JPH01209445A - Radiation sensitive material - Google Patents

Abstract

PURPOSE:To develop various functions by irradiation of radiations by incorporating a specific compd. as a radiation sensitive material into the above material. CONSTITUTION:This material contains the compd. expressed by the formula I or the like as the radiation sensitive material. In the formula I, (Nuox)<1>, (Nuox)<2> denote =O, =N-R<4> (R<4> denotes a hydrogen atom., hydrocarbon group, etc.) L denotes the formula II (R<6>, R<7> denote a hydrogen atom., hydrocarbon group, substd. hydrocarbon group, etc.; Z denotes a bivalent atom. group which is electrically negative with a carbon atom. carrying R<6>, R<7>; UG denotes a group which is released in the form of Z-UG by irradiation of radiations.) R<1>-R<3> respectively denote a hydrogen atom., substd. and unsubstd. hydrocarbon group, halogen, sulfo group, etc. The various functions are thus developed properly according to purposes by the irradiation of the radiations.

Description

[Detailed description of the invention] ■ Background of the invention Technical field The present invention relates to radiation-sensitive materials.

Prior art and its problems There are many known optical functional materials that function by irradiation with light, which is a type of radiation. classified into groups.

For example, the material itself functions as a light sensor, and the receiver effectively uses the energy of the light it receives in subsequent processes.The material itself causes a photoreaction, resulting in the formation (or inability to form) of useful substances such as pigments. There are also known materials that cause significant changes in physical properties due to photoreactions, and those that make effective use of these changes. Representative examples of substances that function as optical sensors are silver halide in silver halide photography and photoconductors in electrophotography, and both have established a firm position as excellent image forming technologies. However, these systems have problems such as complicated image forming processes and complicated full color systems, and a simpler image forming method has been desired.

In addition, photofunctional materials that undergo photoreactions to form or disappear useful substances include diazonium salts, azide compounds, and color photosensitive materials such as radical photographic compositions consisting of carbon tetrabromide and aromatic amines. Image forming methods and image forming methods using photoionization reactions of organometallic compounds and charge transfer complexes are known, but the general characteristics of materials belonging to this group are poor stability of the materials, and the useful materials that can be formed are limited. The problem is that it is limited. Although the photoredox reaction has relatively good material stability, the functions that can be expressed are limited, and its applications are severely limited.

Additionally, a wide variety of optically functional materials are known that undergo significant changes in physical properties as a result of photoreactions.

Photosensitive resins for plate making include systems using dichromate as a photosensitive material, systems using photocrosslinking reaction of polyvinyl cinnamate,
Mixed systems of azide compounds and novolak resins, systems that combine photopolymerization initiators and vinyl monomers, systems that use diazonium salt polymers, systems that combine 0-quinone diazides with novolac resins, Systems with acryloyl groups or cinnamic acid groups introduced into the side chains are in practical use.

In addition to plate-making materials, these photosensitive materials are also used in UV-curable inks, paints, and the like. Most of the materials belonging to this group undergo polymerization or crosslinking as a result of photoreactions and become insolubilized, but on the other hand, they are so-called positive-type photosensitive materials that become solubilized in the areas exposed to light, and are susceptible to UV light. At present, only 0-quinone diazides are useful, and it has been desired that a new positive-type fluorescent material will appear.

On the other hand, as a photoredox reaction (as a known example,
For example, there is a photoreduction reaction of aromatic ketones and quinones.
It is well known that benzopinacol can be obtained in high yield when hensifhenone is irradiated with light in alcohol.

Photooxidation of alcohols using quinones is also well known.

These are thought to occur when the n-π1 excited state (sometimes π-π0) of carbonyl abstracts a hydrogen atom from the solvent.

For example, B. Atkinson, M. Di et al.
ns, FaradaySoc,, 54 1331 (
P. (1958).

It has been reported that when benzoquinone is photoexcited in the n-π absorption band in the presence of alcohol, an oxide of hydroquinone and alcohol is produced.

Also, FJilkinson is J, Phys chem.
66. 2569 (1962), 9.10-anthraquinone was photoexcited in an isopropanol solution to produce 9.10-dihydroxyanthracene and acetone with a quantum yield of 1.

These are just examples of research, and research on the photo-dox reactions of quinones has been actively conducted in recent years, both in basic and applied research. However, it is actually difficult to utilize the mechanism of reacting the reduction product produced by a photoredox reaction with another compound for sensitive materials such as image formation.

Therefore, considering its use in image formation, for example, it was considered advantageous to directly utilize the reduced product produced as a result of this photoredox reaction.

On the other hand, there is a group of compounds called positive-working compounds in silver halide photosensitive materials. Among these, many compounds have been studied that are used in combination with a reducing agent for silver halide photography and release photographically useful groups through a redox reaction with the reducing agent remaining in the silver development and inverse image.

For example, U.S. Pat. No. 4,139,389;
．． No. 379, No. 4.564,577, JP-A No. 1983-1
No. 85333, a compound which releases a photographic reagent by an intramolecular nucleophilic substitution reaction after being reduced as disclosed in JP-A-57-84453, and U.S. Pat. No. 4,232.1.
No. 07, JP-A No. 59-101649, Research Disclosure (1984) TV No. 24025, or JP-A No. 61-88257, after being reduced, the photographic reagent is released by an intramolecular electron transfer reaction. Examples include compounds that cause separation.

These compounds are compounds that release photographic reagents when reduced using a photographic reducing agent under alkaline conditions in a film unit containing photosensitive silver halide.

However, since these film units use silver halide as a photosensitive component, it is necessary to use expensive silver, resulting in high costs.

Furthermore, its usage is limited to image formation.

■Object of the Invention An object of the present invention is to provide a radiation-sensitive material that can exhibit various functions upon irradiation with radiation. Another object of the present invention is to provide a novel radiation-sensitive material that does not use photosensitive silver halide.

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

That is, the present invention provides the following general formula (1-A) or (1-B
) is a radiation-sensitive material that does not use photosensitive silver halide and is characterized by containing a compound represented by the following as a radiation-sensitive substance.

General formula (1-A) General formula (1-B) (Nuo
x)” R3 Nichu (Nuox)’
, (Nuox) 2 can be the same or different <=
O,=NR' is represented. Here, R4 is a hydrogen atom, a hydrocarbon group, a converted hydrocarbon group, or -3Oz R' (
R' represents a substituted or unsubstituted hydrocarbon group.

? It is -C-Z-LIG or -(R”-)-, N-E-Y-UG it.

Rh, R here? may be the same or different (,
Represents a hydrogen atom, hydrocarbon group or substituted hydrocarbon group, Z
represents a divalent atomic group that is electronegative with respect to the carbon atom supporting Rh and R'L.

R1 is a divalent alkylene group (containing 1 to 3 atoms in the divalent bond), and n is O or 1.

R9 is a hydrocarbon group or a substituted hydrocarbon group, E is carbonyl or thiocarbonyl, and Y is an amino group, oxygen atom, selenium atom or sulfur atom.

By irradiating UC with radiation, Z-UG or
It represents a group released in the form of Y-UG.

In addition, R1, RZ, and R3 are each a hydrogen atom, a substituted or unsubstituted hydrocarbon group, a halogen, a sulfo group, a carboxyl group, an alkoxycarbonyl group, a carbamoyl group, an alkoxy group, an acyl group, an alkylthio group, a sulfonyl group,
Represents a sulfamoyl group, acyloxy group, or sulfonyloxy group. When R1, R2, and R3 are located adjacent to each other on the ring, they may be bonded to each other to form a saturated or unsaturated ring. Further, R1, R2, and R3 may be L.

Examples of the hydrocarbon groups for R4 to R1, R', and R1 to R3 include alkyl groups, aryl groups, alkenyl groups, and alkynyl groups. Substituents include cyan group, nitro group, halogen atom, heterocyclic residue, sulfonyl group, carboxyl group, alkoxycarbonyl group, carbamoyl group, hydroxyl group, alkoxy group, acyl group, alkylthio store, amino group, sulfamoyl group, Examples include acyloxy groups.

An example of Z is 10-1-S-1SOz -1-3e-
1-P- and the like.

The compound represented by the general formula (1-A) or (1-B) is a radiation-sensitive substance with respect to its properties and stability synthesis. Nuox), ', (Nuox)'' is preferably an oxo group.

In addition, -C has a known timing group (JP-A-62-
215270 etc.) as Z-LJC;
It may also be introduced into Y-UG.

When the compound of the present invention is imagewise irradiated with radiation, it quickly and efficiently releases a group (UG) that exhibits a useful function in an imagewise manner, so it has many potential uses. The following examples can be given as applicable examples.

■ If the compound of the present invention is a diffusible dye that exhibits a useful function, the dye can be removed by a diffusion transfer method using water, a solvent, or a mixed solvent, or a thermal diffusion method using heat.
Image formation is possible.

■ In the compound of the present invention, if the group exhibiting a useful function is a ligand of a metal complex, an image of the metal complex can be formed by a diffusion transfer method using water, a solvent, or a mixed solvent, or a thermal diffusion method. be. Alternatively, it is possible to form an image of a metal complex in a fuchu containing the present compound having a group exhibiting a useful function.

■ If the compound of the present invention is soluble in water, a solvent, or a mixed solvent, and a group exhibiting a useful function is soluble in water, a solvent, or a mixed solvent? When fj or insoluble, the compound of the present invention remaining in the unexposed area can be eluted to form an image based on the group exhibiting a useful function. Patterned dye and/or UV absorber and/or infrared absorber filters and light resistance prevention filters can be made from this rLJ.

■ If the group exhibiting a useful function in the compound of the present invention is a colorless compound or a dye with a changed absorption wavelength when bonded, but becomes colored or changes color after release, the color can be changed before and after release. . Therefore, by using this, an image can be formed.

■ In the compound of the present invention, when the group exhibiting a useful function is fluorine, chlorine, bromine, or iodine, glass, silicon dioxide, silicon nitride, -silicon oxide and/or aluminum, aluminum alloy, iron, iron alloy , roots, alloys such as silver, etc. can be etched in the exposed areas. This can enable microlithography in microelectronic devices or create masters for printing plates.

(2) In the compound of the present invention, if the group exhibiting a useful function contains sulfur, the plating activity for palladium metal at the site corresponding to the exposed area may be deactivated. Alternatively, the plating activity for nickel metal can be increased in the exposed area. This allows application to printed wiring and patterned plating.

■ In the compound of the present invention, if a group that exhibits a useful function can become a mordant site that can be dyed with a dye, the mordant site can be dyed with a dye in the region corresponding to the exposed area to form a dye image. Ru. This forms a color microfilter.

(2) When the group exhibiting a useful function in the compound of the present invention is a base precursor, formation of a diazo dye by diazo cuff-pulling or polymerization by the diazo compound can be initiated in the exposed area.

This may form a color image or an image of the polymer.

■ In the compound of the present invention, if a group exhibiting a useful function can be discolored by the light source of the pattern forming apparatus used in microlithography (for example, the G-line or I-line of a high-pressure mercury lamp), contrast enhancement (Contr.
Ast Enhancement) can be performed in a patterned manner, and microlithography can be used to form finer patterns.

[Phase] The group exhibiting a useful function is a resin component, and when a difference in solubility occurs due to separation of the resin component, it functions as a resist film.

Although specific examples of compounds that can be used for the purposes described above are listed, the scope of the present invention is not limited to these specific examples. The meaning is the same as the group listed in column L).

Examples of compounds that can be used in the applications described in (2) include the following.

■-47 Dye■ [1ye■ Dye■ Dye■ Dye■ Dye■ Dye■ 1) ye■ Dye■ Dye@+ Dye@ Dye@ Dye■ Dye■ Dye[phase] Dye@ Dye@ Dye[phase] Dye[phase ] Dye■ - Dye@ Dye ■ Fog Dye ■ Dye ■ Shi13 Dye ■ ■ 0Ja Dye ■ Dye ■ SO, K Dye ◎ 0Ja Dye ■ Dye ■ Dye ■ Dye ■ For the use mentioned in ■ Dye ■ Dye ■ Dye ■ ■ Examples of compounds that can be used include the following.

SD ■ SD ■ SD ■ SD ■ SD ■ SD ■ Next, the synthesis method will be described.

Regarding the compound represented by the general formula (1-A), US Pat. No. 4,139,389, US Pat.
4,564,577, JP-A-59-185333, JP-A-57-84453, and U.S. Pat. No. 4,232,107 for compounds represented by general formula (1-B).
It can be easily synthesized by following the synthesis method described in JP-A-59-101649, Research Disclosure (1984) IV-24025, or JP-A-61-88257.

Some specific synthesis examples will be given and explained.

<Compound Example 1> Synthesis of compound 1-3 (Step 1) 2-pentaten-5-propionyl-
Hydroquinone - (A) Gold Bottom Pentadecyl Hydroquinone 100g and Propionic Acid 3
Blow BF3 gas into the tank until it is saturated, and heat to 85°C.
The mixture was stirred for 5 hours. The reaction solution was poured into 1 kg of ice, and the resulting crystals were collected by filtration and washed 3 times with water to give 67.4 g of pale yellow crystals.
(yield 57%).

(Step 2) Add 2-pentadecyl-5-propyl-hydroquinone (B) to an OC 1h 101 autoclave with 600 g of (A) obtained in the above step.
, Pd/c (10%) 50g1 Acetic acid 25001R1,
Add t-butyl alcohol 25001R1 and reduce the hydrogen pressure to 5
Stir vigorously for 21 hours at 5 atm and reaction temperature of 70°C.
The filtrate was cooled to 0°C and Pd/c was filtered off, and the filtrate was concentrated under reduced pressure. The residue was recrystallized from toluene 000-
410 g (yield 71%) of pale yellow crystals were obtained. Melting point 109~
1) 1℃.

(Step 3) Bis(isobutoxymethyl)methylamineisobutyl alcohol 31.21! While stirring 9 kg of an aqueous methylamine solution (40%) at room temperature, 5.9 kg of paraformaldehyde was gradually added, resulting in a zero-exothermic reaction in which the internal temperature rose to 60°. The external temperature was set to 140°C, and 30.51% of the solvent was distilled off at a constant temperature of 1-. After further reducing the pressure with an aspirator and producing an initial distillation of 4.92, the book and (object) 8
．． 0kg 100°C/15■■Hg was obtained. Yield 34%
.

(Step 4) 20 i of xylene was added to 5.4 kg of 5-pen decyl-2,3,4° hydroquinone (B) and 7.7 kg of the amine compound obtained in (Step 3) and heated under reflux for 3 hours. Furthermore, 1.5 kg of amine compound was added, and 1.
．． The mixture was heated under reflux for 5 hours. The internal temperature was lowered to 100°C and methanol 1281 was poured. The resulting crystals were filtered using a centrifugal filter to obtain 6.0 kg of white crystals (yield: 85%). Melting point: 99-101°C.

-Henzoquinone (D) person h 3.0 kg of (C) obtained in the above step and 18 ethanol
1 was added, and the mixture was dissolved by heating under reflux.

There, add 8.6 kg of ferric chloride hexahydrate and 13.4 M water.
and a solution dissolved in concentrated hydrochloric acid (3.4%) was added dropwise over 45 minutes, and the mixture was heated under reflux for 5 hours.

After distilling off 121 ethanol, it was extracted twice with chloroform (151, 51). After drying this chloroform solution with Glauber's salt, the Glauber's salt was filtered, and after adding 3.0 kg of triethylamine to the chloroform solution, 2.5 kg of p-nitrochloroformate was added little by little. After stirring at room temperature for 2 hours, 201 parts of water, 1 part of concentrated hydrochloric acid, 51 parts of ethanol
In addition, it was extracted. After washing with brine, drying with mirabilite in a chloroform layer, reduce the volume under reduced pressure to 81 cm, add 1 ml of methanol, reduce the volume again to 3 g, and reduce the volume to 10 methanol.
I poured it into 1. The formed crystals were collected by filtration and washed with methanol to obtain 3.85 kg (yield: 78%) of yellow crystals. Melting point: 99-101°C.

(Step 6) 3-pen decyl-2,5-bis101
In the autoclave, 1 kg of (D) synthesized in the above step,
50 g of Pd/c (10%), 51 g of ethyl acetate, and 1 portion of acetic acid were added, and the mixture was vigorously stirred at room temperature under a hydrogen pressure of 75 a Lm for 2 hours. After filtering out Pd/c, iJt? f! ;t under reduced pressure? After condensation, the residue was recrystallized from 31 cm of acetonitrile to obtain 790 g of pale yellow crystals (yield: 85%). Melting point: 126-128°C.

(Step 7) Put 1.52 kg of (E) obtained in the above step into chloroform 1
51, 750 g of manganese dioxide was added thereto, and the mixture was stirred at room temperature for 2 hours. After manganese dioxide was filtered through Celite, 685 rnl of pyridine was added to the filtrate, and 1.56 kg of the following D-3* was gradually added while stirring at room temperature.

After 1.5 hours, water 51, concentrated hydrochloric acid 0.5β, ethanol 401
The resulting crystals were collected by filtration. Recrystallized from THF 101, acetone 151, ethanol 201, yellow crystals 2
．． 64 kg (yield 88%) was obtained. Melting point 208-21
5°C (decomposition) Synthesis Example 2 Compound ■-34 200 g of paraformaldehyde was added to 600 g of 7 volumes of dimethylamine 50% water, and 2-pentadecyl-5-propylhydroquinone (synthesized in steps 1 to 2 of Synthesis Example 1) was added.
B) After adding 200g, add 800g of ethanol and
Heat vigorously to reflux for an hour. The mixture was slowly cooled to room temperature, and the precipitated crystals were collected by filtration and washed with methanol to give 210 g of pale yellow crystals (yield: 80%).

(Step 2) 2.5-bis N,N-dimethylkoshi Etto the (F)loOg obtained in the above step. 700-ml of alcohol was added and the mixture was refluxed. This is G.

2.30g of ferric chloride 6 permanent compound in water 800-1 hydrochloric acid water 10-1
Water dissolved in 0-? 8 liquid was added and heated under reflux for 5 hours.

After cooling, the mixture was extracted with chloroform, and the extract was washed with brine and potassium carbonate, and then concentrated under reduced pressure. Crystallization was performed from acetonitrile to obtain 85 g of yellow crystals (yield: 85%).

(Step 3) 280 g of 2,5-bis(trimethylammonol) was added to 60 g of (G) obtained in the previous step and heated under reflux for 4 hours. Concentrated under reduced pressure, and the compound (
96 g (yield: 100%) of crystals of H) were obtained.

30 g of (H) obtained in the above step, 22.7 g of 2-methoxy-5-acetylaminobenzenesulfinic acid, 16.3 g of sodium acetate, 100 g of acetic acid, and 200 g of dichloromethane.
1R1, dimethylformamide 400m+! Add 6
The mixture was stirred at 0°C for 6 hours. After cooling, the mixture was extracted with ethyl acetate and subjected to silica gel column chromatography to obtain (1) from a chloroform-methanol (100/1) fraction. Acetate ethyl ester/hexane (5/6
) Recrystallized from solvent to give 6.4 g of yellow crystals (yield 19%)
I got it.

(Step 5) 2.5-bis((5-amino-?) 120 ad of ethanol and 24 g of concentrated hydrochloric acid were added to 6.3 g of (1) obtained in the previous step, and the mixture was heated under reflux for 3 hours. The yellow crystals were collected by filtration. 4.6 g of the hydrochloride of (J) (
A yield of 75% was obtained.

(Step 6) Adding 1-34 dichloromethane to 4.6 g of (J) obtained in the previous step.
, 2.9 g of pyridine was added to the JJD, and while stirring, 7.9 g of the following compound D-[phase]* was added in the form of crystals. After reacting at room temperature for 4 hours, diluted hydrochloric acid was added and extracted with dichloromethane. After condensing the extract, the residue was subjected to column chromatography and chloroform-methanol (100/
1) Crystallization was performed using l-34 obtained from the fraction and methanol to obtain 9.1 g of red crystals (yield: 83%). Melting point 13
5-145℃.

*D-0 The compounds represented by the general formulas (1-A) and (1-B) in the present invention directly absorb radiation, and the compounds represented by the above-mentioned formulas (1-A) and (1-B)
It is used for various purposes such as phase]. Therefore, U.S. Pat. No. 4,139,389, U.S. Pat.
No. 57-84453 and U.S. Pat. No. 4,232
, No. 107, JP-A-59-101649, Research Disclosure 1984-24025, JP-A-61-88257, etc. It is.

Usable radiation includes visible light, UV light, X-rays, and gamma radiation.
In addition to electromagnetic waves such as rays, examples include electron beams and sulfur rays.

The substance present in the system and capable of transferring electrons may be water, a binder, a solvent, or a dispersing oil, or a substance generally known as a reducing agent may be separately added. Good too.

Furthermore, one or more compounds known as photoreducing agents, such as quinones, carbon disulfide, zenadinium salts, β-ketosulfide nitroarene, diazoanthrone, etc., may be added to -II.

Further, electron-donating compounds such as amines, alkoxy-substituted aromatic compounds, etc. may be added.

It is also good to add a compound generally known as a hydrogen source compound or use it as a binder or oil. Although many hydrogen source compounds are known, organic compounds having a hydrogen atom weakly bonded to a carbon atom are generally effective.

Such compounds are described, for example, in U.S. Pat. No. 3,383.21.
No. 2 and Japanese Unexamined Patent Publication No. 58-3219.

The radiation vA perceptive material of the present invention may be formed from the above-mentioned compounds alone. Further, the material may be formed in combination with one or more of the electron-donating compounds, photoreducing agents, and hydrogen source compounds.

Usually in a specified solvent? This is coated and used as a film, but in this case, various resins and other components may be used. In addition, bases or acids or their precursors, dispersion aids (high-boiling oil, surfactants, etc.), etc. may be added to the membrane depending on the intended use.

In addition, it can also be used as a molded body or as a solution system.

The radiation-sensitive composition containing the compound represented by the general formula (1-A) (1-8) of the present invention can be used in various image forming methods and etch knobs, as shown in the examples of (1) to [phase] above. , can be applied to Metsuki, etc.

(2) Specific effects of the invention According to the present invention, a radiation-sensitive material can be obtained which can exhibit various functions depending on the purpose by irradiation with radiation.

(2) Specific Examples of the Invention Hereinafter, specific examples of the present invention will be shown and the present invention will be explained in more detail.

Sample 1 was prepared by coating each layer in the following order on a hand-applied polyethylene terephthalate support.

+1) Mordant layer containing 3.0 g/rtl of gelatin and 3.0 g/n of the following polymeric latex mordant.

(2) Hydroxyethyl cellulose o, s g /
A layer containing =.

(3) Compound 1-34 at 1.0 g/po, tricyclohexyl phosphate 0.05 g/=, gelatin 2
．． Layer containing 0g/d.

Next, sample 1 was exposed to light for 5 minutes using a 500W xenon lamp as a light source through a continuous tone wedge, and then stored for 30 minutes at 60° C. and 90% RH. After making one cut with a cutter knife on the coated side of this sample, apply adhesive tape evenly, and then peel off this tape, and the layer containing the coloring material in layer (3) will be on the tape side. A layer (1+ mordant layer) remained on the support side, and a magenta negative image (high density where the amount of light was high and low density where the amount of light was low) was clearly formed on this mordant layer.

When the transmission density of this color image was measured, Dmax = 2.
53, Dmin-1), 06.

Main practice For sample l of Example 1, layer (3) was removed except for layer (2).
) with hydroxyethyl cellulose 2 instead of gelatin.
．． Sample 2 was prepared using 0 g/m.

[
A very sharp image was obtained in (1).

When this image was observed under a microscope, even minute lines with a line width of 5 μm appeared sharp.

Sample 3 was prepared by coating the following layers on a general polyethylene support.

■) A layer containing 1.0 g/m of compound f-3, 0.05 g/g of tricyclohexylphosphate, and 2,087 m of gelatin.

2) Protective layer containing gelatin 0.5 g/m, triacryloyltriazine (0,02 g/m) as hardener.

After exposure in the same manner as in Example 1, 10% of buffer solution (Britton-Robinson's) at pH 1),0 was added.
After soaking for a minute, washing with water for 30 seconds, and air drying.

This sample had a yellow positive image (low density where the amount of light was high).

The dye released in the photoreaction was eluted in the buffer solution, and the reason why the amount of light was low was because the coloring material remained without photoreaction and did not release the dye.

Sougai±1 Undercoated polyethylene terephthalate film (
The following coating solution was applied onto a sample (100 μm thick) and dried with warm air to create a film with a dry film thickness of 4.0 μm (Sample A).

Gelatin 2.5g Compound 1-40 of the present invention 1.8g Mucochloric acid (1% water? 8M) 3mf water
Polyethylene with a thickness of 80 μm was provided on both sides of 5Qmffi paper, and poly(methyl acrylate-co-N,
A copolymer of N,N-trimethyl-N-vinylbenzyl ammonium chloride (the ratio of methyl nacrylate and vinylbenzyl ammonium chloride is 1:1) was applied to create a film with a dry film thickness of 3.0 μm (sample). B).

The sample was imagewise exposed to light for 70 seconds using a high-pressure mercury lamp, then moistened with water, brought into close contact with sample B, and left for 60 seconds. When sample A and sample B were peeled off, a magenta dye image was formed on sample B corresponding to the exposed area of sample A, and the density of the exposed area of sample A was 20% or less compared to the unexposed area. .

[Major launch] Primed polyethylene terephthalate film (
0.1 of the compound l-19 of the present invention was added to the
A coating solution in which 0.2 g of polyvinyl butyral resin and 0.2 g of polyvinyl butyral resin were dissolved in 5-ethyl alcohol was applied using a rod bar to form a film with a dry thickness of 3.4 μm (Sample C). On the other hand, a coating solution containing a copolymer of styrene and trihexylaminomethylstyrene in a molar ratio of 50:50 was coated to a dry thickness of 30 μm on a polyethylene terephthalate film (thickness 20 μm) that had been coated with another undercoat (Sample D). ).

After exposing sample C to imagewise light for 90 seconds with a xenon lamp,
It was heated to 100° C. for 10 seconds, and Sample C and the sample strip were peeled off. A yellow dye image corresponding to the exposed area of sample C was formed on the sample plate, and the density of the exposed area of sample C was 1/9 or more of that of the unexposed area.

Next, 400 pieces of silicon dioxide were deposited on a 41-square-meter silicon wafer by the CVD method. To this, compound V-10 of the present invention
, 5 g and alcohol-soluble butyrate 0.3 g dissolved in methyl alcohol was applied using a spinner, and after drying, it was exposed to a 150 W high-pressure mercury lamp through a mask for 10 minutes. Then add methyl alcohol 10- to hydrochloric acid 1) R1
Did you add? When the coating film was dissolved with liquid 8, the silicon dioxide in the irradiated areas was etched away.

Example 7 On a glass substrate, 600 layers of resin were deposited by vacuum deposition. 5 g of the compound v-7 of the present invention was dissolved in a solution prepared by dissolving 1.2 g of polystyrene in 6.M benzene.

This solution was applied onto a glass substrate on which silver was vapor-deposited, and the thickness was 0.
．． A 5 μm film was made. In addition to this, the xenon lamp 42
After irradiating with light of 0 nm or less for 5 minutes, the coating layer and most of the silver iodide were removed with benzene. Silver reflected little in the light irradiated area, and silver iodide was formed. Trace amounts of remaining silver iodide were removed with a 0.1M aqueous solution of ammonium thiosulfate. In this way, we were able to create a conductive pattern.

Add polyvinyl butyral Ig to 7 ml of ethyl alcohol.
and 3N1 ethyl acetate, and 0.7 g of the compound Vl-2 of the present invention was dissolved therein to prepare a coating solution αυ.

A solution prepared by dissolving 0.1 g of nickel chloride and 0.5 g of polyvinyl formal resin in dimethylformamide was coated on a glass substrate to a dry thickness of 2 μm. The above coating liquid was applied to this using a spinner (dry film thickness: 2 μm). After irradiating xenon light through a density mask for 60 seconds, only the upper layer was dissolved and removed, and then immersed in a silver electroless plating bath, silver was deposited only on the exposed areas. It is thought that nickel-containing sulfur compounds were generated in the exposed areas and became plating nuclei.

Next, the JLIL Kame ABS resin plate was immersed in a roughening solution for 10 minutes, then immersed in a catalytic solution containing 30 g/l of tin dichloride and 20 dll of hydrochloric acid for 1 minute, and then 0.25 g/l of palladium chloride.
AB
Metallic palladium was deposited on the surface of the S resin. A solution prepared by dissolving 8 g of the compound Vl-4 of the present invention in 10 LR1 of a 4% polyvinyl alcohol aqueous solution was applied using a spinner. The coating did not dry completely, but formed an almost solid film. This was irradiated with G-line from a mercury lamp for 4 minutes by stretch exposure, and then the coating film was removed with warm water. The unexposed areas were then immersed in a commercially available electroless copper plating bath for 90 seconds at room temperature, and the unexposed areas were copper plated. From this, it appears that palladium is deactivated in the exposed areas.

1.0 g of Compound X-3 of the present invention was mixed with 7 ml of toluene and methyl serotonin. 800% silicon dioxide on silicone wafer
A vacuum-deposited plate was pretreated with hexamethine disilazane, and the above coating solution was spin-coded onto it to give a dry film thickness of 1.
A 0 μm photoresist film was made. This was placed on a hot plate and heated at 90°C for 30 seconds, and then exposed to a
Second exposure.

Further, as a post-hake, it was heated at 140°C for 50 seconds.

Then, when it was developed for 30 seconds with an alkaline developer containing tetraethylammonium hydroxide, 1.
A pattern capable of resolving lines and spaces of 5 μm was obtained.

Major Aim ■ The following coating solution was applied to a top and bottom coated polyethylene terephthalate film (thickness: 100 μm) and dried with warm air to create a yellow film with a dry film thickness of 2.5 μm.

Polyvinyl butyral 1. Og Compound of the present invention [1-121,2g Ethyl alcohol 9.0-Butyl alcohol 1. For each Qmi, a solution of 1.0 g of polyvinyl butyral, 0.6 g of nickel chloride, and 8 ml of ethyl alcohol was applied to a polyethylene terephthalate film (1'7°, 20 μm) to prepare an image-receiving sheet with a film thickness of 3.0 μm.

A 100 μm thick polyethylene terephthalate film containing the compound of the present invention was imagewise exposed for 80 seconds using an IKW xenon lamp, and then the film and image receiving sheet were brought into close contact and heated at 150°C for 10 seconds. ? 1) Shita. A magenta image is formed on the image receiving sheet corresponding to the exposed area, and the maximum absorption wavelength of that color is 530n.
m, optical 4th degree is Maches? When measured with a gray filter attached to a 3-degree meter, it was 1.15.

Claims (1)

[Claims] (1) A radiation-sensitive material characterized by containing a compound represented by the general formula [I-A] or [I-B] as a radiation-sensitive substance. General formula [I -A]▲ There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [I -B]▲ There are mathematical formulas, chemical formulas, tables, etc.▼ Even if (Nuox)^1 and (Nuox)^2 are the same in the formula They may be different and represent =O, =N-R^4. Here R
^4 represents a hydrogen atom, a hydrocarbon group, a substituted hydrocarbon group, or -SO_2R^5 (R^5 is a substituted or unsubstituted hydrocarbon group). L represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. Here, R^6 and R^7 may be the same or different and each represents a hydrogen atom, a hydrocarbon group, or a substituted hydrocarbon group, and Z is a carbon atom supporting R^6 and R^7. Represents an electronegative divalent atomic group. R^■ is a divalent alkylene group (containing 1 to 3 atoms in the divalent bond), and n is 0 or 1. R^9 is a hydrocarbon group or a substituted hydrocarbon group, E is carbonyl or thiocarbonyl, and Y is an amino group, oxygen atom, selenium atom, or sulfur atom. UG can be transformed into Z-UG or by irradiating with radiation.
It represents a group released in the form of Y-UG. In addition, R^1, R^2, and R^3 are each a hydrogen atom, a substituted or unsubstituted hydrocarbon group, a halogen, a sulfo group, a carboxyl group, an alkoxycarbonyl group, a carbamoyl group,
Represents an alkoxy group, an acyl group, an alkylthio group, a sulfonyl group, a sulfamoyl group, an acyloxy group, and a sulfonyloxy group. When R^1, R^2, and R^3 are located at adjacent positions on the ring, they may be bonded to each other to form a saturated or unsaturated ring. Also R^1, R^2, R^3
may be L.