JPH0348500B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel photographic or photolithographic materials. This specification describes coatings useful in photography and photolithography, and photoresists using diacetylenes and new types of coatings for photography and other purposes. According to the invention, multiple regions (domains) exhibiting a unique regular structure
The coatings are made to provide photographic film and photolithographic materials with superior high resolution and efficiency.

The diacetylene compositions comprising the materials of the present invention provide greatly improved photographic and photolithographic properties compared to materials known in the prior art. That is, greatly improved efficiency, opacity, structural regularity, resolution, contrast, and adhesion to substrates are demonstrated. A direct comparison was made with commonly used photoresist materials. Known substances such as glycidyl methacrylate, polybutadiene sulfone and polymethyl methacrylate are 0.1
It has a quantum efficiency of an order of magnitude or lower, but
The diacetylene samples of the present invention have quantum efficiencies of 10 ⁸ to 10 ¹² molecules reacted per photon of light. Similarly, while conventional materials require radiation absorption of 10-20 to 300-500 joules per cm ³ to reach the above quantum efficiency, the diacetylene of the present invention requires only a radiation absorption of 10-20 to 300-500 joules per cm ³ . about 0.03
All you need is joule. Furthermore, the resolution of currently used photoresists is approximately 10,000 Å.
, and even in extreme cases it is 2000-3000Å,
The resist of the present invention resolves structures of about 100 Å. Therefore, it will be readily appreciated by those skilled in the art that the diacetylenic coating compositions of the present invention represent a very substantial advance in photography and photolithography.

Photoresist is a photoresist in 1852, British Patent No. 565 was awarded to Tolbot for a photosensitive gelatin coating of dichromate effective for differential etching of copper with ferric chloride. It has its beginning in the year.
Since this time, many compositions and methods have been developed and
It serves to transfer a pattern of light or other radiant energy onto a substrate through a coating intermediate sensitive to such radiant energy. The technology of lithography has been widely developed in recent decades, encompassing a variety of printing, etching, and image reproduction techniques, from macroscopic to microscopic, and has fostered the development of an entirely new industry. For an overview, see "Photoresist Materials and Methods" by William DeForest, McGraw-Hill, 1975.

One industry that relies heavily on the use of photolithography is the microstructure fabrication industry.
This industry produces structures placed on the surface of thin films of very small dimensions, and is used in the manufacture of information processing, electronics, switches and other devices that rely on integrated electronics, and on a single piece of silicon or other substrate. is the basis for the fabrication and interconnection of large numbers of very small devices to

A typical use of photolithography, commonly referred to in the industry as a photoresist, is described by RWKeyes in Science, Volume 196, No. 4293, pp. 945-949. It is described in. As in the Keith article, a substrate, usually silicon, is coated with a layer of a non-conductor, often silicon dioxide, "grown" from the substrate itself by a suitable oxidation process. The substrate is then coated with one or more layers of photoresist. Selected portions of the photoresist are then exposed to a suitable type of radiant energy, and the radiation alters the structure or physical properties of the portions of the photoresist so exposed. That is, light, particularly electromagnetic energy such as ultraviolet radiation, used to change.

As a result of irradiation of selected portions of the photoresist and associated changes in structure or physical properties, a distinction is made between selected and unselected portions of the resist based on changes in structure or physical properties. That is, selected portions are seen to be more or less suitable to be removed from the underlying substrate than unselected portions by appropriate means. The selected portion is more or less soluble in the liquid medium, has a higher or lower vapor pressure, or is more susceptible to chemical attack than the unselected portion. or exhibit lower resistance or exhibit other structural or property differences that make them uniquely amenable to removal from the substrate. Based on one or more of these distinctions, selected (illuminated) portions of the photoresist are removed from the substrate leaving unselected (non-irradiated) portions on the substrate; or Remove the unselected parts and leave the selected parts. By analogy with traditional photographic methods, in the case of photoresists, the former method is carried out using a so-called positive-working photoresist, and the latter uses a negative-working photoresist.

Selection of the portion of the photoresist for irradiation may be done in a variety of ways, all of which are well known to those skilled in the art. Masking is a common method carried out by placing a mask, usually photographically produced, on the surface of a photoresist-coated substrate (or composite substrate) and passing radiation through the mask. It will be done. The mask is designed to have transparent and opaque areas, depending on the parts of the resist layer that are to be irradiated and the parts that are not, respectively. As is well known to those skilled in the art, the radiant energy used in masking techniques is subject to the benefits of collimate, focusing, monochromatic light, or close contact. Also, all parts of the electromagnetic spectrum are used in masking techniques, such as various forms of particle irradiation such as electron beam, ion, beam, and plasma irradiation.

It is also known to irradiate selected portions of a resist layer without masking. i.e. direct projection of radiant energy beams, especially lasers, electrons or particles.
projection) may be used to irradiate selected portions of the layer. Such projection is generally controlled by automated equipment and computers. It is understood that equipment and mechanisms for irradiating selected portions of photoresist are well known to those skilled in the art. For example, IEEE Bulletin, Volume 62, No. 10,
Henry, October 1974, pages 1361-1387. "Surface-Acoustic-Wave and thin-film optical device fabrication technology; X-ray optics: Application to solids" by Hery I. Smith [H. J.A. Edited by HJQueisser].
E. E.Spiller and R. "X-ray lithography" with R.Feder
(1977) pp. 35-92 Springer, Ann. Rev. Mat.
Sci.), Vol. 6, pp. 267-301.
LFThompson and Earl. E.
"Polymer resist system for photo and electron resist" with REKeruin
I want to be seen.

Irradiation of selected portions of the photoresist and selective removal of selected or unselected portions results in irradiated or unirradiated photoresist, depending on whether a negative or positive tone is used. It will be appreciated that the pattern created by the resist will remain on the substrate.
This pattern of photoresist will normally alternate with silicon oxide. The exposed segment or portion of the silicon oxide (or other substrate) layer is then subjected to processing. In almost all cases, the oxide layer is removed or etched by methods well known to those skilled in the art. Silicon oxide etching aims to expose the underlying silicon substrate for processing and processing.
It is intended that the silicon oxide etch be carried out only in areas not covered with photoresist. Therefore, the photoresist must be relatively insensitive to the etching means used to remove the exposed oxide portions.

After etching away the oxide layer, the remaining photoresist is removed to produce a pattern of exposed silicon and silicon oxide or other substrate material. The exposed silicon is then treated to change its electrical properties. This treatment often involves a process called "doping."
Doping is well known to those skilled in the art and involves diffusing elements such as phosphorous or boron into exposed silicon or other substrate materials. Post-photoresist removal processing is not directly relevant to this embodiment of the invention and is well known to those skilled in the art. The processed article is then recoated with photoresist, selectively exposed, subjected to specific removal of the resist, etched, and so processed one or more times to form a substrate. results in a complex surface structure. Also, as is well known to those skilled in the art, resist layers that are selectively exposed and removed can deposit metals or other conductive materials onto the substrate surface to make electrical contact with variously treated surface areas. It is also used to form

The background of the above is microfabrication.
It is not meant to be a strict delineation of the technical divisions;
and it should be understood that many variations, both in materials and methods, are known. Furthermore, it should be understood that the term "photoresist" is used by those skilled in the art as a general technical description of all types of radiation-sensitive coatings useful in lithography. . The term therefore encompasses microfabrication, etching, printing and many others. Similarly, the term "photoresist" is also used for coatings that are sensitive to particle radiation, such as electron beams.

It is clear from the foregoing that the properties of photoresists useful in particle photolithography are of critical importance to the success of the process. It is generally recognized by those skilled in the art that an ideal photoresist will exhibit certain typical qualities. That is, the photoresist should be capable of ultra-fine resolution and exhibit a high degree of response to incident radiation. Additionally, typical photoresists must be easily applied to a substrate, coat the substrate uniformly, and remain tightly adherent to the substrate until removal is required. Furthermore, when exposed to incident radiation, the resist undergoes a substantial change in physical properties, thus making it possible to remove the exposed areas from the substrate to facilitate removal of the unexposed areas from the substrate when required. A clear distinction must be provided between the parts.

As already indicated, many compositions have been developed for photoresist methods. Also, as already explained, it depends on whether selective removal or selective remaining of the exposed portions of the resist is expected.
Resists are divided into "positive type" and "negative type." Generally, negative photoresists work through bond-forming mechanisms such as cross-linking or polymerization. That is, such resists generally include monomers that polymerize or polymers that crosslink when exposed to radiation. Thus, in negative resists, the effective molecular weight of the system
molecular weight), which facilitates specific removal of non-irradiated areas. The conventional means for effecting such removal is dissolution with a solvent, but other means such as volatilization are also used. Positive-tone resists, on the other hand, generally operate via a bond disassembly mechanism that decreases molecular weight. Therefore, the exposed portions of the positive resist are specifically removed in such systems.

The materials of the invention are also well suited for photographic applications. Those skilled in the art will appreciate that the advantageous properties of the materials making up the materials of this invention and the advantages of these properties are applicable to photographic systems. That is, photographic materials and systems with excellent sensitivity, resolution and efficiency are created with these materials. In addition, these materials have been found to polymerize to exhibit a broad spectrum of vivid colors, resulting in novel color photographic materials.

The photographic and photolithographic materials of the invention are
It has single-layer and multi-layer structures consisting of a plurality of domains with a regular structure. It is thought that such multiple domains play a role in providing the excellent properties shown here.

Recognized by those skilled in the art as the preeminent work in the field, Doforest's textbook provides an educational background for understanding negative photoresists. That is, it is known to include a cinnamic acid derivative in a photoresist composition in order to take advantage of the cinnamic acid ester's ability to form intramolecular crosslinks upon irradiation. One such derivative is cinnamate ester of polyvinyl alcohol, which has been used as a resist since 1953. Polystyrene-cinnamate esters have also been used. It has been reported that cinnamylidene acrylate ester exhibits high photoreactivity in resist compositions. US Pat. No. 3,767,415 to TanaKa teaches the use of polyvinyl cinnamylidene acetate in such systems.

The deforest literature contains many isoprenoids.
Rubber specifically mentions "cyclized" isoprenoids, which are suitable for photolithography, especially for macroscopic applications. Furthermore, Doforest explains that even in systems using monomers that are themselves sufficiently photoreactive, photosensitizers are almost commonly included in commercially available negative resists. There is.

A number of negative resist systems have been reported that are particularly useful for polymerization or crosslinking by electron beam radiation. That is, epoxidized polybutadiene, polysiloxane, and polyacrylics, particularly copolymers of (glycidyl) methacrylate and ethyl acrylate, are reported to be effective. See the Thompson and Kelwin report cited above.

U.S. Patent No. 3840369 to Carlick et al.
The issue teaches the use of isocyanate-modified polyfunctional ethylenically unsaturated monomers in photoresist agents. The use of thienyl acrylics in negative resist systems was disclosed in U.S. Patent No. 1 by Satomura.
Disclosed in No. 3945831.

Spiller and Feder's work describes polymethyl methacrylate, poly(butene-1) sulfone,
Polyvinyl, ferrocene, barium-lead, acrylate, polybutadiene, poly(diallyl-ortho, phthalate), poly(dichloropropyl acrylate) and epoxidized polybutadiene are disclosed.

The use of diacetylenes in photography and elsewhere is disclosed in several US patents. That is,
Cremeans U.S. Patent No.
3501297, Foltz U.S. Patent No.
No. 3,501,302 and US Pat. No. 3,501,303 to Foltz et al. have a common assignee and share similar disclosures. These patents disclose dispersing crystals of certain diacetylenes in a carrier means to create reactive compositions for direct imaging. As these patents teach, certain microcrystalline diacetylenes can be incorporated into resins, gelatin or gum matrices.
matrix) and selectively exposed to light, demonstrating a color change in the areas so irradiated. The electronic efficiency is reported to be between 8 and 16.

Additionally, Adelman's U.S. Patent No.
No. 3501308 provides microcrystalline diacetylenes in photographic binders. However, in addition, organic pi acid (pi
-acid) Electron acceptors are mixed to improve the sensitivity of the composition. Cremins U.S. Patent No. 3679738
The issue describes crystalline photosensitive diacetylenes with specific chemical formulas that include alkali metal carboxylates. Photosensitive coatings are provided by dispersing fine crystals in a binder matrix.

US Pat. No. 3,723,121 to Hauser relates to thermochromic laser bleaching of preformed polymers of diacetylenes.

No. 3,743,505 to Bloom et al. discloses the use of amine salts of diacetylene carboxylates in photographic processes. Although pure crystals of polyacetylenes are deposited from solution onto the substrate, it is preferred that the crystals be dispersed in a carrier means or binder.

Guevera et al., U.S. Pat. No. 3,772,011, discloses that when a polymer is created in a microcrystalline layer adjacent to a photoconductive layer, it photopolymerizes to produce a highly colored polymer that can be directly imaged. A diacetylene composition for making is provided. Such polymerization occurs upon exposure to light while applying an electrical potential to the layer. In some cases, organic photoconductors may be included in a layer of crystalline polyacetylenes.

Luckey, US Pat. No. 3,772,027 provides crystalline polyynes with improved sensitivity and, through the inclusion of inorganic salt sensitizers, a broad absorption spectrum. Fico et al., US Pat. No. 3,772,028, obtains the same results with the inclusion of pyrylium or thiopyrylium salts. A similar improvement in sensitivity was also achieved by Ehrlich in U.S. Pat. No. 3,811,895.
have been obtained in such systems. These disclose the use of organometallics as sensitizers and the use of such sensitized systems as X-ray film media.

Amplification of weakly imaged crystalline diacetylene compositions is obtained by Borsenberger et al., US Pat. No. 3,794,491. The slight image is enhanced by exposure radiation.

In order to ensure diacetylene imaging compositions with better resolution, Rasch, in US Pat. No. 3,822,134, produced compositions with a much finer grain structure than previously available. The use of vacuum evaporation facilitates the isolation of such fine crystallites.

No. 3,844,791 to Bloom et al. discloses suitable components for dispersed crystalline polyacetylene photosensitive compositions. That is, ammonium carbonate is included in the diacetylene moiety to improve its sensitivity. In related US Pat. No. 4,066,676, Bloom et al. provide amine salts as such inclusions.

Russian Chemical Review
A report by Khimii (1963) in Vol. 32, No. 5, pp. 229-243 (1963) shows that certain polyacetylenes exhibit high photoelectric sensitivity in modulated light. has been disclosed.

Applied Chemistry (Angewandte Chemie) Volume 65, No. 15
Bohlmann, No. 385-408, relates to the use of certain polyacetylenes as radiographic substrates.

Hartlein US Patent No.
No. 3,702,794 discloses improving adhesion between silicon-based compounds and polyolefins such as polypropylene and polyethylene through the use of silanes and chlorinated organic compounds.

U.S. Pat. No. 4,154,638 to Franz et al. discloses coupling agents between inorganic materials containing tin or similar metal groups and organic polymers.
polyfunctional silane as agent). The use of silicon-functional end groups in the primer is disclosed.

U.S. patent no.
Nos. 3,911,169 and 4,103,045 disclose methods for improving the adhesion of photoresist coatings to inorganic oxide surfaces. Aminosilane-polysilazane and siloxane copolymers are disclosed as promoting adhesion of polymeric resists to oxide films. No disclosure is made regarding covalent bonding.

The compositions, methods or techniques described or cited above do not anticipate or define the photographic or photolithographic materials of the present invention.

FIG. 1 is a schematic diagram of the polymerization of the composition constituting the material of the present invention, by which the mechanism is postulated. The regularity of the monomer population and the resulting polymer are shown.

FIG. 2 is a representative illustration of certain embodiments of the invention, particularly photographic film. 1 is a coating containing the material of the invention and 2 is a substrate containing one or more layers. It should be understood that the coating 1 can be a single layer, multiple layers or other layers. Additionally, substrate 2 may include non-uniform materials or aggregates. In one embodiment, substrate 2 includes a flexible film and coating 1
is one or more diacetylenic materials; in other cases, 2 is doped silica.

FIG. 3 shows the microstructural regions of the material of the invention.
That is, it indicates that the region as indicated by 3 has an essentially regular arrangement of the constituent molecules. The direction of this array is as indicated by the hatching above it. 4 indicates the average size of those areas.

In general, the novel materials of the present invention are useful in photography and photolithography. That is,
The materials of the invention are useful in photography, new means of macroscopic and microlithography, printing, etching and engraving, and new means for the fabrication and assembly of microstructures, particularly in the fields of electronics and integrated electronics. provide the means. Additionally, certain chemical compositions are taught in the materials of the present invention, along with the fabrication and assembly of objects utilizing them.

The photolithographic material of the present invention exhibits excellent performance in the fabrication and assembly of electronic microstructures, requires only a small amount of radiant energy during use, and produces highly detailed resist pattern structures on the surface of the substrate. It is characterized by the ability to That is, the material of the present invention utilizes a type of energy efficient photoresist material. This energy efficiency is demonstrated by comparing the X-ray photoresists of the present invention with typical components currently used in the industry. Spiller and Feder report that the currently used negative X-ray resist is 1 cm ³
It has been reported that an absorption amount of 1 to about 60 joules per unit is required. In contrast, the compositions of the present invention require only about 0.001 to 0.01 joules per cm ³ for polymerization. This high efficiency is evidenced by short exposure times and is accompanied by savings in radiant energy output and production costs.

The materials used are mechanically negative-type. That is, upon exposure to radiant energy, it polymerizes to form areas of polymer that specifically survive exposure to solvent compared to unexposed areas of the photoresist. Furthermore, the substance exhibits a physical and electronic structure that is highly suitable for polymerization;
That is, they are characterized by exhibiting exceptional efficiency or quantum yield of polymerization when exposed to radiant energy.

Other features of the compositions used in practice of the invention result from the unique physical and electronic structure of the compositions. The composition exhibits regularity such that very fine exposure patterns are resolved in the photoresist produced. For example, currently used X-ray photoresist compositions have a structural resolution of about 10,000 Å, and in extreme cases only 2,000 to 3,000 Å.
It is. The compositions of the present invention are used to enable structural resolution on the order of 100 Å. This improvement in resolution results in a direct increase in the number of microstructures incorporated on a given surface area of the substrate. This allows a reduction in the dimensions of the articles made thereby and results in substantial economic advantages.

Amorphous polymer resists undergo a physical "relaxation" phenomenon in some systems, causing microstructural lines to become unclear and
It is known to come as a blur. Furthermore, it is known that in many systems known in the prior art, some of the polymer that is desired to remain during dissolution dissolves, resulting in edge undercuts during the removal process. . However, the compositions of the present invention are ideally suited to overcome these problems. When exposed to incident radiation, the composition polymerizes very easily and with high efficiency into a regular polymer. The resulting polymer has physical properties that are very different from the unpolymerized composition. In particular, there is a significant difference between them in solubility. In fact, the polymerized composition
It is nearly insoluble in commonly used solvents compared to unreacted compositions. Therefore, as a result, the unexposed and therefore unpolymerized areas are almost completely removed upon exposure to the solvent, while the exposed areas remain largely intact in place. at the same time,
The great regularity of the polymerization process and the geometric similarity of the polymer to its constituent monomers minimizes the "relaxation" experienced by the system during polymerization. This provides sharp line definition and avoids blurring.

Other advantages have also been obtained by using the materials of the present invention. That is, although it is not necessary to use a sensitizer in the composition of the present invention, it may be used if desired. Furthermore, in the materials of the present invention, the polymerizable composition can be uniformly coated over the entire substrate, thus providing uniformity of lithographic resolution and clarity.

In one embodiment of the present invention, radicals are generated when heat is applied.
Includes substances that release radical trapping agents. Compounds of this type, such as the dimers of nitroso compounds known in ethylene systems (see Pazos, US Pat. No. 4,168,982), reduce thermal polymerization and
This will help you avoid "katsuto". It has been discovered that diacetylenes particularly benefit from their inclusion.

The compositions used in the materials of the invention exhibit excellent adhesion to substrates and exhibit a high degree of heterogeneity in physical properties upon polymerization, thus resulting in ease of processing and excellent results. In fact, the preferred form of the invention uses a siloxyl moiety to form a covalent bond between the photoresist layer and the substrate, resulting in very good adhesion between the substrate and the resist. Other forms of covalent bonding may also be used.

For example, the use of the materials of the present invention in photographic systems, such as photographic film, is similar in some respects to their use as photoresists. That is, thin films or film deposits using the materials of the invention are used either as directly printed positive-working photographic films or as negative-working films. The color change and intensity known to be possessed by these substances upon polymerization are useful in color photography, and their excellent resolution and sensitivity make them useful in photographic materials with unprecedented resolution and efficiency. Become.

Briefly, compositions useful in the materials of this invention include photoresist materials that include one or more types of compounds known as diacetylenes. Diacetylenes have at least two carbon-carbon triple bonds (acetylene bonds)
and at least two of its triple bonds are conjugated to each other. In other words, 1-3 as expressed by the following formula
It is known that there is a relationship between

．． R ₁ -C≡C-C≡C-R ₂ As known to those skilled in the art, an acetylene bond is
It has an almost straight shape. Therefore, we can define an approximately linear arrangement of six atoms with the four carbon atoms participating in the "backbone" of the diacetylene and the two carbon atoms attached to each end of the backbone. It has acetylenes. Furthermore, it is clear that the diacetylene structure is rich in electron density and has a novel electronic structure. This electronic structure and geometrical structure possessed by diacetylenes makes compounds such as those taught by this invention particularly uniquely suited for inclusion in photoresists and other compositions. I believe it is contributing.

Diacetylenes suitable for use in the practice of this invention follow the general formula:

R ₁ -C≡C-C≡C-R ₂ (wherein R ₁ and R ₂ may be the same or different and have 1 to about 50 carbon atoms, alkyl, aryl, (including alkaryl or aralkyl groups). Furthermore, R ₁ and R ₂ may have heteroatom substitution or unsaturation. That is, R ₁ or R ₂ represents one or more ester, acid, alcohol, phenol, amine, amide, halogen, sulfonyl, sulfoxyl, sulfinyl, silyl, siloxyl, phosphoro, phosphate, keto, aldehyde, or other moiety. May be included. Additionally, metal modifications of any of the above may be included, such as acid or phenolate salts. Additionally, R ₁ or R ₂ or both may be ester, acid, alcohol, phenol, amine, amide, halogen, sulfonyl, sulfoxyl, silyl, siloxyl, phosphoro,
It may be a phosphate, keto, aldehyde, or metal salt or phenolate. in short
It is contemplated that any diacetylene is suitable for use in practicing one or more embodiments of the invention, except for diacetylenes in which R ₁ or R ₂ or both are hydrogen. R ₁ or R ₂
Diacetylenes in which either or both are hydrogen are generally unsuitable due to the fact that they are explosive.

The compounds cited in this description of the invention may be straight-chain,
It is to be understood that it may be cyclic, aromatic or branched. It must also be understood that compositions of the invention that are diacetylenes do not exclude the presence of additional acetylene bonds therein. That is, 3
Compounds having 1, 4 or more acetylene bonds are contemplated as long as at least two or more of the bonds are conjugated to each other. Additionally, additional unsaturations such as carbon-carbon, carbon-oxygen, carbon-nitrogen or other double bonds, aromatics or heteroaromatics may be present. Halogens, hydroxyls, amines, thiols, silyls, siloxyls, phosphates, sulfates, sulfonates, or other functional groups are also useful.

For the practice of certain embodiments of the invention, diacetylenes preferably have the following general formula:

R ₃ -C≡C-C≡C-R ₄ (wherein R ₃ is a hydrophobic chemical moiety and R ₄
is a hydrophilic chemical moiety). Those skilled in the art will recognize that "hydrophobic" is a term that generally describes a chemical moiety or residue that is not attracted to water or electrically charged compounds. That is, hydrocarbon structures that are unsubstituted or lightly substituted with heteroatomic functional groups are considered hydrophobic. In contrast, a "hydrophilic" moiety is one that is attracted to water or an electrically charged compound and is considered to be substituted with a heteroatom substituent. That is, hydrophilic compounds have one or more acid, ester, alcohol, amino, thiol or similar heteroatom substituents, whereas hydrophobic compounds are characterized by their essential absence. The substituent R ₃ is
Diacetylenes of formula () containing a hydrocarbon moiety having from 1 to about 30 carbon atoms, preferably from 2 to about 20 carbon atoms, wherein R ₄ is Particularly useful.

−R ₅ −(A) _o (wherein R ₅ is 1 to about 50, preferably 1
is a hydrocarbon having from 1 to about 30 carbon atoms; n is an integer from 1 to about 10, preferably from 1 to 3, and A is halogen, COOH, COOR ₆ ,
CONH ₂ , CONHR ₆ , OH, SH, NH ₂ , NHR ₆ ,
N(R ₆ ) ₂ , silyl, siloxyl, sulfate,
One of the group consisting of sulfonates, phosphates, etc.
and R ₆ is a hydrocarbon having 1 to about 8 carbon atoms). Certain preferred forms of the compositions include styryl moieties in the hydrocarbon portion of R ₃ or include other polymerizable unsaturations such as dienyl, vinyl, or acrylic.

Certain embodiments of the invention are effectively carried out using compositions of the following formula:

R ₃ -C≡C-C≡C-R ₃ or R ₄ -C≡C-C≡C-R ₄ (wherein R ₃ and R ₄ are any of the same as above).

Other embodiments of the present invention advantageously employ diacetylenes of formula () in which R ₁ or R ₂ or both have the formula:

(wherein p is an integer from 0 to about 20, preferably from 1 to about 10; Y is O, NH, S, SO ₂ ,
SO ₃ , SiO ₂ , PO ₃ , PO ₄ , CH ₂ , amido, acetyl, acetoxy, acrylic, methacryl or styryl; R ₆ to R ₉ may be the same or different, H, NO ₂ , NH ₂ , monohalomethyl, dihalomethyl, trihalomethyl, halogen,
alkyl, alkenyl or aryl having 1 to about 6 carbon atoms, SO ₂ , SO ₃ , PO ₃ ,
PO ₄ , siloxyl, silyl, etc.). Some preferred compositions contain ethylene groups, resulting in a styryl diacetylene formula. In certain compositions, materials that have centers of chirality or asymmetric centers in their molecular structure and are optically active are useful for certain embodiments. That is, for example, R ₁
Also useful are compounds of formula () in which R ₂ or both have the following formula:

−(CH ₂ ) _q −R ₁₀ (wherein, q is an integer from 0 to about 20, and R ₁₀
is a residue with a chiral or optically active center). optical center
It should be understood that any substituents having ceenter) are considered useful herein;
Some exemplary embodiments are represented by the following formula.

or (In the formula, the * mark indicates the optical center, and Ar represents an aromatic group, preferably phenyl or naphthyl.) Similarly, chiral amino acids or other optically active residues are It may also be included in the acetylene composition.

In some embodiments of the invention, particularly those in which polymerization by ultraviolet or X-ray radiation is expected, it has been found to be advantageous to include some heteroatomic groups in the compositions of the invention. . Thus, halogens, especially fluorine, sulfur, selenium, phosphorus and similar atoms are preferably included. This serves in particular to improve the cross-section of energy absorbed by the composition, ie to improve its overall efficiency. To this end, particular attention is given to the use of polyfluorinated alkyl substituents in the practice of this invention, so that special uses of this type of residue are contemplated.

It should be clear from the above that no limitations are intended or implied as to diacetylenes suitable for one or more embodiments of the invention. All compositions containing one or more compounds having at least two acetylene bonds, at least two of which are conjugated to each other, are suitable.

Typical synthesis agents for diacetylenes are Garito et al., “Synthesis of N-(nitrophenyl)amine-substituted diacetylene monomers,” Makromolecular Chemie (in press); Garito et al., “Chiral (ehiral) Diacetylene Polymers” Polymer Chemistry (in press); Keter Pub.House, Jerusalem
1974, “Chemistry of Diacetylenes”; Kalyanaraman, Galitou et al., “Nitrophenoxymethyl-substituted diacetylene monomers”, Polymer Chemistry Vol. 180, June 1979; Baughman et al. “Solid-phase synthesis and properties of polydiacetylenes” Annals of NY Academy of Science, Vol.
Volume 313 (1978); Day et al., "Polymerization of acidic monolayers of diacetylene carboxylic acid at the gas-water interface," Journal of Polymer Science, Polymer Bulletin (J.
Polymer Sciences. Polymer Letters ed.) No. 16
Vol. 205, (1978) and Baugmann, US Pat. No. 3,923,622.

As a class, diacetylenes are thin films, multilayer films,
and exhibit a unique regular structure in the polymers made from them. Diacetylenes take on a regular orientation in a thin film formed on a substrate. This regular orientation is maintained to a high degree during polymerization, resulting in a polymer having regular orientation. This phenomenon, illustrated in FIG. 1, is known. Galatow et al., “Kinetics of solid-state thermal polymerization: 2,4-hexadiyne-1,6 diol, bis(p-toluenesulfonate)”, Journal of Polymer Science, Vol. 16, pp. 335-338; (1978);
Galitou et al.'s "2,4-hexadiyne-1,6-
Kinetics of solid-state polymerization of diol-bis(p-toluenesulfonate),” edited by Hatfield, “Molecular Metals,” Plenum.
Wegner, "Recent Advances in the Chemistry and Physics of Poly(Diacetylenes)", edited by WE Hatfield, "Molecular Metals", published by Plenum, (1979);
(1979). Other reports are
Journal of Polymer Science, Polymer Chemistry Edition
Polymer Science. Polymer Chemistry Ed.) No.
17, pp. 1631-1644 (1979), "Polymerization of diacetylenes in multilayers"; and Polymer Chemistry, Vol. 179, pp. 1639-1644 (1979);
It is also included in ``Quantum Yield of Topochemical Photopolymerization of Diacetylenes in Multimolecular Layers'' by Wegner et al., p. 1642 (1978). References were made in particular to reviews and references cited within them. Galitou and Wegner report on the chemistry, synthesis, structure, orientation, and polymerization of diacetylenes and poly(diacetylenes) and describe the multilayer behavior of some of them. The regular orientation in thin films has been reported to be a "herringbone" arrangement.
This array is believed to be very large and spread throughout the membrane. Wegner observed large areas where regions of regular orientation appeared to have been created. single domain polymer
single domain membranes that can be polymerized within
It is possible to make a film.

The chemical molecular structure of this type of polymer is poorly understood but will be explained. As shown in FIG. 1, polymers of diacetylenes are believed to have triple and double bonds in a 1-3 relationship within the subunits of the polymer. The two "resonance structures" shown for polymers are similar to those of poly(acetylenes), as they are for many organic molecules.
It will be understood by those skilled in the art that this also represents the fact that structural descriptions regarding bond orders such as triple, double, etc. are less precise than regular formulas. That is, the polymer is
It will be understood that such polymers will be described as having acetylene linkages in their subunits, having bonding properties that are not fully expressed as any single structure. Alternatively, it may be described as having repeating subunits of four carbon atoms aligned in a nearly direct configuration. That is, a polymer produced by the practice of the present invention (1) is essentially properly oriented in at least any polymer region, (2) has acetylene bonds within its subunits, and ( 3)
It may alternatively be described as having subunits having four carbon atoms in a substantially linear configuration.

In general, it is possible to coat substrates with diacetylenes and use the coatings for photoresists and other purposes. It is believed that the ordered orientation of the diacetylene background within the layer so produced places the acetylene bonds in the correct orientation for polymerization to proceed with high efficiency. This factor, combined with the amenability of diacetylenes to absorb radiant energy and undergo optical generation of free radicals or reactive intermediates such as carbenes, makes them highly reactive to incident radiation and highly irradiated. This gives rise to such oriented arrays of diacetylenes that sometimes polymerize rapidly.

Preferably, the coating of the substrate with the diacetylene composition is carried out by the Langmiuir-Brodgett method.
-Blodgett technigue). This technique is well known to those skilled in the art and results in a thin film of precipitated diacetylene on the surface of the fluid. next,
To make the arrangement close-packed, the surface layer is compressed to minimize the surface area occupied by diacetylene. This closely packed and aligned diacetylene composition is then transferred to a substrate by dipping. The use of diacetylenes having hydrophobic and hydrophilic substituents at their ends, respectively, facilitates the use of this method. This method results in multilayer (multilayer)
is created. These multilayers may be uniform or dissimilar in composition. They number from two to several hundred. That is, it includes thin films or thick films.

Other means of placing diacetylenes on the substrate may also be used. That is, in order to apply a diacetylene compound to a substrate, a "whirling" method as described in the Doforest literature is used.
techniques, roller coating, or even dipping, which are currently practiced in the industry, can be used. Coating by vapor deposition can also be used. The thickness of the membranes used in the practice of this invention will vary depending on the intended application. Layers of 2 to about 40 Langmiur-Brodgett films, or films of equivalent thickness made by other methods, are most suitable for photoresist applications, but other embodiments such as those shown in the photo may be used. is useful regardless of its thickness.

Compositions useful in the practice of this invention may also contain other diacetylenes in addition to the diacetylenes described above. That is, catalyst, photoinitiator (photo-
Additional polymeric materials such as initiators, pigments and fillers may also be added. Additionally, organic or inorganic substances may be added to modify the electrical properties of the composition, particularly when used in thin film devices. Additional polymeric materials included are:
It encompasses a wide range of polymeric materials known to those skilled in the art.
Olefins such as vinyl, styryl, acrylic, dienyl, etc. are suitable. Among these, dienyl compounds and acrylic compounds are preferred. Dimers of nitroso compounds are also included in the above.

The composition may optionally include a sensitizer or catalyst to improve the photochemical interaction between the composition and the incident radiation. Sensitizers of this type are well known to those skilled in the art and include, for example, dyes or other compounds such as acetophenone, acyloin derivatives, benzophenone, indigo derivatives. The sensitizer may comprise an amount up to about 5 percent by weight of the composition, preferably between about 1 percent and about 3 percent. In other embodiments, one or more layers of the diacetylene composition are sandwiched between layers containing a sensitizer;
We are getting good results.

Other compositions may include polymerizable moieties within the diacetylene compound in addition to the diacetylene bond itself. That is, good results can be obtained using diacetylene compounds having acrylic, styryl, vinyl, or other polymerizable functional groups. In such cases, the polymerization of such additional polymerizable structures is carried out concurrently or sequentially with the polymerization of the "backbone" diacetylenes.
Multiple monolayers of oriented diacetylenes
It can be seen that the polymerization of the "spine" occurs almost exclusively within one layer when a single layer is deposited on the substrate. The presence of other polymerizable compounds creates the possibility of interlayer polymerization or cross-linking. The inclusion of styrene residues is particularly suitable for this purpose.

For photography and photography, it is highly desirable to use photosensitive materials that combine high resolution with high sensitivity to radiation. Such goals are achieved by the present invention, which uses organized arrays of highly sensitive diacetylene membranes arrayed in multiple regions.

The inherently ordered arrangement exhibited by the diacetylene films of the present invention, especially those produced by the Langmiur-Brodgett method, contributes to the high photosensitivity of these films, which is reflected in the high quantum yield mentioned above. .
Although such high yields are desirable from a reaction rate standpoint and an overall savings in energy used, it has been recognized that such high yields seem to be contrary to one of the two objectives: high resolution. It will be done. It is believed that the high yield photoresists of the present invention exhibit uncontrolled polymerization or reaction when exposed to radiation, reacting not only in the exposed areas but also in their surroundings and unexposed areas. Dew. Preferred embodiments of the present invention overcome this difficulty and provide photoresists with both very high yield and high resolution.

This goal is achieved through a technique in which substantially aligned or aligned membranes on a layer of diacetylenes are placed in multiple regions within a membrane or layered structure. Although the essentially ordered arrangement of molecules is preserved within the regions thus provided, the regions are randomly oriented, so that the molecular arrangement orientation of a region generally does not deviate from the arrangement orientation of its neighbors. It will be acknowledged that it will not be repeated. That is, within any region, an essentially regular arrangement of diacetylene molecules will prevail, but the arrangement will terminate at the boundaries of the region. The sensitivity of diacetylenes arranged within the region will remain unchanged, but 1
It will be clear from the above that a photoreaction initiated within one region will not normally migrate to adjacent regions. It will also be clear that the embodiments described above will produce photographic materials and films of high sensitivity and high resolution.

Many methods can be used to form a diacetylene film consisting of multiple regions (domains). For example, a partially ordered film or layer of diacetylene material is heated by conventional methods such as laser or microwave heating, or other methods, to form a plurality of domains. When using conventional heating, heating to just below the melting point of the layer is preferred. Or Langmiyur
When using Brodgett's film formation technique, the pH, temperature, or specific gravity of the aqueous phase is adjusted to form multiple domains within the resulting film. Other techniques for forming the multiple domains of the invention will occur to those skilled in the art. It will also be appreciated that routine experience is required to establish optimal conditions for the formation of multiple domains with any given acetylene system.
However, when using the Langmiur-Brodgett film forming technique, the pH, temperature, or specific gravity of the subphase of water used in the process is adjusted to simulate the area within the resulting film. Those skilled in the art will conceive of other techniques by which regions according to the invention may be determined. It will also be appreciated that routine experience is required to establish optimal conditions for region formation with any given diacetylene system.

It is believed that the size of the area produced by the practice of the present invention will be reflected in the ultimate resolution of the photoresist. In fact, the average dimensions
It is possible to create regions of less than 1000 Å, and larger and smaller regions are specifically envisioned. That is, preferred embodiments have an average size of about 10,000 Å or less, more preferably about 2,000 Å.
It encompasses the following areas:

Another method of forming multiple domains within the diacetylene layer is to include less polymerizable molecules in the composition. These molecules can be any of a wide range of materials including long chain olefins or low reactivity diacetylenes with fatty acids. Alternatively, it may be entirely advantageous to polymerization by disrupting the essentially ordered sequences present within the membrane or layer, or by providing molecular or low reactivity to the ongoing polymer chain. A diacetylene compound having a steric or electronic structure that is not Such inclusions are found to suppress the reactivity of the membrane or layer and provide an alternative means of system control.

For certain applications, it is highly advantageous to provide strong adhesion of the coating to the underlying substrate. It is also possible to bond such a coating covalently to the substrate using certain techniques. That is, hydroxyl or other functional groups commonly found on the surface of many substrates are used to complete a silyl or siloxyl bond with an appropriately silicon-substituted diacetylene compound. Brautman, Krock (ed.), Composite Materials, Academy Press, No. 6 (1974).
Volume, Chapter 6 of E.P. Proidemann (EP
Plueddemann), ``Adhesion Mechanism Using Silane Coupling Agents.'' film to substrate or film pre-driver compound (film to substrate)
Other means of covalent attachment of precursor species will readily occur to those skilled in the art. That is, it is desirable to coat the substrate with a composition that forms a covalent bond with such a substrate and also forms a covalent bond with the diacetylene compound containing the photoresist layer. Although any composition that will form a covalent bond can be used, a compound suitable for effecting such a covalent bond is represented by the formula:

XI (R ₁₁ −O) ₃ −Si(R ₁₂ )−Z (wherein R ₁₁ may be the same or different,
a hydroxycarbyl group having 1 to about 6 carbon atoms, R ₁₂ is a hydrocarbyl group having 1 to about 6 carbon atoms, and Z is covalently bonded to the selected diacetylene compound. ). Preferably Z is an amine;
Although used to form an amide bond with the carboxyl group on the diacetylene, other suitable substituents may also be used. One example of such a composition is 3-3
Aminopropyltriethoxysilane, R ₁₁
is ethyl, R ₁₂ is propyl, and Z is amino. It will be appreciated that other covalent linkages other than the siloxyl and amide linkages described above may be satisfactorily used in the practice of this invention.

Several nitrosodimers are included in the photoresist compositions of the present invention, such as 1-nitrosooctadecane dimer, 1-nitrosododecane dimer, and 1-nitrosocyclohexane dimer, and these materials are included in the photoresist compositions of the present invention. It has been found that it can be used as a resist to inhibit thermally induced polymerization that is unhindered by photochemical polymerization centers. In this regard, it is believed that the dimer thermally dissociates into chemical species, inhibiting polymerization. That is, thermal polymerization is inhibited, but photopolymerization is not affected. Any other compound that provides free radicals that react thermally to trap the species is also effective in this regard.

It should be clear that any form of irradiation may be used to effect polymerization of the compositions of the invention. Of the commonly used formats, particle beam, electron beam, X-ray, laser and ultraviolet irradiation are most preferred. As should also be clear, irradiation with masking, irradiation with a controlled beam, or irradiation without effective spatial control, i.e., blanket irradiation, is not suitable for carrying out one or more embodiments of the invention. used. Generally, substantial polymerization will occur within the irradiated area. Substantial polymerization occurs when at least 50 percent of the monomer is incorporated into the polymer portion. Preferably an uptake of 75 percent, more preferably 85 percent or more is desired. In the construction of devices that include diacetylene polymers as constituents, selective exposure is desirable for photolithography and microfabrication. It can be seen that both modes of irradiation are effective.

For use as photographic media, it follows that many applications that respond to visible (or infrared) light become highly desirable. Thus, films or other materials may optionally employ well-known sensitizers to alter the spectral response of the material or product. Of course, diacetylene compounds with inherent sensitivity in the visible (infrared) region are suitable for this application even without the use of sensitizers.

Example 1 4-Nitrophenyl propargyl ether: A solution of propargyl alcohol (10 g) in dimethyl sulfoxide (DMSO) (10 ml)
_{K2CO3 (} 1.5) was added and the mixture was kept stirring. 4
-Nitrofluorobenzene (28 g) was added slowly and the mixture was stirred at room temperature for 3 days. It was poured into excess water and made slightly acidic with HCl. Thin layer chromatography (TLC) shows two spots,
One of them was the same as 4-nitrofluorobenzene. Recrystallization from cyclohexane gave a pale yellow solid (15.8 g, 50%).

Melting point: 108-110℃ Infrared absorption spectrum (KBr): 3174 (=CH),
1582, 1315, 847 (Ar ^- NO ₂ ) cm ^-1 Example 2 2,4-hexadiyne-1,6-diol-bis(4-nitrophenyl)ether: The substance of Example 1 (1 g) was dissolved in DMSO (15 ml) The solution was added to a solution of cuprous chloride (1 g) and ammonium chloride (3 g) dissolved in water (10 g) while stirring the solution at 55-60° C. while passing oxygen. After 4 hours, the mixture was poured into a dilute aqueous solution of ammonium chloride (500ml). The yellow precipitate was separated, washed with cold water, dried and recrystallized from dioxane-ethanol (1.3 g, 70%).

Melting point: 213℃ (decomposition) Infrared absorption spectrum (KBr): 1592, 1336,
847 (Ar ^- NO ₂ ) cm ^-1 Example 3 2,4-hexadiyne-1,6-diol-bis(2,4-dinitro-5-fluorophenyl)ether 2,4-hexadiyne-1,6- Diol (5
Diethylamine (2 ml) was added to a solution of g) in DMSO (15 ml). 2,4-dinitro-1,5-difluorobenzene (20 g) was slowly added with stirring at room temperature. After stirring overnight at room temperature,
The mixture was poured into water, and the product was separated, washed with water, dried, and then recrystallized from dioxane-water (16 g, 75
%). The compound decomposed without melting at temperatures above 190°C.

Infrared absorption spectrum (KBr): 1587, 1333,
846 (Ar ^- NO ₂ ), 1176 (Ar ^- -F) cm ^-1 Example 4 2,4-hexadiyne-1,6-diol-bis-(2-nitro-4-trifluoromethylphenyl) ether, 2,4-hexadiyne-1,6-diol (1
The reaction of g) with 4-fluoro-3-nitro-benzotrifluoride (4 g) was carried out according to the method of Example 3 to obtain the desired product. Recrystallization from ethanol gave pale yellow needles (1.1 g, 25%).

Melting point: 137℃ Infrared absorption spectrum (KBr): 1620 (NO ₂ ),
1120,682 (CF ₃ ) cm ^-1 Example 5 4-Nitrophenyl 1-bromopropargyl ether Aqueous solution of KOBr (22 g of KOH, 5 ml of BR ₂ and 100 g of water)
A solution of 4-nitrophenyl propargyl ether (3.5 g) dissolved in diosan (80 ml) was added dropwise to the solution (manufactured by ml) at 0°C with stirring. After stirring for a further 15 minutes, the solution was added to excess ice water and the precipitate was separated and recrystallized from dioxane to give a white powder (4.5 g, 90%).

Melting point: 156-157℃ Infrared absorption spectrum (KBr): 1587, 1324,
847 (Ar ^- NO ₂ ) cm ^-1 Example 6 1-(4-nitrophenoxy)2,4-hexadiyn-6-ol Cuprous chloride (20 mg), ethylamine (70%, 1.4
ml) and hydroxylamine hydrochloride (0.12g)
A solution of propargyl alcohol (1 g) in DMSO (2 ml) was added with stirring to a suspension of 100 g in water (5 ml). To the yellow mixture was added the bromoether of Example 5 (0.6 g) in DMSO. (20 ml) was added dropwise over 40 minutes at 20°C. After stirring for a further 1 hour, the solution was poured into excess water and the yellow precipitate was separated and recrystallized from methanol to form short needles. (0.4g, 74%).

Melting point: 172-173℃ Infrared absorption spectrum (KBr): 3448 (-OH),
1582, 1333, 846 (Ar ^- NO ₂ ) cm ^-1 Example 7 1-(2,4-dinitrophenoxy), 6-(4
-Nitrophenoxy)2,4-hexadiyne The compound of Example 6 (0.23 g) was dissolved in DMSO (3 ml).
Triethylamine (0.5 ml) was added at room temperature with stirring, and 2,4-dinitrofluorobenzene (0.2 g) was added dropwise. After stirring for 4 hours, the reaction mixture was poured into water and the precipitate was separated and recrystallized from dioxane to give pink crystals (0.35 g, 88%).

Melting point: 125℃ Infrared absorption spectrum (KBr): 1589, 1333,
846 (Ar ^- NO ₃ ) cm ^-1 Example 8 N-(2-propynyl)-2-methyl-4-nitroaniline Triethylamine was added to a suspension of potassium carbonate (20.0 g) in DMSO (7 ml). (3 ml) and 2-propyn-1-amine (7.10 g, 1.29 x 10 ^-1 mol)
added. 2-Fluoro-5-nitrotoluene (20.00 g, 1.29 x 10 ^-1 mol) was added with stirring and the reaction mixture was heated to 50°C for 3 days. The mixture was cooled, poured into excess water and extracted with methylene chloride. The methylene chloride solution was dried over sodium sulfate, filtered and evaporated. The residue was chromatographed on a silica column eluting with benzene and recrystallized from benzene to give yellow crystals.

Melting point: 121-123℃ Yield: 15.02g (61%) Infrared absorption spectrum (KBr): 3344 (NH),
3226 (CH), 1580, 1282 cm ^-1 (Ar ^- NO ₂ ) Example 9 N,N'-bis(2-methyl-4-nitrophenyl)-2,4-hexadiyn-1,6-diamine Cu (OAc) A suspension of ₂ H ₂ O (1.5 g) in pyridine-methanol (1:1, 15 ml) was added
(2-Propynyl)-2-methyl-4-nitroaniline (1.00 g, 5.26 x 10 ^-3 mol) was added. The reaction mixture was stirred at 50°C for 2 hours. The mixture was poured into excess water and filtered. The crude solid was recrystallized from nitromethane to give yellow crystals. Yield: 0.70g,
(71%). This substance does not melt below 200℃, and
It turned red at ℃.

Infrared absorption spectrum (KBr): 3390 (NH),
1585, 1280 cm ^-1 (Ar ^- NO ₂ ) Example 10 N-(2-propynyl)-4-nitro-2-trifluoromethylaniline Suspension of potassium carbonate (20.0 g) in DMSO (7 ml) Triethylamine (3 ml) and 2-propyn-1-amine (7.92 g, 1.44 x 10 ^-1 mol) were added. The reaction mixture was cooled in an ice bath and 1-fluoro-4-nitro-2-trifluoro-methylbenzene (30.13 g, 1.44 x 10 ^-1 mol) was added slowly with stirring. The mixture was gradually warmed to room temperature and stirred for 24 hours. The reaction mixture was poured into excess water and extracted with ethyl acetate. The ethyl acetate solution was dried over sodium sulphate, filtered and evaporated. The residue was chromatographed on a silica column eluting with benzene and recrystallized from benzene to give yellow crystals.

Melting point: 71-72℃ Yield: 24.24g, (69%) Infrared absorption spectrum (KBr): 3450 (NH),
3290 (CH), 1588 (Ar ^- NO ₂ ), 1300 cm ^-1 (CF ₃ ) Example 11 N,N'-bis(4-nitro-2-trifluoromethylphenyl)-2,4-hexadiyne-
1,6-diamine Cu(OAc) A suspension of _{2.H 2} O (4.5 g) in pyridine-methanol (1:1, 30 ml) was added with N-
(2-Propyl)-4-nitro-2-trifluoromethylaniline (3.01 g, 1.23 x 10 ^-1 mol) was added. The reaction mixture was stirred at 50°C for 2 hours. The mixture was poured into excess water and filtered. The crude solid was recrystallized from nitromethane to give pale pink crystals. Yield: 2.54g, (84%). This substance is heated to 200℃
It did not melt at temperatures below 135°C and turned dark red.

Infrared absorption spectrum (KBr): 3405 (NH),
1580 (Ar ^- NO ₂ ), 1290 cm ^-1 (CF ₃ ) Example 12 N-(2-propynyl)-2,4-dinitro-5
-Fluoroaniline A suspension of potassium carbonate (6.0 g) in acetone (25 ml) is mixed with triethylamine (1.5 ml) and 2-fluoroaniline.
Propyn-1-amine (2.35 g, 4.25 x 10 ^-2 mol)
added. Add 1,5-difluoro-2,4-dinitrobenzene (10.00 g, 4.90 x 10 ^-2 mol),
The reaction mixture was stirred at room temperature for 24 hours. The mixture was poured into excess water and filtered. The resulting dark solid was chromatographed on a silica column, eluting with benzene, and recrystallized from benzene to give yellow crystals.

Melting point: 113-115℃ Yield: 8.33g, (82%) Infrared absorption spectrum (KBr): 3340 (NH),
3280(CH), 1615, 1260(Ar ^- _NO2 ), 1210cm
^-1 (Ar ^- F) Example 13 N,N'-bis(2,4-dinitro-5-fluorophenyl)-2,4-hexadiyne-1,
_N- ( ₂
-propynyl)-2,4-dinitro-5-fluoroaniline (1.00 g, 4.18 x 10 ^-3 mol) was added.
The reaction mixture was stirred at room temperature for 17 hours. The mixture was poured into excess water and filtered. Crude solid to silica
It was subjected to column chromatography and eluted with chloroform/acetic acid. The resulting solid was soxhlet recrystallized from ethyl acetate to give yellow crystals.

Melting point: 225℃ (decomposed) Yield: 0.21g (12%) Infrared absorption spectrum (KBr): 3360 (NH),
1680, 1315 cm ^-1 (Ar ^- NO ₂ ) Example 14 N-d(+) (α-methylbenzene)-10,12-
Preparation of Pentacosadiinamide 138 mg (1.36 mmol) of triethylamine was added to a solution of 510 mg (1.36 mmol) of 10,12 pentacosadiinoitsuccinic acid in 10 ml of tetrahydrofuran. The resulting cloudy solution was cooled to 0° C. and 129 mg (1.36 mmol) of methyl chloroformate was added dropwise over 1 minute. A white solid formed immediately upon addition. The mixture was stirred for 1 hour at 0°C, then 165 mg (1.36 mmol)
of d(+)-α-methylbenzylamine was added and the mixture was heated to reflux for 1 hour. At this time, gas generation was observed within 5 minutes and stopped after 15 minutes.
The mixture was cooled to room temperature and filtered. The solution was washed with 10 ml portions of 1M HCl, water, a saturated aqueous solution of potassium bicarbonate, and dried (MgSO ₄ ). Evaporation gave 540 mg (83% crude yield) of a white solid. Recrystallization from ether-petroleum ether gave white crystals.

Melting point: 65.5-66.5℃ Infrared absorption spectrum (film): 1470,
1545, 1640, 2860, 2925, 3310 cm ^-1 Specific optical rotation: [α] ³¹ _D (CHCl ₃ ) = 44° Example 15 N,N'-bis-(α-methylbenzyl)-10,
Preparation of 12-docosadiindiamide 405 mg (4.00 mmol) of 725 mg (2.00 mmol) of 10,12-docosadiindiamide dissolved in 50 ml of tetrahydrofuran (THF) was added.
of triethylamine was added. The solution was cooled to 0° C. and 378 mg (4.00 mmol) of methyl chloroformate was added dropwise over 1 minute. The resulting white mixture was stirred for 1 hour at 0°C and 485 mg
(4.00 mmol) of d(+)-α-methylbenzylamine was added. The reaction mixture was heated to reflux for 1 hour (gas evolution started immediately upon addition of the amine and stopped after 20 minutes). The mixture was cooled to room temperature and filtered. Add 25ml each of 1M HCl, water,
Washed with saturated aqueous sodium bicarbonate solution and dried (MgSO ₄ ). Distillation gave 842 mg (74% crude yield) of a white solid that polymerized rapidly upon exposure to UV light.
Recrystallization from ether-petroleum ether gave 456 mg of white crystals.

Melting point: 87.5-89℃ Infrared absorption spectrum (film): 1530,
1635, 2850, 2920, 3300 cm ^-1 Example 16 2,4-hexadiyn-1,6-diol-bis-(2,4-dinitrophenyl)ether 2,4-hexadiyn-1,6-diol (1.1 g in acetone (15ml) in a solution dissolved in
_K2CO3 ( _0.5g ) was added. While stirring the solution at room temperature, 2,4-dinitrofluorobenzene (3.8 g) was added slowly and the dark red solution was stirred overnight at room temperature. This was poured into excess water, and the pale yellow solid was separated, washed with water, and dried. Recrystallized from dioxane and ethanol, melting point 210℃ (4.2g, 95%)
Pale pink short needle-like crystals were obtained.

Infrared absorption spectrum (KBr): 1592, 1333,
834 (Ar ^- NO ₂ ) cm ^-1 Example 17 N-(2-propynyl)-2,4-dinitroaniline 2-propyne was added to a suspension of potassium carbonate (1.0 g) in acetone (10 mg). -1-amine (0.26
g, 4.73×10 ⁻³ mol) were added. 2,4-dinitrofluorobenzene (1.32 g, 7.10 x 10 ^-3 mol)
was gradually added with stirring and the reaction mixture was refluxed for 2 hours. After cooling, it was poured into excess water and filtered. The crude solid was recrystallized from ethanol to give yellow crystals.

Yield: 0.99g (95%) Infrared absorption spectrum (KBr): 3367 (NH),
3268 (CH), 1618, 1590, 1333 ^{, 1311cm -1}
(Ar ^- NO ₂ ) Example 18 N,N'-bis(2,4-dinitrophenyl)-
_{N- _}
(2-Propynyl)-2,4-dinitroaniline (1.00 g, 4.52 x 10 ^-3 mol) was added. The reaction mixture was stirred at 50°C for 30 minutes. The mixture was poured into excess water and filtered. The crude solid was recrystallized from nitromethane to give pale green crystals. Yield: 0.86g (86
%). This compound does not melt below 200℃ and 120℃
The color changed from green to bronze. When it was recrystallized from dioxane, orange crystals of a different crystal form were obtained. It turned dark orange at 140°C.

Infrared absorption spectrum (KBr): 3380 (NH),
1617, 1592, 1333, 1312 cm ^-1 (Ar ^- NO ₂ ) Example 19 Synthesis of diacetylene-alkyl acid monomer Diacetylene-alkyl acid monomer for monolayer (monolayer) and multilayer (multilayer) The polymers were synthesized by the Chodkiewicz coupling method using bromoacetylenes prepared by Strauss. Chiyodokiewicz Annual Report on Chemistry (Parry) [W.
See Ann. For example, 1-bromo-
Pentacosyl-10,12-dioitsucic acid was prepared by coupling undecyne-10-oitsucic acid with tetradecyne. 50 dissolved in 5 ml of ethanol
Millimoles of tetradecine were added to a stirred solution of 100 millimoles of ethylamine in 50 ml of ethanol to form a yellow solution. The solution was cooled to 15°C with stirring and 50 mmol of 1-bromo-undecine-10- dissolved in 60 ml of ethanol was added.
Oytschic acid was added dropwise over a period of 30 minutes, during which time
The temperature was maintained at 15-20°C. After the addition was complete, the reaction mixture was stirred for 3 hours at 15-20°C. The mixture was then acidified to PH1 and extracted twice with 100 ml of ethyl acetate. The orange layer was separated, dried over magnesium sulfate, filtered over Florosil, evaporated and
A colorless viscous oil was obtained. The oil was dissolved in methanol-petroleum ether and the solution was filtered. The liquid was cooled to obtain pentacocer 10,12-diioscinic acid as colorless plate-like crystals (melting point: 59-60°C). When the platelet crystals were exposed to laboratory light for a short period of time, they turned intensely blue.

Example 20 The apparatus used for the production of the multilayer consists of a Langmuir trough made of Teflon with dimensions of 12.2 x 30 cm (area and depth of 2 cm). Surface pressure is applied by a movable Teflon barrier connected to a motor-driven screw gear. Continuously measure surface pressure using a Wilhelmy balance. Vibration-free solid substrate
(free) Connected to a solid rod, using a motor with a reversible device, insert it into the gutter at a speed of 1 to 3 cm/hr.
I'll put it out.

A solution of 4×10 ⁻³ M pentacocer 10,12-diinoitsuccinic acid in n-hexane was spread over a 1×10 ⁻³ M aqueous cadmium chloride solution. The pH of the _CdCl2 solution was adjusted to 6.1 with sodium bicarbonate in advance. Successive layers were deposited onto a solid substrate at a constant surface pressure of 15 dyne/cm and a dipping speed of 0.5 mm/sec. The surface pressure area curve shows that the monomer molecule occupies 20 Å ² at about 23° C. and a surface pressure of about 15 dyne/cm.
A Y-type deposited layer was obtained.

Example 21 Using the amide produced in Example 14, a cumulative layer of 14 Y-shaped multilayers was made on an iron stearate-coated quartz plate by the Langmiur-Boldget method, and heated at 60°C for 2 hours in a furnace. Warmed and slowly cooled. The cumulative layers were exposed to ultraviolet or X-ray radiation through a mask to obtain excellent pattern writing.

Example 22 In another experiment, 12 to 30 pentacers
A layer of 10,12-deinoitsic acid was deposited on a solid substrate such as glass, silicon, or gold foil deposited on glass. Exposure to X-rays through a mask polymerized the cumulative layer in spatially defined areas to produce a negative-tone device pattern on the substrate. For example, 30 cumulative layers of pentacosyl-10,12-diinoitsuccinic acid on a silicon single-crystal substrate are placed after a metal pattern, and a cumulative layer of multilayers is
X-rays were exposed through lines of a mask 5 μ wide and 1 cm long. polymerized and re-resultant
The total x-ray energy absorbed by the pattern was approximately 10 millijoules/cm ³ . After exposure, the remaining monomer in the masked non-exposed area is washed away with an organic solvent such as acetone and dissolved, leaving the pentacose-10,12-dinoic polymer on the silicon substrate. A line pattern remains. After etching the substrate, the polymer was removed by washing in a dilute aqueous solution of hydrofluoric acid.

Example 23 Preparation of diacetylene covalently bonded to a silicon surface A silicon plate with a 65μ thick oxide layer was immersed in concentrated nitric acid for 2 hours. The water contact angle (α _w ) after washing was 44°. After completely drying, the board is
-amino-propyltriethoxysilane vapor. On top of a boiling solution of 2 ml of silane dissolved in 100 ml of dry para-xylene, under a nitrogen stream,
The substrate was left on for 16 hours. The substrate was placed in a steam bath and the vapor condensed 5 cm above the substrate. The substrate was washed with absolute ethanol and then water. α _w was 45°. The silanized substrate was treated with 22 mg (0.06 mmol) of
A solution of 10,12-pentacosadiinoscinic acid in 10 ml of anhydrous pyridine was immersed. A solution of 14 mg (0.07 mmol) of N,N-dicyclohexylcarbodiimide in 1 ml of pyridine was added. The wafers were processed for 22 hours at room temperature under nitrogen flow. The substrate was washed with pyridine, ethanol, boiling pyridine, then boiling ethanol, and dried. α _w was 78°.

Example 24 A cumulative layer of 15 multilayers of the composition of Example 19 was made on a quartz plate by the Langmiur-Boldget method, placed in an oven at 55°C for 6 hours, and then cooled to room temperature. Thus, multiple regions have been established within the cumulative layer that provide excellent resolution and response when selectively exposed to ultraviolet or X-ray radiation.

Example 25 A conventional transparent, flexible film was coated with 15 Langmiur-Brodget layers of the amide of Example 14. The coated film was heated to 55-60°C for 2 hours and cooled. The film was then exposed to a test pattern through a lens, yielding a glossy, purplish bronze colored image with excellent resolution and resolving power.

[Brief explanation of drawings]

FIG. 1 is a conceptual diagram of polymerization of the composition in the present invention. FIG. 2 is a representative illustration of certain embodiments of the invention, particularly photographic film. FIG. 3 shows a microstructured region of a preferred embodiment of the invention. Explanation of symbols of main parts, 1...Coating, 2...Substrate,
3...Area.

Claims (1)

[Scope of Claims] 1. A photographic or photolithographic material comprising a substrate and at least one substantially continuous layer thereon, the layer comprising at least one substance having at least two acetylene bonds. at least two acetylene bonds are conjugated to each other, the layer is comprised of a plurality of domains, each domain having an average size of 10,000 Å or less, and in a substantially regular arrangement of the composition. A material characterized in that the layer is image-polymerized with high resolution when a predetermined portion of the layer is irradiated. 2. The material according to claim 1, wherein the layer is formed by the Langmiur Bloggett method. 3. The material according to claim 1, wherein the layer is formed from a plurality of layers. 4. The material of claim 1, wherein said layer is covalently bonded to said substrate. 5. The material according to claim 4, wherein the covalent bond is a siloxyl bond. 6. A patent in which the substance is a compound represented by the formula R ₁ -C≡C-C≡C-R ₂ (wherein R ₁ is a hydrophobic residue and R ₂ is a hydrophilic residue) The material according to claim 1. 7 The substance has the formula R ₃ -C≡C-C≡C-R ₄ (wherein R ₃ is a C ₁ -C ₃₀ hydrocarbon residue,
R ₄ has the formula -R ₅ -(A) _o (wherein R ₅ is a C ₁ -C ₃₀ hydrocarbon group, n is an integer from 1 to 10, and A is
COOH, COOR ₆ , CONH ₂ , CONHR ₆ , CON
( _R6 ) ₂ , OH, SH, _NH2 , _NHR6 , N( _R6 ) ₂ , silyl, sulfate, sulfinate, phosphate and siloxy ( _R6 is a _C1 - _C8 hydrocarbon group) A material according to claim 1 selected from the group. 8. The material according to claim 1, wherein the substance is an optically active substance. 9. The material according to claim 1, wherein the substance has three acetylene bonds and is conjugated to each other. 10. The material of claim 1, wherein the layer further comprises a second polymerizable composition. 11. The material of claim 1, wherein the composition further comprises a dimer of a nitroso compound in an amount sufficient to reduce thermal polymerization. 12. The material of claim 1, wherein said material is substantially fluorinated. 13. The material of claim 1, wherein the substrate is suitable for photolithographic processes. 14. The material of claim 1, wherein the substrate is silicon or silicon dioxide. 15. The material of claim 2, wherein the substrate is a lithographic plate. 16. The material of claim 1, wherein the domains have an average size of 2000 Å or less.