prior art and its problems Phthalocyanine compounds are stable against light, heat, humidity, etc. and have excellent robustness. In particular, metal phthalocyanines are widely used as various dyes and pigments due to their high stability and strong color tone, and because metal ions exist in a large π-electron conjugated system, metal phthalocyanines are used for electrical conduction, photoconductivity, energy conversion, etc. It has attracted attention as a material for electrodes, catalysts, etc., and as a polymeric material for films and thin films that have advanced functions when blended with polymers, and various studies are being conducted on it.

One of the uses of these phthalocyanine compounds is as a light absorber.

However, when used as an absorbent, there is a demand for phthalocyanine compounds that do not absorb in the near-infrared and infrared regions but have absorption in the near-infrared and infrared regions.

TI Object of the Invention An object of the present invention is to provide a phthalocyanine compound having absorption in the near-infrared and infrared regions.

■ Disclosure of the invention - Such objects are achieved by the invention described below.

That is, the present invention formula %formula%) (In the formula, M represents I[[B metal atom.

X represents a halogen atom.

Pc represents a substituted or unsubstituted alkyl group, aryl group or heterocyclic group.

Y represents a hydrogen atom or a halogen atom.

(n represents a positive integer of 8 to 16) This is a phthalocyanine compound characterized by the following.

■Specific structure of the invention Hereinafter, a specific configuration of the present invention will be explained in detail.

The phthalocyanine compound of the present invention has the following formula % formula MX-Pc(-OR) (Y) (
I)n 1B-n In the above formula (I), M is a BIB metal atom (AJI,
Ga, In, Ti), among which AfL, G
a, In is preferred.

or a halogen atom, such as F, C, Br.

1, etc., and among them, Cl, Br, and 'I are preferred.

Pc is a phthalocyanine nucleus represented by the following formula (II).

In the above formula (■), the position where -OR or Y is substituted is 1
-16.

R is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, such as a methyl group or an ethyl group.

Propyl group, butyl group, pentylhexyl group, phenethyl group, cyclohexyl group, allyl group, dodecyl group,
CH20-C2H40゜impropenyl group, -C2H4
-C-free, -CH2-NH2, etc.; Substituted or unsubstituted 7-aryl group having 6 to 24 carbon atoms 1 For example, phenyl group, tolyl group, methoxyphenyl group, naphthyl group, phenyl chloride group, xylyl group, 00C2H5゜0CH2C , OCR20Hl -C)-C00CH3, etc.; Substituted or unsubstituted heterocyclic group 2 such as pyridyl group, pyrrolyl group, quinolyl group, furyl group, furfuryl group, chenyl group, piperidyl group, pyrimidyl group, etc.

Y is a hydrogen atom; a halogen atom, such as F, Cu, Br, I, etc.;
Among them, C1 and Br are preferred.

n represents a positive integer of 5 to 16, especially 8 to 16
It is preferable that

Specific examples of the 7 thalocyanine compounds of the present invention are listed below.

(1) Octa-3,6-(-0CH3)-An'
C5L'Pc(2) Octa-3, [1-(-002
Hs )-In CIPc (3) Octa-3,6-(-
00)-Ga CI Pc(0 octa-3,8-C-0
C3H7)-1nBrPc(5) Octa-3,13
-(-0C2Hs)-TI CIPc(6) octa-3,6-(-0i〉])--8heclPc (7) deca-(-000H3)-A-cross BrPc(8
) Deca-(-0-Cz Hs) All P
c(9) Undeka-(-〇 Bez)-GaBrP
c (10) Pentadeca-(-ooCl) In CI
Pc(11)pentadecarC-0-C>O(IB)A
ll CI Pc (12) Pentadeca-(-000C
2H5) Ga(!LPa(■3) Pentadeca-(-0-
C2H5) In I Pc (14) Pentadeca-
(-0-02H5) Ga I Pc (15) Hexadeca-(-〇
7) Hexadeca-(-0-Cz H5) InBrP
c(18) hexadeca-(-0C3H7) kl C
IPc(19) Hexadeca-(-0-C>CH3)
GaBrPc(20) hexadeca-(-00C1)
An BrPc (21) '77 decal (-0-02
H5) In CI Pc The 7-talocyanine compound of the present invention can be synthesized by a method according to the scheme -a &.

Scheme I Li 2 P c (-OR) +s + nMXY2
Purification of the reaction product using this method is carried out as follows.

The reaction product is cooled to 100° C., diluted with ethanol, then returned to room temperature and filtered. This filtered material is washed with ethanol, further washed with an ethanol-aqueous solution,
dry. The crude product thus obtained is developed on a silica column with toluene and purified by one separation.

Scheme 2 140°C, 1 hr nRo-◆ + MXPc (Y) IG purification is performed as in Scheme 1.

(2) Specific effects of the invention Since the phthalocyanine compound of the present invention is represented by MX P C+ OR) (Y) 1B, one having absorption in the near-infrared and infrared regions can be obtained.

Therefore, near-infrared light, which is extremely robust against light and heat,
Infrared absorbers have been realized and are useful as absorbers for optical recording media, electrophotographic photoreceptors, etc.

(1) Specific Examples of the Invention One specific example of the present invention will be shown below to explain the present invention in further detail.

4 mol of ethanol (EtoH) at 140°C.

Let it react for 2 hours.

To 4 moles of this compound, 2 moles of Li''(OC5Hll) was added and reacted at 150°C for 2 hours to form Li2Pc(
-OEt)IG was obtained. Furthermore, 1131 mol of InC was added to 1 mol of this compound.

The reaction was carried out in amyl alcohol at 130°C for 1 hour to obtain the desired product. After cooling this reaction product to 100°C,
Dilute with ethanol (E t OH), warm to room temperature, and filter. a The separated material was washed with EtOH, and further Et
Washed with OH-H2O (1:1) solution and dried.
The crude product thus obtained was developed with toluene on a silica column, separated for 1 time, and purified to obtain the desired product.

Yield 18.6% Elemental analysis CHN In Calculated value 7% 54.44 5.87 7.94 8.1
4Actual value/%54.52 5.88? , 91 8
．． 16 Absorption maximum λ = 830n (measured by forming a thin film with a thickness of 0.1 IL by spinner coating) Example 27 2゛A target product was obtained in the same manner as in Example 1.

Yield 23.2% elemental analysis CHN In The target product was obtained in the same manner as in Example 1.

Yield 28.4% Elemental analysis CHN Ga Total 3 results (I direct 7% 5B, 94 2.48
8.88 4.28 Actual value/%57.9
4 2.47 B, 91 4.30 Example 4
6 6 The desired product was obtained in the same manner as in Example 1.

Yield 31.8% Elemental analysis CHN Ga Calculated value 7% 8B, 25 2.7B 5.52 3.
44 actual value/%f15.84 2.72 5.58
3.49 Example 5 Synthesis 15f 16 moles of β-naphthol and 6 moles of KOHl were reacted in quinoline at 140° C. for 1 hour.

Add 1 mol of I ncuPc (C1)IG to this,
It was made to react at 160-180 degreeC for 1 hour.

The obtained reaction product was purified in the same manner as in Example 1.

Yield 23.6% Elemental analysis CHN In Calculated value 7% 78.52: lB2 3.82 3.
91 actual value/%77.94 3.85 3.88 3
．． 89 absorption maximum input + ma violet 840 ns (measured by forming SS with a thickness of 0, IIL + 1 by spinner coating) Example 6 A target product was obtained in the same manner as in Example 5 of 11 Hexachemicals.

Yield 28.5% elemental analysis Watch CHNA The target product was obtained in the same manner as in Example 5.

Yield 22.8% Elemental analysis CHN In Calculated value 7% 37.29 3.10 8.22 8.3
7 Actual value/% 37.11 3.12 8-21 8.
39 Example 8 B 21 The desired product was obtained in the same manner as in Example 5.

Yield 29.4% Elemental analysis CHNIn Calculated value/% 49.15 4.17 B, 49 8.
71 actual value/%48.93 4.19 8.51 8
．． 70 Applicant TDC Co., Ltd. Agent Patent Attorney Yo Ishii - Procedural amendment (voluntary) August 7, 1985 Michibe Uga, Commissioner of the Patent Office 2. Name of the invention: phthalocyanine compound 3. Person making the amendment Relationship to the incident Patent applicant address: 13-1 Nihonbashi-chome, Chuo-ku, Tokyo
(306) Representative of TDC Co., Ltd.
Hiroshi Otoshi 4, Agent 101 Telephone 864-4498 Address 3-2-2 Iwamoto-cho, Chiyoda-ku, Tokyo Column 6 of “Claims” of the specification, [2, Patent The description in the section "Scope of Claims" is amended as follows.

“2. Scope of claims formula %formula%) (In the formula, M represents an InB metal atom.

Or represents a halogen atom.

Pc represents a phthalocyanine nucleus.

R represents a substituted or unsubstituted alkyl group, aryl group or heterocyclic group.

Y represents a hydrogen atom or a halogen atom.

n represents a positive integer from 5 to 16) A phthalocyanine compound characterized by

Claims (1)

[Claims] Formula MX-PC-(OR)_n(Y)_1_6_-_n {wherein M represents a IIIB metal atom. X represents a halogen atom. Pc represents a substituted or unsubstituted alkyl group, aryl group or heterocyclic group. Y represents a hydrogen atom or a halogen atom. n represents a positive integer from 5 to 16. } A phthalocyanine compound characterized by: