JP2729939B2 - Photosensitive film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] TECHNICAL FIELD The present invention relates to a photosensitive composition and a photosensitive composition.
, Especially short wave composed of novel barbituric acid compounds
Deep UV [Deep Ultraviolet (DU
V)] Positive photoresist containing a photoresist sensitizer
The present invention relates to a distaste composition and a positive photoresist layer. [0002] 2. Description of the Related Art A photoresist is irradiated with actinic radiation, for example, purple.
After exposure to external radiation, the solubility in the developer solution changes.
Is a photoresist. Photoresist composition
The product is a photosensitive compound (hereinafter sometimes referred to as a sensitizer [sensit
iser or photo-sensitizer]
And film forming polymer resin and solvent. Other types
Compositions such as photopolymers in suitable solvents are also possible.
You. Substrate to be patterned with photoresist composition
And then remove the solvent, typically with heat, to remove the substrate
The photoresist is left as a coated thin film. Photo cash register
As a result of irradiating the resist, the exposed portion of the resist film
Different between exposed (masked) parts
Solubility, which creates a surface relief pattern after development.
Occurs. Exposed area becomes more soluble by developer solution
The photoresist is called a "positive" photoresist. Dew
"Negative-type" photoresist that makes the optical region hardly soluble
Call. The present invention is used for a positive photoresist composition.
To a class of compounds suitable for [0003] Positive-acting photoresists are typically aqueous solutions.
Resin soluble in lukari, such as novolak resin or poly
(P-hydroxystyrene) and diazonaphthoquinone
Consists of a sulfonic ester photosensitizer. Dissolve resin and photosensitizer
For example spin coating, spray coating or from a medium or solvent mixture
The substrate, e.g., a silicon wafer or crystal, may be
Apply to chrome-plated glass plate. Positive photoresist
The developer used for the processing is an aqueous alkaline solution, for example,
Sodium tasilicate, potassium hydroxide, tetramethylan
With monium hydroxide and ammonium hydroxide
is there. The developer is coated with light or other forms of irradiated coating.
The area of the photoresist film is removed and the photoresist film is
Create a roof pattern. Use of photoresist film for various substrates
Doing so is an essential step in integrated circuit manufacturing. One board
Generally a silicon wafer with a thin oxide coating or other coating
For example, they may contain silicon nitride or aluminum.
You. Exposure (through mask pattern) to resist layer
Develop the relief pattern and apply the pattern to the substrate
During a series of steps, including substrate etching into the material
An optical film is used to form a pattern on the substrate. Ma
The mask pattern is accurately reproduced in the substrate etching pattern
Is essential. To achieve this high degree of accuracy
Mask pattern is sufficiently resolved in the photoresist layer
Must have been. The laws of optics and diffraction are
This indicates that the resolution is improved by shortening the wavelength.
Therefore, the short wavelength ultraviolet (DUV) region (200-300n)
m) Photoresist that can be operated in the near ultraviolet (NUV) region
Limited to operation in the wavelength range (300-400 nm)
Should have higher effective resolution than gyst
You. Novolac as alkali-soluble, film-forming polymer
Conventional photoresist using resin is about 1 micron thick
Even membranes are highly absorbing in the DUV range, and
Can not be used in the area. Diazonaphthoquinonesulfonic acid
STELL is a traditional NUV photoresist sensitizer.
Always used. These ester sensitizers are DUV
Optically active (photosensitive), but as a DUV photosensitizer
Significant limiting conditions for the use of These exposures
The agent shows strong absorption in the DUV range, up to the resist composition
Make it too light absorbing. These DUV absorptions are exposed to radiation
However, since it is slightly exposed to light, the film is absorbed during the exposure process.
The luminosity does not increase greatly. Ideally, the light of the photosensitizer
Chemical products are in the area of the radiation used to expose the resist
Not absorbed, all absorbed light is chemically available
The sensitivity needs to be maximized. These prior art
The photosensitizer also has an NUV absorption band, which is
It can be used as a V photoresist. Naturally
And filter the exposure source to prevent a drop in resolution.
Need to remove long-wavelength radiation as
NUV response is considered a drawback in true DUV resist
Like. Therefore, during the integrated circuit manufacturing process, the DUV
A novel photosensitizer with specificity that works effectively in the optical domain
There is a need for formulas with photosensitive compounds and photosensitizers
It is clear. The present invention is suitable for use in desired areas.
It relates to the use of a class of compounds which are particularly well suited. Constructing a photoresist system for the DUV region
Several other attempts have been made. For example, Rei
chmanis, Wilkins, Chordross
And Gooden in UK Patent Application (Published) No. 2,092.
As described in No. 9,168, polymer and sensitizer components
Photochemistry of ortho-nitrobenzyl groups bound to both
Some systems based on statistical properties are shown. Orthoni
Use of trobenzyl chemistry for photoresists.
Another disclosure is U.S. Pat. No. 3,849,137. Chemical properties suitable for DUV photoresists
Of the chain breakage of a high molecular weight polymer into a low molecular weight polymer
There are also properties. In this case, the energy of DUV light is polymer
Enough to break the bonds in the chain and increased solubility
This produces low molecular weight substances. The most commonly used example of this method is
Poly (methyl methacrylate) is used. This resist
The main drawback is that high enough to make a significant difference in molecular weight
Requires the use of an organic solvent as the developing medium.
That is what you need to use. [0008] Another example of DUV photoresist technology is photoresist.
High moment to remove selected area of photoresist film
With the use of a fluence DUV excimer laser.
This technique is called Laser Photo-Abrasion
You. See, for example, U.S. Pat. No. 4,414,059. DU
Another disclosure of V photosensitizers is found in European Patent Application 0.
No. 129694, used in photoresist compositions
Diazo homotetrameric acid compounds
You. [0009] Specified photoresist for DUV region
References to photoresist processes and requirements
For further background on the Americana
nChemical Society Symposi
um Series # 266,Materials
for Microlithography, L .; F.
Thompson, Ed. , ACS 1984;
J. Bowden, "A Perspective o
n Resist Materials for Fi
Ne-Line Lithography ".
German publicationsAngew.Chem. 92 (9) 7
54 (1980), Von Bruno Kokel,
et al. 1,3-dimethyl-5-diazoba
Although rubituric acid is disclosed, the compounds of the present invention
Useful as a sensitizer for positive photoresist compositions
Sex was not known prior to the present invention. [0010] SUMMARY OF THE INVENTION According to the present invention,
A new type of compound showing excellent sensitizing performance in the long ultraviolet region
A photoresist film using a product is provided. [0011] SUMMARY OF THE INVENTION The present invention provides a structural formula: [0012] Embedded image And [0014] Embedded image However, R₁And R_TwoIs C_ThreeOr C₁₂Archi
Group, cyclohexyl group, benzyl group and alkyl moiety
Is C_TwoOr C₆Selected from the group consisting of aralkyl groups
Substituents, R_ThreeAnd R_FourIs C₁Or C₁₂Archi
Group, cyclohexyl group, benzyl group and alkyl moiety
Is C_TwoOr C₆Selected from the group consisting of aralkyl groups
Substituents and R_FiveIs α, ω-disubstituted C_TwoNo
To C₁₂Alkyl group, methylenedicyclohexyl group or
Ruquil part is C₁Or C₆Dialkylphenylene
Selected from the group consisting of groups;
5-diazobas selected from chromophore derivatives and bichromophore derivatives
It consists of a substituted derivative of rubituric acid and a film-forming resin.
Photosensitive film. The unique compound of the present invention is a positive type photoresist.
When used in a dysto formula, it has an absorption maximum at about 260 nm.
Gives only one DUV response. Furthermore, these specificities
Compounds enable effective photobleaching of sensitizers upon exposure
Has a non-light-absorbing alkyl group. [0017] The photosensitive film of the present invention is the above-mentioned enhancement of the present invention.
Contains a sensitizer compound as an active ingredient. Usually this compound
About 2 to about35Contains dry weight%. The rest is preferable
Is a resin soluble in aqueous alkali (ie, alkaline aqueous solution)
(Binder), usually about 65 to 98% by dry weight
Contained. Such a photoresist film is placed on a substrate
Photoresist for film formation
The composition is obtained by dissolving the above in a suitable solvent. The sensitizer of the present invention is used in the DUV region.
Important in that it is configured to work only with
One. Novolak type tree used for NUV resist
Fat has high absorbance (opacity) in this spectral region.
Not preferred. Useful resins are aqueous as described above
A resin that is soluble in alkalis.
Imide (maleimide) and 4-isopropylstyrene or
Is 4-ethylstyrene or 4-methylstyrene or 2,
4-dimethylstyrene or copolymers with styrene, or
Is a resin containing a maleimide homopolymer. This
These resins have the properties required for DUV photoresist resins.
Have. Such properties include the spectral region of interest.
Low absorbance, solubility in aqueous alkaline developer solution,
Compatibility with photoresist sensitizers and solvents, appropriate photoresist
Film forming ability by spin coating from dist solvent,
Adhesiveness, thermal stability under processing conditions, under substrate etching conditions
Physical and chemical stability of the substrate
Easy to remove. These resins are compatible with the sensitizer of the present invention.
A photoresist composition for use. Example 1 of the present invention
A typical resin used in Example 10 was 4-tert-butylstyrene.
And a 1: 1 copolymer of maleimide and maleimide. The present invention
The use of sensitizers of specific
Not limited to use with fats; sensitizers of the invention
Is another DUV photoresist resin that meets the above requirements.
Can be used with polymer resins. Used in making photoresist formulations
The sensitizer compounds of the present invention can be used as membranes of suitable polymers and mixtures.
Solvents useful for formation, such as 2-methoxyethyl ether
4-tert-butylstyrene / male in (diglyme)
An imide copolymer and from about 3: 1 to 10: (by weight)
Mix at a polymer / sensitizer ratio in the range of 1. Spin the mixture
Coating on a silicon wafer, then baking
Except for the grim, a dry film of about 1μm thickness can be left.
You. Pass the film through a resolving mask, for example, chrome on quartz.
About 50 mJ / cm of DUV radiation centered on 60 nm
^TwoHit The exposed film is then developed in an aqueous alkaline medium.
That is, the film is favorably held in the non-irradiated area, and
Creates a positive relief image that completely exposes the substrate
put out. Preparation of the novel photoresist composition of the present invention
The key component of the photoresist is the sensitizer-resin-solvent set
Novel diazobarbituric acid sensitization included in the product
Agent compound. According to the present invention, (appropriate spectrum
Better with aqueous alkaline developer when exposed to light
The sensitizer compound that makes it soluble is 1,3-disubstituted-
5-diazobarbituric acid, ie the formula: [0021] Embedded image The single chromophore structure and formula: [0023] Embedded image A bichromophore structure [where R is₁And R_Two
Is C_ThreeOr C₁₂Alkyl group, cyclohexyl group, benzyl
And the alkyl moiety is C_TwoOr C₆Aralkyl that is
A substituent selected from the group consisting of_ThreeAnd R_Four
Is C₁Or C₁₂Alkyl group, cyclohexyl group, benzyl
And the alkyl moiety is C_TwoOr C₆Aralkyl that is
A substituent selected from the group consisting of_FiveIs
α, ω-disubstituted C_TwoOr C₁₂Alkyl, methylene disilic
Rohexyl or alkyl moiety is C₁Or C₆Zia is
Selected from Lucylphenylene]. The substituent of these compounds is about 26
Select to have a single DUV absorption maximizing 0 nm
Huh. Good for NUV absorption (no absorption)
Can be replaced. In a preferred embodiment, the desired properties are achieved
As alkyl substituents used for₁= R_Two= Shi
Clohexyl; R_Three= R_Four= Butyl and R_Five= Dodeci
Or R_Three= R_Four= Cyclohexyl and R_Five= Dodeci
There is. Particularly preferred diazobarbituric acid
Compounds include 1,3-dicyclohexyl-5-diazobas
Rubituric acid; 1,12-bis (3- [1-cyclohexyl
Sil-5-diazo-2,4,6- (1H, 3H, 5H)
-Pyrimidinetrionyl]) dodecane; 1,12-bis
(3- [1-n-butyl-5-diazo-2,4,6 (1
H, 3H, 5H) -Pyrimidinetrionyl]) dodeca
1- (1-butyl) -3-cyclohexyl-5-dia
Zobarbituric acid; and R_ThreeAnd R_FourIs cyclohexyl
And R_FiveIs methylenedicyclohexyl
There are chromophore compounds. Typically these diazobarbituric acids
Suitable for sensitizer with alkali-soluble polymer in spinning solvent
Compounded at a sharp polymer / sensitizer ratio and spun onto a Si wafer.
To form a film having a dry thickness of about 1 μm. preferable
In one embodiment, one of the five sensitizers shown immediately above is
4- so that the ratio of fat to sensitizer is 7: 1 by weight.
Formulated with butylstyrene / maleimide copolymer. Good
Preferred solvent is 2-methoxyethyl ether (diglyme)
And the solid% in diglyme is 25% depending on the desired film thickness.
It is from 35% by weight. After spin coating the substrate with resist,
Bake wafer to remove solvent; at 80 ° C. in convection oven
30-40 minutes are preferred. After baking, place the film on quartz
Exposure to DUV light through a chrome light mask. preferable
Irradiation is centered at 260 nm, matching the absorption of the sensitizer
40-60mJ / cm^TwoDUV light. After exposure,
Photoresist is developed in aqueous alkaline solution to DUV
The areas of the film exposed to light are removed and the photoresist layer is exposed to light.
Create a J-shaped relief image. The sensitizer is a photoresist in an alkaline developer.
It has the effect of reducing the solubility of the strike resin. Exposed to light
The sensitizer undergoes a photochemical reaction and develops the resin alkaline.
It is a new type that does not prevent dissolution in the agent. Photochemically reacted
The type of sensitizer, at least at the initial stage after exposure,
It is considered to be a carboxylic acid. The resin used for the resist is a component for forming a film.
And a physical vehicle for the sensitizer. D as described above
To work well as UV photoresist polymer
The resin must have a number of properties. With substituted styrene
Maleimide copolymers are suitable for this application.
The example of fat is shown. The present invention is used for manufacturing a novel photoresist.
The solvent used has good solubility in resin and sensitizer
It is characterized by having. Preferably also a solvent set
The product is less likely to produce streaks and has good wetting properties.
Need to be Other suitable solvents besides diglyme
Dimethylformamide, N-methylpyrrolidone and
There is rohexanone. Solvent composition is a mixture of suitable solvents
It may be. The following examples further illustrate the invention. But
These examples describe in detail certain preferred embodiments of the invention.
However, they are shown primarily for illustrative purposes.
Thus, the present invention in its broader aspects is not limited here.
Please understand that there is no. (General Method) 32% by weight of the solution
The resist was formulated in the diglyme to account for it. Regis
The solution is a 0.2 μm PTEE filter (Schlei
clean gala through cher and Schuell)
The solution was filtered into a container. The substrate is a polished silicon wafer (Pe
nsilco) or thermally grown silicon dioxide layer
Polished silicon wafers (Semimetals)
there were. Before using, clean the substrate and prepare the common wafer
In principle, 1,1,1,3,3,3-hexamethyldisi
Steamed with Razan (HMDS) for 10 minutes. The substrate is He
adway Research Spinner (Model EC-
101) Attach to vacuum chuck
Was applied to the wafer with a pipette. The membrane is about after baking
Spin to give 1 μm thickness. Typically
It had a spin speed of 6000 rpm in 40 seconds. S
After the pin treatment, the resist-coated wafer is heated at 80 ° C. in a convection oven.
Bake for 40 minutes. After baking, remove the wafer
The block was exposed to DUV light passed through the contact method. 26 for irradiation
OAI (Optical) adapted to 0 nm optical characteristics
Associates) series 30 light sources
Was. Lamp output is further 260nm wide band filter
(Omega Optical, 50nm FWHM)
Filter so that only DUV radiation falls on the resist
I made it. Masks have a characteristic size range up to nominally 1 μm
Chromium on quartz (Ditric Optics)
Was. The irradiation intensity after the secondary filter is
Calibrated with Mopile. Loss of film in unirradiated area before development
Later, the thickness of this region is referred to as Rudolf FTM interference film thickness model.
It was determined by measuring with a nita. Developer is optical and electron microscope
Inspected. Example 1 1,3-Dicyclohexyl-5
-Jig using diazobarbituric acid as spinning solvent
4-tert-butylstyrene / maleimideco in rim
Compounded with polymer at a polymer / sensitizer ratio of 6: 1 (w: w)
did. The polymer was produced by free radical polymerization. Regis
Spin on a Si wafer and bake at 80 ° C for 40 minutes
After the coating, a film having a dry thickness of about 1 μm was formed. Dry membrane
60 mJ / cm of DUV light centered at 260 nm
^TwoAnd exposed through a positive mask. Exposure film at room temperature
Present in 0.20N potassium hydroxide (KOH) aqueous solution for 60 seconds
Imaged, positive type relief with unirradiated area of 81% film retention
I made an image. Example 2 A resin / sensitizer ratio of 7: 1 (w:
A resist was manufactured by the method of Example 1 instead of w). Regis
The membrane was produced in the same manner as in Example 1. Through a positive mask
To make the film 48 mJ / cm of 260 nm DUV light.^TwoDew
Lighted. Exposure film for 230 seconds with 0.14N KOH solution
Developed. Generates a positive relief image with a film retention of 78%
did. (Example 3: Comparative example)
According to the method of Example 1 as tyl-5-diazobarbituric acid
Thus, a resist was manufactured. The same resist film as in Example 1
Manufactured by the method. The film is passed through a positive mask at 260 nm.
80mJ / cm of DUV light^TwoExposed. Exposure film
0.15N tetramethylammonium hydroxide
Developed for 90 seconds in a mask and only has a film retention of 21%.
A relief image was obtained. (Even if you increase the exposure,
Less than about 1/4 that of Example 1)
R₁= R_Two= Methyl compounds have been prepared earlier,
This example is not described in the lithographic context
Is not enough for this compound to be used in context
Is shown. R group is resist for protection purpose
Large enough to give the membrane considerable hydrophobicity
Indicates that it is necessary. Example 4 The sensitizer was 1,12-bis (3-
[1-cyclohexyl-5-diazo-2,4,6 (1
H, 3H, 5H) -Pyrimidinetrionyl]) dodecane
A resist was compounded by the method of Example 2. This is the formula
R in_Three= R_Four= Cyclohexyl and R_Five= 1,12-2
This corresponds to the structure of substituted dodecane. Use a positive resist
48mJ / cm of DUV light through the disc^TwoExposed to
Was. Exposure film is developed in 0.14N KOH solution for 225 seconds
did. A positive relief image is formed with a film retention of 82%.
Was. Looking at the scanning electron micrograph of this relief image,
Show free standing photoresist lines on recon board
And the developed image hole in the resist film on silicon is a residue
There are no features and the features are clearly specified. Example 5 The sensitizer was 1,12-bis (3-
[1-n-butyl-5-diazo-2,4,6 (1H, 3
H, 5H) -pyrimidinetrionyl]) dodecane, ie
R of the structural formula_Three= R_Four= N-butyl and R_Five= 1,12-2
A resist is applied to the substituted dodecane compound by the method of Example 2.
I combined. 48 mJ / resist film through positive mask
cm^TwoOf DUV light. 0.14N exposure film
Developed in KOH solution for 135 seconds, 74% unirradiated area
A positive-type relief image having a film retention of was formed. Example 6 A resist was manufactured by the method of Example 2.
Was. A film was formed and exposed by the same method. Exposure film next
Developed in 0.20N KOH solution for 55 seconds, unirradiated area
A positive relief image with a film retention of 76%
Was. (Example 7) A resist is manufactured by the method of Example 4.
Then, a film was formed in the same manner and exposed. Set the exposure film to 0.
Develop in a 20N KOH solution for 55 seconds.
A positive relief image having a film retention of 7% was produced. (Example 8) A resist is manufactured by the method of Example 5.
Then, a film was formed in the same manner and exposed. Set the exposure film to 0.
Develop in a 20N KOH solution for 30 seconds,
A positive relief image having a film retention of 2% was produced. (Example 9) A resist was manufactured by the method of Example 4.
Was. Si substrate with thermally grown silicon dioxide layer
The film was spun on. The oxide layer is 885 nm thick and wafer
Harr did the same preliminary treatment with HMDS. Baking and
Exposure was in accordance with the method of Example 4. Exposure film is 0.2N KOH
Developed in solution for 90 seconds, 72% film retention in unirradiated area
I made a positive relief image with. (Example 10: Comparative example)
Example 4 to show lack of response to incoming NUV light
A film was formed by the same method as in Example 4 in which a resist was formed by the method described in Example 4.
However, irradiation was performed using 2 NUV light centered on 360 nm.
00mJ / cm^TwoMet. Exposure film is 0.20NKOH
Developed in solution for 120 seconds (about twice as large as Example 6). Irradiation
And non-irradiated areas have the same thickness, so a positive relief image
Did not occur. This is because the sensitizer of the present invention is
Diazonaphthoquinone sulfonic acid ester used for strike
In contrast, it confirms that it does not respond in the NUV region.
Therefore, to prevent the resolution from being reduced due to the presence of long wavelength light
There is no need to attach a filter. (1,3-dialkyl-5-diazobarbi
Synthesis of tool acids General method) 1,3-dialkyl-5
-Diazobarbituric acid is the appropriate corresponding market available
Using isocyanate and primary amine as raw materials,
It can be prepared as shown in the schematic reaction below. [0043] Embedded imageWhere R and R 'are R₁And R_TwoAbout
Each has what is shown. The synthesis step is performed by using 1- (1-butyl
) -3-cyclohexyl-5-diazobarbituric acid
Are shown in connection with the synthesis of (Example 11) (The synthesis of 1- (1-butyl) -3-cyclohexylurea
Composition) Pressure equalization addition leak with thermometer and drying tube at the top
500 m dry, equipped with a funnel, nitrogen inlet and magnetic stir bar
l round bottom three-necked flask with 100 ml
Run (THF) was added. 98% n-butyl under nitrogen
17.24 ml (0.15 mol) of isocyanate
added. 99% cyclohexylurea in 46 ml THF
17.33 ml (0.15 mol) of min was added to the addition funnel.
First, a stirring solution of n-butyl isocyanate was added at 40 ° C.
At a constant speed to keep the temperature
T) Drops slowly. After completion of the reaction, the reaction mixture is
Stirred for hours. Remove solvent with rotary evaporator
did. The white residue was vacuum dried at room temperature for 12 hours. Dry
Also, the yield of the crystalline white product was quantitative. Product
Melted sharply at 107-108 ° C (uncorrected). (Example 12) (1- (1-butyl) -3-cyclohexyl barbituo
Synthesis of luic acid) Pressure equalization with thermometer and drying tube on top
250 ml with dropping funnel, nitrogen inlet and magnetic stirrer
15. Add 35 ml of reagent grade acetic acid in a three neck round bottom flask.
87 g (0.080 mol) of 1- (1-butyl) -3-
Cyclohexyl urea and 8.33 g (0.080 mol)
Was added to form a solution. Stir the mixture
Heat slowly to 60 ° C. in a corn oil bath. Temperature 6
All solids dissolved before reaching 0 ° C. 32ml in total
Acetic anhydride into the dropping funnel and slowly (about 45 minutes
D) into the stirred reaction flask. Gradually raise the temperature
Take about 90 ° C for 7 hours, then allow to cool to room temperature, overnight
I left it. Water aspirator suction type rotor with heated solvent
It was removed with a reevaporator. 24 hours at 50 ° C.
Vacuum dried for hours. Slightly yellow crude product (20.7
g) was isolated in 97% yield. This is 103-106
Melted at ℃. Sample of crude product in hot ethanol
/ Recrystallized from water and dried. This white crystal is above 95 ° C
Sublimed and melted at 107-108 ° C. Crude product is PM
Pure in R and IR, following synthesis
Used for the process. (Example 13) (1- (1-butyl) -3-cyclohexyl-5-dia
Synthesis of zobarbituric acid) Thermometer and drying tube at the top
With pressure equalizing dropping funnel, nitrogen inlet and magnetic stir bar
80 ml into a dry 250 ml three-necked round bottom flask
Reagent grade acetonitrile and 6.65 g (0.025
1)-(1-butyl) -3-cyclohexylbarbi
Tool acid was added. Cool the stirred solution to 2 ° C in an ice bath
Was. Next, 5.75 g (0.029 mol) of p-toluene
Reaction with 20 ml of acetonitrile solution of sulfonyl azide
Added to flask. 3.20 g (0.0317 mol)
20ml reagent grade dichloromethane solution of triethylamine
Into a dropping funnel and slowly add to the reaction flask,
Meanwhile, the temperature was kept below 3 ° C. Flask temperature 3 ℃
Lowered for one hour. Stir the reaction flask to room temperature (20
C) and kept at room temperature for 12 hours. Solvent at room temperature
Was removed with a rotary evaporator. 3 dark red residues
Dissolve in 50 ml of dichloromethane and add 350 ml of 50
(W / v) Washed with aqueous sodium hydroxide solution. Dichloro
Wash the methane solution twice with 300 ml portions of distilled water and dry
Dry over sodium sulfate and put on a rotary evaporator
Dry over. Dry viscous residue at 40 ° C for 15 hours
The remaining residue was a dark viscous liquid. Crude material
Silica gel packed with chloromethane (Brinkma
n # 7733) chromatography on the column
Was. The crude product is added as a dichloromethane solution and
Unreacted p-toluenesulfonate eluted with chloromethane
Luazide is removed and then 2: 1 (v / v) dichlorometa
Eluting with hexane / acetonitrile to remove the desired components from the column.
Started. After solvent evaporation, pale yellow residue is very viscous at room temperature
Liquid remained. (Α, ω-bis (3- [1-alkyl-5
-Diazo-2,4,6 (1H, 3H, 5H) -pyrimidi
Trionyl]) Synthesis of alkanes) (General method) The title compound is shown by the following abbreviated reaction.
Manufactured from commercially available starting compounds: [0049] Embedded image Where R is R_ThreeAnd R_FourWas shown earlier
R ′ is R_FiveIs described above. (Example 14) (1,18-dicyclohexyl-1,3,16,18-
Synthesis of tetraaza-2,17-octadecanedione)
Meter, magnetic stir bar, pressure equalizing dropping funnel, nitrogen purge and
1000ml round bottom with heating mantle
3 in 400 ml of 1: 1 THF / toluene in Lasco
0.04 g (0.240 mol) of cyclohexyl isocyanate
The anate was dissolved. Heat the solution in the flask to 40 ° C
Was. 24.04 g (0.240 mol) of 1,12-dode
400 ml of candiamine in 1: 1 THF / toluene
Dissolve in the isocyanate and stir slowly into the heated solution
Was dropped. After adding the diamine, add another 100 ml
The ene was added to the flask. Raise the temperature to 80 ° C and mix
The mixture was refluxed for 12 hours. Heated vacuum rotary evaporator
The solvent was removed with a porator. Quantification of solid white product
Obtained in a typical yield. Vacuum dry product at 50 ° C for 15 hours
did. The completely insoluble product is sheared at 207-208 ° C.
Melted. (Example 15) (1,12-bis (3- [1-cyclohexyl-2,
4,6 (1H, 3H, 5H) pyrimidinetrionyl])
Synthesis of dodecane) [0053] Embedded imageMagnetic stirrer, nitrogen inlet, thermometer and drying
Dry three with pressure equalizing dropping funnel with tube at the top
One neck, 900ml reagent grade in 1000ml round bottom flask
Glacial acetic acid was added. 8.33 g (0.080 mol) of malo
Acid and 18.03 g (0.040 mol) of 1,18-
Dicyclohexyl-1,3,16,18-tetraaza-
Add 2,17-octadecandione to the flask and stir
While heating slowly in an oil bath. Temperature of 85 ° C or higher
All solids dissolved in degrees. Keep the temperature at 85-90 ° C
Of acetic anhydride over a period of 1 hour.
It was dripped slowly into Rusco. After adding acetic anhydride, stir and dissolve
The liquid was heated at 90 ° C. for 7 hours and then cooled to room temperature. solution
Was filtered and evaporated to dryness on a rotary evaporator. solid
Was vacuum dried at 50 ° C. for 12 hours. > 97% crude product
Isolated in yield. Recrystallization of a sample of the crude product has a melting point (1
75-176 ° C), proton magnetic resonance spectrum, infrared
No significant change in the spectrum or ultraviolet spectrum
Was. (Example 16) (1,12-bis (3- [1-cyclohexyl-5-di
Azo-2,4,6 (1H, 3H, 5H) -pyrimidine
Lyonyl]) Synthesis of dodecane) [0056] Embedded image Magnetic stirrer, thermometer, pressure dropping funnel
Three-necked, 1000 ml round bottom frus with nitrogen and nitrogen inlet
The ice was cooled in an ice bath. 8.88 according to the synthesis method described above.
g (0.015 mol) of barbituric acid in 175 ml
Dissolved in dichloromethane and placed in a flask. 150ml
Of acetonitrile is then added to the barbituric acid solution
Was. The stirred solution was cooled to 3 ° C. Then 30 ml of aceto
6.51 g (0.033 mol) of p-tol in nitrile
Ensulfonyl azide was added to the reaction flask. 3.5
30 ml of 8 g (0.035 mol) of triethylamine
Into a dropping funnel and adjust the temperature to 3 ° C.
Into the reaction flask slowly over 60 minutes
Was added. Initially the solution was clear but at 3 ° C for 2 hours
It turned violet. After 3 hours at 3 ° C., the solution was <
Dry with a rotary evaporator at an addition bath temperature of 40 ° C
did. Vacuum the solid reddish residue at 40 ° C. for 24 hours
Dried. Dissolve crude material in minimal amount of dichloromethane
And silica gel packed with dichloromethane (Brin
kman # 7733) on the column
/ Chromatography eluting with acetonitrile
Was. An intermediate fraction was secured. Intermediate cut to solvent
Is evaporated to a total of 6.8 g (0.011 mol) of dry
The dried product was obtained with a yield of 71%.

   ────────────────────────────────────────────────── ─── Continuation of front page    (72) Inventor Michael James McFarland               United States New Jersey               08846 Middlesex East               Leanroad Avenue 212

Claims (1)

(57) [Claims] Structural formula: And [However, R ₁ and R ₂ are C ₃ to C ₁₂ alkyl group, a cyclohexyl group, a substituent a benzyl group and an alkyl moiety is selected from the group consisting of aralkyl groups are C ₂ to C _6, R ₃ and R ₄ is a substituent selected from the group consisting of a C ₁ -C ₁₂ alkyl group, a cyclohexyl group, a benzyl group and an aralkyl group wherein the alkyl moiety is C ₂ -C ₆ , and R ₅ is α, ω-dialkyl. When the substituted C ₂ -C ₁₂ alkyl, methylenedicyclohexyl or alkyl moiety is C
Selected from a compound having ₁ to those selected from the group consisting of dialkyl phenylene is C _6] 5-
A photosensitive film comprising a substituted derivative of diazobarbituric acid and a film-forming resin. 2. The photosensitive film according to claim 1, wherein the film-forming resin is an aqueous alkali-soluble resin. 3. 3. The photosensitive film according to claim 1, wherein the derivative is present in an amount of 2 to 35% by dry weight and the resin is present in an amount of 65 to 98% by dry weight. 4. The photosensitive film is present on a substrate.
The photosensitive film according to any one of the above items. 5. (A) Structural formula: And [However, R ₁ and R ₂ are C ₃ to C ₁₂ alkyl group, a cyclohexyl group, a substituent a benzyl group and an alkyl moiety is selected from the group consisting of aralkyl groups are C ₂ to C _6, R ₃ and R ₄ is a substituent selected from the group consisting of a C ₁ -C ₁₂ alkyl group, a cyclohexyl group, a benzyl group and an aralkyl group wherein the alkyl moiety is C ₂ -C ₆ , and R ₅ is α, ω-dialkyl. When the substituted C ₂ -C ₁₂ alkyl, methylenedicyclohexyl or alkyl moiety is C
Selected from a compound having ₁ to those selected from the group consisting of dialkyl phenylene is C _6] 5-
A photosensitive film comprising 2 to 35% by dry weight of a substituted derivative of diazobarbituric acid; (b) 65 to 98% by dry weight of an aqueous alkali-soluble resin; and (c) a solvent. A composition for forming.