JPH0412886B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to polyethynyl acetylene derivatives.

[Industrial application field]

The polyethynyl acetylene derivative of the present invention is a conjugated polymer and can be used as a conductive polymer and a pattern-forming resist material.

[Prior art and problems]

Until now, in the following formula (), R ₁ is −
C≡C-R'(R' is a hydrogen atom or -SiX ₁ X ₂ X ₃ , and X ₁ , X ₂ and X ₃ are each a hydrogen atom or an alkyl group) is known. However, these materials have a short conjugated system and lack order in the direction of development of the conjugated system, resulting in poor conductivity and low contrast and resolution as pattern-forming resist materials.

[Means for Solving the Problems] In view of these problems, the present inventors have conducted intensive studies to obtain a polyacetylene compound in which the conjugated system is sufficiently long and the conjugated system has developed in an orderly manner. An ethynyl acetylene derivative was obtained.

That is, in the present invention, the repeating unit is represented by the formula ()
A polyethynyl acetylene derivative whose number of units is represented by an integer in the range of 10 to 1000 (in the formula (), R is -(CH ₂ ) _o -COO・¹ / _n M, and n is an integer of 8 or more and 22 or less, M is a divalent, trivalent or tetravalent metal ion or proton,
m is the valence of ion M. ).

In addition, divalent, trivalent or tetravalent metal ions include cadmium, iron, cobalt, nickel,
copper, zinc, mercury, palladium, platinum, rhodium,
Examples include chromium, manganese, aluminum, tin, lead, magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum metals, and preferably cadmium,
These are iron, aluminum, and tin ions.

Therefore, M in formula () may be a plurality of types of metal ions or protons, or may be only one type.

The polyethynyl acetylene derivative of the present invention is a monosubstituted diacetylene compound represented by the following formula (), where n is an integer of 8 or more and 22 or less (where M is a divalent, trivalent or tetravalent metal ion or a proton , m is the valence of the ion M), γ rays, electron beams,
It can be obtained by applying energy irradiation (hereinafter simply referred to as "energy irradiation") such as X-rays, ultraviolet rays, visible light, and infrared rays (heat).

H−C≡C−C≡C−(CH ₂ ) _o −COO・¹ / _n M
() Preferably, a Langmeur-Blodget film of a monosubstituted diacetylene compound of the formula (hereinafter "
Create a LB film (referred to as “LB film”) and irradiate ultraviolet rays, visible light,
It can be obtained by applying energy irradiation such as infrared rays (heat), electron beams, X-rays, and γ-rays.

An example of the synthesis method is shown below. First, H-C≡C-(CH ₂ ) _o -COOH(1) (n is 8 or more 22
The following integer) is methylated to synthesize H-C≡C-(CH ₂ ) _o -COOCH ₃ (2).
CuC≡C-(CH 2 ) _o -COOCH ₃ (3) is obtained by adding the ethanol solution of ₍₂ ) to an equimolar ammonia aqueous solution of copper iodide () and reacting. When this acetylide (3) is reacted in an iodine tyl ether solution, I-C≡C-(CH ₂ ) _o -COOCH ₃ (4) is easily obtained.

On the other hand, CuC≡C-COOH (5) was synthesized from H-C≡C-COOH in a pyridine solvent.
(4) at 120℃ for 16 hours to obtain HOOC-C≡C-C≡C-(CH ₂ ) _o -COOCH ₃ (6)
Synthesize. By decarboxylating (6) and hydrolyzing the ester, a monosubstituted diacetylene compound H-C≡C-C≡C-(CH ₂ ) _o -COOH (7) is obtained.
When n is an integer of 23 or more, the hydrophobicity of the molecule is too strong, making it impossible to obtain a high-quality LB film, and the sensitivity to energy irradiation also decreases. On the other hand, when n is an integer of 7 or less, photopolymerization proceeds simply by leaving it under white light, and the reaction rate of photopolymerization is extremely high. It cannot be obtained well, and the hydrophobicity of the molecule is too weak, so the ability to form an LB film is reduced. Therefore, in the present invention, n in (7) is 8
An integer of 22 or less is used as a raw material.

This monosubstituted diacetylene compound is combined with cadmium,
Any one of iron, cobalt, nickel, copper, zinc, mercury, palladium, platinum, rhodium, chromium, manganese, aluminum, magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum metals, etc.
Alternatively, an LB film can be created by spreading it on a water surface containing one or more types of ions or on a water surface not containing metal ions and applying the Langmiur-Blodget method (hereinafter referred to as "LB method").

For example, apply a 100W low-pressure mercury lamp to this LB film for 10cm.
By irradiating from a distance of 1 second to 12 hours,
The polyethynyl acetylene derivative of the present invention can be obtained.

Considering the ease of photopolymerization and the orderliness of the LB film, n in (7) is preferably an integer of 12 or more and 16 or less.

The polyethynyl acetylene derivative of the present invention is
Its molecular structure can be investigated by measuring IR spectra, Raman spectra, and UV-VIS spectra.

From the IR spectrum, ν (C=C) is around 1600 cm ^-1 , ν (C-H) of =CH- is 3000 to 3300 cm ^-1 , and ν (C≡C) of -C≡C- is 2100 to 3300 cm -1. 2320 cm ^-1 , ν(C-H) of -CH ₂ - is 2835 to 2980 cm ^-1 , scissor vibration of -CH ₂ - is 1435 to 1490 cm ^-1 , lateral vibration is 720 to 740 cm ^-1 , ν of carboxylic acid metal salt
(C=O) is observed near 1400 cm ^-1 and from 1520 to 1610 cm ^-1 . Furthermore, ν(C-H) and ν(C≡C) of the molecular terminal ethynyl group -C≡CH are clearly observed in the monomer stage of (7), but their intensity decreases and disappears with photopolymerization.

In addition, Raman spectra (He-Ne laser,
6328 Å), ν(C=C) becomes 1460~1520 cm ^-1 ,
ν(C≡C) is observed near 2120 cm ^-1 . 2120
ν (C≡C) of cm ⁻¹ is also observed for the monomer before photopolymerization, indicating that it is not shifted by photopolymerization. This is because in the photopolymerization of monosubstituted diacetylene derivatives, 1,2' polymerization occurs between the ethynyl groups at the end of the molecule, and the other C≡C group is dangling from the polyacetylene skeleton as a side chain. It will be done. The conjugated chain length of this polymer is
It can be determined from the Raman shift value of ν (C=C).

In the UV-VIS spectrum, an absorption edge is observed near 600 nm. Compared to before photopolymerization, the absorption edge is red-shifted, and the 240n derived from diacetylene group
Absorption near m has decreased or disappeared.

The above spectrum data shows that the monosubstituted diacetylene compound (7) was 1,2' polymerized in the LB film and transformed into the polyethynyl acetylene derivative of the present invention.

In (7), LB of the compound H-C≡C-C≡C-( _CH2 ) _20- COOH(8) where n=20 and M is a proton
It is known that polymers can be obtained by irradiating films with UV light. [A. Roedel-Taixier,
Molecular Crystal and Liquid
Crystal (A.Ruaudel−Teixier, Mol.Cryst.
Liq.Cryst., 96 , 365-372 (1983). )]. but,
Since the LB film of free carboxylic acid (8) was created on a water surface that does not contain metal ions, the LB film lacked uniformity and a high-quality thin film was not obtained. The LB film of free carboxylic acid in (8) is formed by UV photopolymerization, where λ=
It becomes a red polymer with an absorption peak at 500 nm. This indicates that 1,4' polymerization occurs between molecules and polydiacetylene is produced.

The polyethynyl acetylene derivative of the present invention has λ=
Since it does not have an absorption peak at 500 nm, A. Ruaudel-
This is different from the polymer reported by Teixie.

The polyethynyl acetylene derivative of the present invention is a type of conjugated polymer and can be used as a conductive polymer. In addition, compared to monomer diacetylene compounds, polyethynyl acetylene has
Since it has low solubility in solvents, it can be separated using the difference in solubility.

Furthermore, since polyethynylacetylene has a structural characteristic in which polyacetylene has a C≡C bond attached as a side chain, it is thought that it can be used for the synthesis of polyacene, which is expected to be used as a metal conductor and high-temperature superconductor. It will be done.

〔Example〕

The present invention will be explained in more detail with reference to Examples below.

Example 1 (Synthesis of 10,12-tridecadiinoic acid) 2 g of 10-undecinoic acid H-C≡C-( _CH2 ) ₈ -COOH(1')
(11 mmol) and 8.5 mg of para-toluenesulfonic acid were added to 30 ml of anhydrous methanol and refluxed for 2 hours. After cooling the reaction solution, mix it with an aqueous sodium hydrogen carbonate solution.
After shaking, the precipitate was washed with water and saturated brine to obtain 1.97 g of methyl ester H-C≡C-(CH ₂ ) ₈ -COOCH ₃ (2').

To an ammoniacal aqueous solution of 1.9 g (10 mmol) of copper iodide (2), add 1.97 g (10 mmol) of (2') to 50
A solution in ml of methanol was added and stirred for 15 minutes under nitrogen atmosphere. The precipitate was filtered, washed with water, methanol, and ether, and then dried under vacuum to obtain the copper acetylide derivative CuC≡C-( _CH2 ) _8-
COOH(3′) was obtained. Dissolve this in diethyl ether and react with iodine to obtain 2.1 g of I-C≡C-(CH ₂ ) ₈ -COOH (4')
(6.5 mmol) was obtained.

Next, while stirring 7 ml of a 33% aqueous solution of ethylamine containing 6.4 mg of copper chloride, a solution of 0.455 g (6.5 mmol) of propylic acid H-C≡C-COOH in 3.5 ml of methanol was added. This mixture was kept at 40 °C under nitrogen atmosphere, and 2.1 g (6.5 mmol) of (4') was
3.5 ml of methanol solution was gradually added. The reaction mixture was treated with a KCN aqueous solution, acidified and extracted with ether to give 0.66 g (2.5 mmol) of HOOC-C≡C-C≡C-(CH ₂ ) ₈ -COOCH ₃
(6′) was obtained.

A mixture of 0.66 g (2.5 mmol) of (6'), 5 ml of dioxane, and 53 mg of copper powder was decarboxylated by refluxing for 2 hours, resulting in 0.45 g (2.0 mmol) of H-C≡C-C≡C- ( _CH2 ) ₈ - _COOCH3 (9) was obtained. 0.45 g (2.0 mmol) of this (9) was hydrolyzed in a mixed solvent (1:1) of 10% aqueous sodium hydroxide and xane, treated with dilute hydrochloric acid, and -C≡C-C≡C-( _CH2 ) ₈ -COOH(7')0.14
g (0.68 mmol) of white crystals were obtained.

(Synthesis of polyethynyl acetylene derivative using 10,12-tridecadiinoitsukacid) A 2mM chloroform solution of the previously synthesized 10,12-tridecadiinoitsukacid (7') was prepared.
A 0.5mM Cdcl ₂ aqueous solution was poured into a Langmiur trough (film balance) manufactured by LAUDA, and a chloroform solution of (7') was dropped onto the water surface. The surface pressure of a monomolecular film formed on the water surface
A 69-layer cumulative film was created by the LB method on a calcium fluoride substrate while maintaining a constant pressure of 25 dyn/cm.
The cumulative ratio was 0.96.

This LB film was irradiated with a 100W low-pressure mercury lamp to undergo photopolymerization.

In the IR spectrum, ν(C=C) (1600 cm ^-1 ),
ν(C-H) of =CH in polyacetylene structure (3250
cm ^-1 ), ν of -C≡C- (C≡C) (2310 cm ^-1 ), ν _a of methylene group -CH ₂ - (C-H) (2930 cm ^-1 ), ν _s
(C-H) (2855cm ^-1 ), CH ₂ scissor vibration (1465cm
^-1 ), CH ₂ lateral vibration (725 cm ^-1 ), and carboxylate ν(C=O) (1410 cm ^-1 , 1547 cm ^-1 ) were observed. ν(C-H) of ≡C-H was not observed.
In addition, ν (C=O) of free carboxylic acid was also observed at 1690 cm ^-1 .

Raman spectrum (He-Ne laser, 6328Å)
Then, ν(C=C)(1480cm ^-1 ), ν(C≡C)
(2120cm ^-1 ) was observed. The conjugate chain length was 30 from the Raman shift of ν(C=C).

In the UV-VIS spectrum, an absorption edge was observed around 600 nm. No absorption peaks were observed at 240 nm and 500 nm.

The part not subjected to UV photopolymerization remained as monomer (7') and was dissolved in ethanol, but the photopolymerized part did not dissolve and formed a negative pattern.

Example 2 (Synthesis of 16,18-nonadecadiinoic acid) In Example 1, 2 g of 16-heptadecinoic acid H-C≡C-(CH ₂ ) ₁₄ -COOH (1″) was
A similar reaction was carried out using 10-undecinoic acid instead of 16,18-nonadecadinoic acid H-C≡C-C≡C-(CH ₂ ) ₁₄ -COOH
0.50 g of white crystals (7″) were obtained.

(Synthesis of polyethynyl acetylene using 16,18-nonadecadiinoic acid) The previously synthesized (7″) was converted into (7′) in Example 1.
A cumulative film of 69 layers was created with a cumulative ratio of 0.98. This LB film is irradiated with a 100W low-pressure mercury lamp,
Photopolymerization was performed.

In the IR spectrum, ν(C=C) (1600 cm ^-1 ),
ν(C-H) of =CH in polyacetylene structure (3250
cm ^-1 ), ν of -C≡C- (C≡C) (2310 cm ^-1 ), ν _a of methylene group -CH ₂ - (C-H) (2930 cm ^-1 ), ν _s
(C-H) (2855cm ^-1 ), CH ₂ scissor vibration (1465cm
^-1 ), CH ₂ lateral vibration (725 cm ^-1 ), and carboxylate ν(C=O) (1410 cm ^-1 , 1547 cm ^-1 ) were observed. ν(C-H) of ≡C-H was not observed.
In addition, free carboxylic acid ν(C=O) (1690 cm ^-1 ) was also observed.

Raman spectrum (He-Ne laser, 6328Å)
Then, ν(C=C)(1465cm ^-1 ), ν(C≡C)
(2120cm ^-1 ) was observed. From the Raman shift of ν (C=C), the conjugate chain length was 200.

In the UV-VIS spectrum, an absorption edge was observed around 600 nm. No absorption peaks were observed at 240 nm and 500 nm.

The portion not subjected to UV photopolymerization remained as a monomer (7″) and was dissolved in ethanol, but the photopolymerized portion did not dissolve and formed a negative pattern.

Example 3 (Synthesis of 12,14-pentadecadiinoic acid) 12-tridecinoic acid H-C≡C-( _CH2 ) ₁₀ -COOH (1) 2 g
(9.5 mmol) and 7.5 mg of para-toluenesulfonic acid were placed in 30 ml of anhydrous methanol, refluxed for 2 hours, cooled, mixed with an aqueous sodium bicarbonate solution and shaken, and then the precipitate was washed with water and saturated brine. A methyl ester H-C≡C-(CH ₂ ) ₁₀ -COOCH ₃ (2″) was obtained.

2.23 g (8.9 mmol) of CuSO ₄ 5H ₂ O to 10 mmol
was dissolved in a 30% ammonia aqueous solution and stirred under a nitrogen atmosphere. Add this to 40ml of water and 1.25g (18mmol)
of hydroxylamine hydrochloride was added and allowed to stand for 5 minutes. Add 2.0g (8.9mmol) (2″) to this solution at 45
ml of methanol was added and stirred for 15 minutes under nitrogen atmosphere. The precipitate was filtered, washed with water, methanol, and diethyl ether, and then dried under vacuum to obtain a copper acetylide derivative CuC≡C-( _CH2 ) ₁₀ - _COOCH3 (3'').

A similar reaction was carried out using this acetylide (3'') in place of (3') in Example 1, and 12,14
-Pentadecadiinoic acid H-C≡C-C≡C-(CH ₂ ) ₁₀ -COOH (7)
0.155g (0.66mmol) of crystals were obtained.

(Synthesis of polyethynyl acetylene derivative using 12,14-pentadecadiinoic acid) Using the previously synthesized (7) in place of (7') in Example 1, 69 layers were accumulated at a cumulative ratio of 0.97. A membrane was created. This LB film was irradiated with a 100W low-pressure mercury lamp to undergo photopolymerization.

In the IR spectrum, ν(C=C) (1600 cm ^-1 ),
ν(C-H) of =CH in polyacetylene structure (3250
cm ^-1 ), ν of -C≡C- (C≡C) (2310 cm ^-1 ), ν _a of methylene group -CH ₂ - (C-H) (2930 cm ^-1 ), ν _s
(C-H) (2855cm ^-1 ), CH ₂ scissor vibration (1465cm
^-1 ), CH ₂ lateral vibration (725 cm ^-1 ), and carboxylate ν(C=O) (1410 cm ^-1 , 1547 cm ^-1 ) were observed. ν(C-H) of ≡C-H was not observed.
In addition, free carboxylic acid ν(C=O) (1690 cm ^-1 ) was also observed.

Raman spectrum (He-Ne laser, 6328Å)
Then, ν(C=C)(1470cm ^-1 ), ν(C≡C)
(2120cm ^-1 ) was observed. The conjugate chain length was 50 from the Raman shift of ν(C=C).

In the UV-VIS spectrum, an absorption edge was observed around 600 nm. No absorption peaks were observed at 240 nm and 500 nm.

The portion not subjected to UV photopolymerization remained as monomer (7) and was dissolved in ethanol, but the photopolymerized portion did not dissolve and formed a negative pattern.

Example 4 (Synthesis of 21,23-tetracosadiinoitsukaside) In Example 3, 2 g of 21-docosinoitsukaside H-C≡C-(CH ₂ ) ₁₉ -COOH (1) was added to (1). Perform a similar reaction using instead 21,
23-Tetracosadiinoic acid H-C≡C-C≡C-( _CH2 ) ₁₉ -COOH (7)
crystals were obtained.

(Pattern formation using 21,23-tetracosadiinoic acid) Previously synthesized (7) was used in place of (7') in Example 1 to create a 69-layer cumulative film with a cumulative ratio of 0.99. . This LB film was irradiated with a 100W low-pressure mercury lamp to undergo photopolymerization.

In the IR spectrum, ν(C=C) (1600 cm ^-1 ),
ν(C-H) of =CH in polyacetylene structure (3250
cm ^-1 ), ν of -C≡C- (C≡C) (2310 cm ^-1 ), ν _a of methylene group -CH ₂ - (C-H) (2930 cm ^-1 ), ν _s
(C-H) (2855cm ^-1 ), CH ₂ scissor vibration (1465cm
^-1 ), CH ₂ lateral vibration (725 cm ^-1 ), and carboxylate ν(C=O) (1410 cm ^-1 , 1547 cm ^-1 ) were observed. ν(C-H) of ≡C-H was not observed.
In addition, free carboxylic acid ν(C=O) (1690 cm ^-1 ) was also observed.

Raman spectrum (He-Ne laser, 6328Å)
Then, ν(C=C)(1490cm ^-1 ), ν(C≡C)
(2120cm ^-1 ) was observed. The conjugate chain length was 20 from the Raman shift of ν(C=C).

In the UV-VIS spectrum, an absorption edge was observed around 600 nm. No absorption peaks were observed at 240nm and 500nm.

The portion not subjected to UV photopolymerization remained as monomer (7) and was dissolved in ethanol, but the photopolymerized portion did not dissolve and formed a negative pattern.

Example 5 (Synthesis of 24,26-heptacosadiinoitsukaside) In Example 3, 2 g of 24-pentacosadiinoitsukaside H-C≡C-( _CH2 ) ₂₂ -COOH(1''''')
Perform a similar reaction using (1) instead of
24,26-Heptacosadioinoic acid H-C≡C-C≡C-( _CH2 ) ₂₂ -COOH(7''''')
crystals were obtained.

(Synthesis of polyethynyl acetylene derivative using 24,26-heptacosadiinoic acid) (7′′′′) was used in place of (7′) in Example 1 to form 69 layers at a cumulative ratio of 1.0. A membrane was created. This LB film was irradiated with a 100W low-pressure mercury lamp to undergo photopolymerization.

In the IR spectrum, ν(C=C) (1600 cm ^-1 ),
ν(C-H) of =CH in polyacetylene structure (3250
cm ^-1 ), ν of -C≡C- (C≡C) (2310 cm ^-1 ), ν _a of methylene group -CH ₂ - (C-H) (2930 cm ^-1 ), ν _s
(C-H) (2855cm ^-1 ), CH ₂ scissor vibration (1465cm
^-1 ), CH ₂ lateral vibration (725 cm ^-1 ), and carboxylate ν(C=O) (1410 cm ^-1 , 1547 cm ^-1 ) were observed. ν(C-H) of ≡C-H was not observed.
In addition, free carboxylic acid ν(C=O) (1690 cm ^-1 ) was also observed.

Raman spectrum (He-Ne laser, 6328Å)
Then, ν(C=C)(1495cm ^-1 ), ν(C≡C)
(2120cm ^-1 ) was observed. From the Raman shift of ν (C=C), the conjugate chain length was 17 to 18.

In the UV-VIS spectrum, an absorption edge was observed around 600 nm. No absorption peaks were observed at 240 nm and 500 nm.

The part not subjected to UV photopolymerization remained as a monomer (7'''') and was dissolved in ethanol, but the photopolymerized part did not dissolve and formed a negative pattern.

Example 6 A 2mM chloroform solution of (7″) synthesized in Example 2 was prepared. A 5mM Cdcl ₂ aqueous solution was poured into the Langmire trough used in Example 1, and the chloroform solution of (7″) above was poured onto the water surface. was dripped. The surface pressure of the monomolecular film formed on the water surface was maintained at a constant pressure of 25 dyn/cm, and the LB was placed on the calcium fluoride substrate.
A 69-layer cumulative film was prepared by the method. This LB film
Photopolymerization was performed by irradiating with a 100W low-pressure mercury lamp.

In the IR spectrum, ν (C=
O) (1410 cm ^-1 , 1547 cm ^-1 ) were observed, but ν(C=O) (1690 cm ^-1 ) of free carboxylic acid was not observed. Other IR absorption and Raman spectra,
The UV-VIS spectrum was observed in the same manner as in Example 2. The conjugate chain length was 200.

The portion not subjected to UV photopolymerization was dissolved in ethanol, but the photopolymerized portion was not dissolved and a negative pattern was formed.

Example 7 A similar experiment was carried out in Example 6 using a mixed aqueous solution of 0.5mM Cdcl _{2 and} 0.5mM ALCl ₂ instead of the 5mM Cdcl 2 aqueous solution to create a 69-layer LB film. This LB film was irradiated with a 100W low-pressure mercury lamp to undergo photopolymerization.

In the IR spectrum, ν (C=
O) (1415 cm ^-1 , 1550 cm ^-1 ) were observed, and ν(C=O) (1690 cm ^-1 ) of free carboxylic acid was also observed. Other IR absorption and Raman spectra, UV-
The VIS spectrum was observed in the same manner as in Example 2.
The conjugate chain length was 200.

The part that was not UV photopolymerized was dissolved in ethanol, but the photopolymerized part was not dissolved and a negative pattern was formed.

Example 8 A similar experiment was carried out in Example 6 using pure water containing no metal ions in place of the 5mM Cdcl ₂ aqueous solution to produce a 69-layer LB film. This LB
The film was irradiated with a 100W low-pressure mercury lamp to undergo photopolymerization.

In the IR spectrum, ν (C=
O) was not observed at all, and ν(C
=O) was observed at 1690 cm ^-1 . Other IR absorption, Raman spectrum, and UV-VIS spectrum were observed in the same manner as in Example 2. The conjugate chain length was 180.

The part that was not UV photopolymerized was dissolved in ethanol, but the photopolymerized part was not dissolved and a negative pattern was formed.

Claims (1)

[Scope of Claims] 1. A polyethynyl acetylene derivative in which the repeating unit is represented by the following formula () and the number of units is an integer in the range of 10 to 1000. (In the formula, R is -(CH ₂ ) _o -COO・¹ / _n M,
n is an integer of 8 or more and 22 or less, M is a divalent, trivalent or tetravalent metal ion or a proton, and m is the valence number of the ion M. )