JPH01163207A - Polymerization, hydrolysis and use of 3, 5-disubstituted-4-acetoxystyrene - Google Patents

Abstract

PURPOSE: To obtain a polymer for film composition excellent in developing, resolution and low resolving speed by free-radical polymerization of a 3,5- disubstituted-4-acetoxystyrene monomer and by hydrolysis of the polymer.

CONSTITUTION: Poly(3,5-disubstituted-4-hydroxystyrene) is prepared by free- radical-polymerizing a 3,5-disubstituted-4-acetoxystyrene monomer (3 and 5- substituents are independently a 1-10C alkyl, alcoxy, primary or secondary amino, halogen) teel the molecular weight reachs about 1,000-800,000, preferably using azo-isobutyronitrile as an initiator and hydrolyzing the poly(3,5- disubstituted-4-acetoxystyrene) with a sufficient amount of a hydrolyzing agent (e.g.: tetramethylammonium hydroxide).

COPYRIGHT: (C)1989,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention This invention relates to novel polymers that are derivatives of 3,5-dimethyl-4-acetoxystyrene, and to methods for their preparation and use. When the above monomers undergo free radical polymerization, the resulting polymer is poly(3,5-disubstituted-4-
It has been found to be useful as an intermediate in the production of hydroxystyrene). The latter polymers have been found useful in a variety of applications such as adhesives, coatings, and binder resins for photoresists. Each of the above 3.5-substituents is independently C1-C8 alkyl or alkoxy, primary or secondary amino, or halo. In a preferred embodiment, the present invention provides poly(3-mono- and 3,5-dino-loginated 4-acetoxy- and 4-
Hydroxystyrene) and their copolymers, these polymers are suitable as compounds which form acids under the influence of radiation in radiation-sensitive mixtures.

[Conventional technology]

The production of positive photoresist formulations is well known in the art, e.g., U.S. Patent No. 3,666,4
No. 75, No. 4,115,128 and No. 4,17
No. 3,470. These formulations contain a photosensitive material (usually a substituted naphthoquinone-diazide compound) along with an alkali-soluble phenol-formaldehyde novolak resin. The resin and photosensitizer are combined with a solvent (or solvent mixture) and applied as a film or coating onto a suitable substrate for the particular desired application. Polyvinylphenols are described in U.S. Pat. No. 3,869,292 and U.S. Pat. No. 4,439,516.

α-acetoxystyrene and β-acetoxystyrene are described in U.S. Pat. No. 4,144,063, and acetoxymethylstyrene is described in U.S. Pat.
It is stated in No. 5. 4,075,237 for U.S. Patent
The issue describes 1,4-dimethyl-2-hydroxystyrene, and the US special efl! , Nos. 56-846 contain poly(3
, 5-dimethyl-4-hydroxystyrene/) is described. JP 59-23747 describes antistatic compounds using poly(acetoxymethylstyrene), and U.S. Pat. No. 4,221.700 describes poly(alkylated Stabilized synthetic polymers using alkenylphenols) have been described. Poly(α-methylvinylphenol) is described in U.S. Pat. No. 4,600.683 and U.S. Pat. No. 4,543,397. 4.5 for US patents
No. 17,028, No. 4,460.770 and No. 4,539,051 describe dimethylvinylphenol. Although the resin components of these photoresist formulations are soluble in aqueous alkaline solutions, the naphthoquinone stabilizer acts as a dissolution rate inhibitor for street fat. However, upon exposure of selected areas of the coated substrate to actinic radiation, the photosensitizer undergoes radiation-induced structural deformation such that the exposed areas of the coating become more soluble than the unexposed areas. This difference in dissolution rate is due to the fact that when the substrate is immersed in an alkaline developer, the exposed areas of the L/cyst coating are dissolved, while the non-exposed areas are not affected much, and this traps the positive deposits on the substrate. Produces a V-leaf pattern.

In most cases, the exposed and developed substrate is treated with a substrate etching solution. Since the photoresist coating protects the coated areas of the substrate from the etching agent, the etching agent only etches the uncoated areas of the substrate;
In the case of a positive photoresist, this corresponds to the area exposed to actinic radiation. That is, the etched pattern can produce a pattern on the substrate that corresponds to the pattern on the mask, stencil, template, etc. used to produce the interpretive exposure pattern on the existing coated substrate. . The VIJ-7 pattern on a substrate produced by the method described above is useful in applications including exposure masks or patterns such as those used in the manufacture of miniaturized integrated electronic components. Properties of photoresist compositions that are important to commercial practice include resist photospeed, development contrast, resist resolution, and resist adhesion. Resist resolution refers to the ability of a resist system to reproduce the smallest equally spaced line pairs and the intervening spacing of the mask used during exposure with high sensitivity of the edges of the developed exposure interval image. In many industrial applications, particularly in the manufacture of miniaturized electronic components, photoresists are required to provide a high degree of resolution for very small line and gap widths (on the order of 1 micron or less).

The ability of resists to reproduce very small dimensions, on the order of one micron or less, is critical to making large scale integrated circuits on silicon chips and similar elements.

The circuit density on such chips can only be increased by increasing the resolution of the resist, assuming photolithography techniques are used. Photoresists are generally classified as either positive working or negative working. In negative-working resist compositions, the image-exposed areas are cured to produce image areas of the resist after removal of the unexposed areas by a developer. In positive working resists, the exposed areas are non-image areas. Although negative resists are most widely used in industrial production of printed circuit boards, positive resists have finer resolution and smaller image geometries. Selected for the production of densely packed integrated circuits.

[The problem that the invention attempts to solve]

The present invention provides novel polymers and photographic compositions using these polymers. In one important aspect of the invention, photoresists using this new polymer as a binder exhibit developability and resolution comparable to phenol-formaldehyde novolac resins, yet are also known for this purpose. It has been found that an advantageously lower ``II4 image speed overall speed than polyvinylphenol.

Polyvinylphenol has the disadvantage of having a fast resolution rate, which makes image differentiation difficult to achieve.

However, they can withstand much higher processing temperatures (temperatures on the order of about 200° C.) K than novolacs. The preferred poly(3,5-dimethyl-4-hydroxystyrene) of the present invention exhibits resolution speeds comparable to novolacs, yet can withstand processing temperatures comparable to polyvinylphenol.

It also has significant improvements over poly(4-hydroxystyrene), which is produced only in low molecular weight, faded, impure form.

Brominated poly(4-hydroxy)styrene is also known. West German patent application? 3730 784.3 According to K.
These can be used in the corresponding photoresists as radiation-sensitive compounds, ie compounds that generate @ under the influence of radiation.

The synthesis of this compound is to convert poly(4-hydroxy)styrene into J
This is done by converting it into a J. The product is about 50 F
It can have a bromine content of up to K. However, the exact substitution pattern for compounds produced by this method is not known. One of the consequences of this is the considerable impact on the range of uses of radiation-sensitive mixtures. This type of post-brominated poly(4-hydroxy)styrene (e.g. Maruzen 84WfIME) is disclosed in West German patent application No. 3730 78.
4.3, as compounds that release acids under the action of actinic radiation, they have several disadvantages when used with substances that can be cleaved by these acids.

One of these drawbacks is the excessively high rate of degradation of radiation-sensitive mixtures containing these polymers, which results in differences in images after exposure and development even when the radiation-sensitive mixtures are stored for only one week. Make identification impossible. Bromination of polymers not only yields pure products substituted in the rings, but also some aliphatic chains are brominated as well;
Alternatively, the bromine may be present in the polymer simply in an adsorbed state, so that the hydrogen norygenide not only occurs upon irradiation in the image-wise irradiated area (cycloconversion).
It is assumed that not only hydrogen halides are generated by cleavage of the halogens, but also acids are generated thermally in the non-exposed areas.

This represents the goal of producing polymers or copolymers that are capable of producing acids under the influence of radiation and in mixtures with other components of radiation-sensitive mixtures and that do not have the above-mentioned disadvantages of the prior art. .

[Means to solve the problem]

One aspect of the invention is a poly(3 , 5-disubstituted-4-acetoxystyrene) and po-17 (3,5-di-fd-substituted-4-hydroxystyrene). Alkyl and alkoxy are preferably C, -C, more preferably C1-q.

The present invention also provides free radical polymerization of the (3,5-disubstituted-4-acetoxystyrene) monomer to reach a molecular weight of from about 1,000 to about 800,000, and then the polymer thus produced is fully polymerized. The present invention provides a process for producing poly(3,5-disubstituted-4-hydroxystyrene) comprising hydrolyzing it with an amount of a suitable hydrolyzing agent. The 3.5-1d substituents are independently Cl-Cl
0 alkyl or alkoxy, primary or secondary amino, or halo.

The present invention further provides polyamides having a molecular weight ranging from about 1,000 to about 800,000, wherein the 3,5 substituents are independently C1-CIO alkyl or alkoxy, primary or secondary amino, or halo. (3,5-di-4-hydroxystyrene; an O-quinone diazide sensitizer; and a suitable solvent; present in an amount sufficient for the polymer to serve as a binder for the composition; the diazide is present in an amount sufficient to provide a distinct and distinguishable image when imagewise exposed to actinic radiation as the composition is coated onto a substrate;
and the solvent is present in an amount sufficient to form a homogeneous solution of the composition; providing a photosensitive composition. The photographic element is converted by coating this composition onto a suitable substrate. The present invention also includes coating the photosensitive composition described above on a substrate; drying the composition until it is substantially non-tacky; The present invention provides a method of forming a photographic image comprising exposing the composition to light to produce a differentiated discrete image; and removing the non-image portions of the composition with a suitable developer.

Furthermore, the present invention particularly provides a polymer containing units of the following general formula (1).

H [R is hydrogen or acetyl; H81 is chlorine or bromine; R1 is hydrogen, alkyl especially (Ct-Ct.

) alkyl or halogen (e.g. chlorine or bromine; and R7 and R8 are independently hydrogen, allyl, alkoxy, or halogen, but when R1 is alkyl, R, and R2 are taken together to specifically It may be a 6- to 12-membered alicyclic group.]Hal is bromine, R8
is <C+~C3)alkyl, especially methyl, and R
, R, and R5 are hydrogen.

The polymers or copolymers according to the invention have high storage stability in radiation-sensitive compositions. - Differences in details within the compounds falling under type (1) are also pointed out.

Polymers or copolymers containing either 3,5-dibromo compounds or 3.5-dichloro compounds as units of general formula (I) have very high resolution.

On the other hand, 3-bromo or 3-chloro-5-alkyl compounds have better differential images and longer residence times in the developer. These polymers can also be composed of various units within the group. 3,5-dibromination,
3-monobromination and/or 3-monopronation-5
Particular attention should be paid to compounds of the type having the general formula (1) which contain units of -fulkylation. It is equally possible for the units mentioned to have free hydroxy groups (E=hydrogen) or to contain units that are still protected by an acetyl group.

However, unprotected units are particularly preferred.

[Specific explanation]

A preferred 3,5-substituent of the present invention is methyl, and this preferred embodiment will be described in detail. Other substituents can be obtained in the same manner.

In the method for producing 3.5-dimethyl-4-acetoxystyrene monomer, commercially available 2,6-dimethylphenol is used as a starting material, which is esterified with acetic anhydride to form 2,6-dimethyl phenol. Generates phenyl acetate. This is then converted into 3,5-dimethyl-4 by Friedel-Krach catalysis or Fries rearrangement reaction.
-hydroxyacetophenone, which is then esterified with acetic anhydride. This product was washed with water and 1-
(3', 5'-dimethyl-4'-acetoxyphenyl)ethanol, which was then dehydrated with acid to give 3,5-
Dimethyl-4-acetoxystyrene monomer is obtained.

These reaction sequences can be expressed as follows.

A general method for producing 3-monosubstituted (or 3,5-disubstituted)-4-acetoxy (or 4-hydroxy)styrene is as follows.

α) ■ Acylate substituted phenol to produce substituted hydroxyacetophenone, or ■ Substitute 4-hydroxyacetophenone to produce a compound having general formula (1), [R1 is hydrogen or alkyl (Ct to C1o ) alkyl, and R2 and R1 are independently hydrogen, alkyl, alkoxy, or
may be taken together to form an alicyclic group, in particular a 6- to 12-membered ring; b) the hydroxy functional group is then esterified (protected) to give/) a rogenated-4-acetoxyacetophenone derivative; C) reduction of the ketone functionality to a hydroxy functionality and d) dehydration to form a 3-mono- or 3.5-disubstituted-
4-acetoxystyrene is produced and, if appropriate, the -) protecting group is hydrolyzed to form 3-mono (or
,5-di)substituted-4-hydroxystyrene.

3.5-Disubstituted-4-acetoxystyrene monomers are then polymerized by free radical initiation to yield approximately 1,000
0 to about so o, o o o, preferably 1,000
~s o, o o o, more preferably about s, o o
Poly(
3,5-disubstituted-4-acetoxystyrene). This intermediate polymer is then hydrolyzed with a base to produce poly(3,5-disubstituted-4-hydroxystyrene) having a molecular weight within the above range.

A preferred free radical initiator 111 is azo-imbutyronitrile. Other azo-type initiators are also suitable.

Other initiators include, non-exclusively, peroxides such as benzoyl peroxide and g-butyl peroxide. It is expected that virtually any free radical initiator will be useful as well. −Format (
In the polymerization of the monomer that forms the basis of 1), this formula (1)
) are used. Particular preference is given to homogeneous polymerization, which can also be understood as including the polymerization of various monomers falling under formula (1).

Particularly preferred are also copolymers containing a small number (at least 10 tmolty) of units of type (I)K.

All monomers that can be polymerized by radical or ionic polymerization are useful as monomers suitable for copolymerization with monomers based on formula (I'l). : styrene, 4-acetoxystyrene, 4-hydroxystyrene, 3,5-disubstituted (especially dialkylated but non-halogenated) acetoxystyrene or hydroxystyrene, acrylic V-) and methacrylates (especially butyl acrylate and methyl methacrylate), manoic anhydride and its derivatives (especially manoic anhydride, maleimide), etc. However, homogeneous polymers are particularly preferred. Homogeneous polymerization or copolymerization is 1.000~s o o, o o o
, preferably with a molecular weight (MW) of s,ooo to 300,000, particularly preferably s,ooo to 15,000.

The non-uniformity (σ) of these polymers is particularly between 0.5 and 1.
Polymerization in 5 is radical polymerization or ion (especially cation)
It can be either superimposed. Particular preference is given to radical polymerizations initiated by initiators such as azobisisobutyronitrile.

Peroxides such as benzoyl peroxide and di-tert-butyl peroxide are also worth mentioning.

Polymerization can be carried out either by solution polymerization (monomers are dissolved in a solvent) or by bulk polymerization. -Format (I)
The styrene derivative (4-
acetoxystyrene derivatives) as well as already hydrolyzed monomers (4-hydroxystyrene derivatives) can be polymerized to enrich the polymer with both protected and unprotected monomer units. Hydrolysis optionally carried out at the monomer stage can be repeated at the polymer stage to deprotect the 4-hydroxy functionality. The choice of both hydrolysis offers the opportunity to match the properties of the polymer produced to industrial requirements.

One preferred hydrolyzing agent is tetramethylammonium hydroxide. Other hydrolyzing agents include aqueous N11. , NaOH and KOH are mentioned non-exclusively.

Hydrolysis at the polymer stage can be carried out in a sieve or in an alkali. Mild modification, ie hydrazinolysis before acid hydrolysis, is also possible.

Possible hydrolyzing agents are MC'l and H, SO,; basic hydrolysis is usually carried out with NH8, A'aOH, KOH and also with tetramethylammonium hydroxide.

In preparing the photosensitive compositions and photographic elements of the present invention,
The binder resin prepared as described above is mixed with a photosensitizer (e.g., an O-quinone diazide photosensitizer) and a suitable solvent until a homogeneous solution is formed. This solution is then applied onto a suitable substrate and dried until non-stick. The use of 〇-quinone diazides is known to those skilled in the art and is described, for example, in Korar J, Light 5ens
tive 5ystan*s (published by John Wiley & Sons, New York, USA, 1965), No. 7.4. Such sensitizers, which are one of the elements of the resist compositions of this invention, are preferably selected from the group of substituted quinone diazide sensitizers commonly used in conventional photoresist formulations.

Such photosensitizer compounds are described, for example, in U.S. Pat.
No. 7,213, No. 3,106,465, No. 3.1
No. 48,983, No. 3.130,047, No. 3,
No. 201,329, No. 3,785°825, and No. 3,802,885.

The photosensitizer is preferably a 1,2-quinone diazide-4-(or 5-)sulfonic acid ester of a phenolic derivative. It appears that the number of fused rings is not important to the invention, but rather the position of the sulfonyl group. That is,
Benzoquino/, naphthoquinones or anthraquinones can be used as long as the oxygen is in the 1st position, the diazo is in the 2nd position and the sulfonyl group is in the 4th or 5th position. Similarly, the e of the attached phenol does not appear to be important. For example, it may be a milphenol derivative as described in U.S. Pat. No. 3,640,992, or a mono-, di- or triphenol derivative as described in U.S. Pat. No. 4,499,171. It may also be a hydroxyalkyl ketone or benzophenone.

Useful photosensitizers include hydroxybenzophenone, especially trihydroxybenzophenone/more specifically 2,3.4-
) Naphthoquinone diazide-4 condensed with a phenolic compound such as lipidroxibe/siphenone (1.2)
-Sulfonyl chloride: 2,3.4-)lihydroxyphenylphenyl ketone 1,2-naphthoquinone-2
-Diazide-4-sulfonic acid ester or other alkylphenones: 2.3.4-trihydroxy-3'-methoxy benzophenone 1,2-7toquinone-2-
Diazido-4-sulfonic acid triester: 2 t 3
14-) IJ hydroxy-3'-methylbenzophenone 1,2-su7toquinone-2-diazide-4-sulfonic acid triester; and 2,3,4-trihydroxy-benzophenone 1,2-naphthoquinone diazide-
Examples include 4-sulfonic acid triester.

The invention also provides the use as acid-generating compounds of compounds which generate acids (initiators) under the action of optical radiation as well as polymers which contain compounds which can be cleaved by acids and which have units according to general formula (1). A positive-working radiation-sensitive mixture is provided, characterized in that:

The content of this polymeric starter in the radiation-sensitive composition is 2
-100% by weight, preferably 5-60% by weight. In addition to this polymer starter, West German patent publication a/'37307
Monomeric and polymeric starters according to 84.3 can also be included in this radiation-sensitive mixture.

However, it is preferred for this polymer starter that no other polymer starters and monomer starters are used in the mixture ~10 The following types of compounds have been successfully used as acid-cleavage materials in radiation-sensitive mixtures according to the invention: It has been proven that

G) At least 18! A compound having an orthocarboxylic acid ester and/or carboxylic acid amide acetal group, which has polymeric properties and in which the above-mentioned group can be seen as a connecting element in the main chain or as a lateral substituent.

b) Oligomeric or polymeric compounds having repeated acetal and/or ketal groups in the main chain.

C) Compounds with at least one enol ether group or N-acryiminocarbonate group.

d) Cyclic acetals or ketals of β-ketoesters or β-ketoamides.

a) Compounds with silyl ether groups.

/) It has a sirenol ether group.

g) The aldehyde or ketone component is 0.1 to 0.1 during development.
100? Monoacetal or monoketal with solubility of /l.

h) Ethers based on tertiary alcohols.

() Carboyyw esters and carbonates of tertiary allylic or benzylic alcohols.

Acid-cleavable type α as a component of radiation-sensitive mixtures
) compounds are EP-A-0022571 and DE-
A-2610842; mixtures containing compounds of type b) are described in DE-C-2306248
and DE-C-2718254: compounds of type C) are listed in EP-,4-QOO6626 and 0006627; compounds of type d) are described in EP-AO202L96: type The compounds of a) are DE-A3544165 and DE-,
4-3601264: Compounds of type f) are described in West German patent application P3730783.5: Compounds of type g) are described in West German patent application P37307.
85, IE and P3730787.8; compounds of type h) are described, for example, in U.S. Pat.
603,101; compounds of type i) are described, for example, in U.S. Pat. No. 4,491,628 and J.
, A1. 1 of Fraeht et al. ImagixgSat,
, 30.59-64 (1986).

It is also possible to use mixtures of the acid-cleavable substances mentioned above.

However, if the file belongs to any one of the above types -
Cleavable materials are preferred. Particular preference is given to substances belonging to types α), b), g) and i). Of type b), polymeric acetals are particularly noteworthy, and type g)
Of particular interest among the acid-cleavable materials are those whose aldehyde or ketone component has a boiling point of 150 DEG C. or higher, preferably 200 DEG C. or higher.

An acid having at least one C-0-C bond in the compound -
Particularly preferred are cleavable materials.

The content of acid-cleavable substances in the radiation-sensitive mixture according to the invention should be from 1 to 50% by weight, preferably from 5 to 25% by weight, based on the total weight of the coating layer.

The radiation-sensitive mixture according to the invention can contain a binder which is insoluble in water but at least swellable in organic solvents or alkalis. Examples of such binders are phenolic resins, mainly of the novolak type, such as phenol-formaldehyde resins, cresol-formaldehyde resins, cocondensates thereof, mixtures thereof, such as phenols and sardines of cresol and formaldehyde.

Also, vinyl polymers such as polyvinyl acetate, polyacrylate, polyacrylate, polyvinyl ether,
It is also possible to use polyvinylpyrrolide/and sterenopolymers (which may be modified with commoners), each alone or with each other.

The following are specific examples: Polymers of styrene with alkenylsulfonylaminocarbonyloxy polymer units: or differential bonding -〇B, 0R (EP-A-01
84044), cycloalkenylsulfonylaminocarbonyloxy polymers such as acrylic acid, methacrylic acid, maleic acid, itaconic acid (EP-A-01848)
08): Alkenylphenol unit (EP-, 4-01
53682): polyvinylphenol, e.g. novolac substituted (DE-C-
2322230), a polymeric binder with side chains of phenolic hydroxy groups (EP-, (-0212439)
and 0212440): Styrene-maleic anhydride copolymer (1) E-A-3130987): Polymer of unsaturated (thio)phosphinic acid iso(thio)cyanate and active hydrogen-containing polymer (West German patent application P3615612
．． 4 and P3615613.2), polymers with vinyl acetate units, vinyl alcohol units and vinyl acetal units (EP-A-o2x6os3): and polyvinyl acetals with hydroxyaldehyde units (West German patent application P3644162.7).

The amount of binder is usually from 1 to 90% by weight, in particular from 5 to 90% by weight, preferably from 5 to 90% by weight, based on the total weight of the radiation-sensitive mixture.

The halogen-containing starter according to the invention also has binder properties. In this case, the binders mentioned above are sometimes unnecessary. However, generally mixtures of the polymer according to the invention (initiator) and conventional binders are used. In particular, the polymer according to the invention is mixed with the novolak resin, preferably in approximately equal weight proportions.

Photosensitive compositions are made by mixing the ingredients in a suitable solvent. In a preferred embodiment, the resin is present in the total composition in an amount preferably from 75 to 95% based on the weight of the solids or non-solvent portion of the composition. A more preferred range of resin is about 80-90%, most preferably about 82-85%, based on the weight of the solids portion of the composition. The diazide is present in an amount ranging from about 1 to 25%, based on the weight of the solid or non-solvent portion of the composition. A more preferred range of diazide is about 1-20%, most preferably about 10-18%, based on the solids portion of the composition.

When producing the composition, the resin and photosensitizer are mixed with a solvent (
Mixed with, for example, propylene glycol alkyl ether acetate, butyl acetate, xylene, ethylene glycol, monoethyl ether acetate, propylene glycol monomethyl ether, and propylene glycol monoethyl ether acetate.

Preferably, the radiation-sensitive mixture according to the invention is carried out in a solvent such as ethylene glycol: glycol ethers such as glycol monomethyl ether, glycol dimethyl ether, glycol monoether ether, or propylene glycol monoalkyl ethers, especially propylene glycol methyl ether; aliphatic esters such as ethyl acetate, hydroxyethyl acetate, alkoxyethyl acetate, exo-butyl acetate, propylene gellicol monoalkyl ether acetate, especially propylene glycol methyl ether acetate or amyl acetate; ethers such as dioxane; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclo pentanone, and cyclohexanone;
dimethylformamide, dimethylacetamide, hexamethylphosphoramide, N-methylpyrrolidone, butyrolactone, tetrahydrofuran, and mixtures thereof). Glycol ethers, aliphatic esters, and ketones are particularly preferred solvents.

Solutions prepared using the components of the radiation-sensitive mixture according to the invention usually have a solids content of 5 to 60% by weight, preferably up to 50% by weight.

The solution of resin, sensitizer, and solvent is mixed with colorants, dyes, anti-striation agents, plasticizers, adhesion promoters, speed enhancers, solvents, and surface active agents before coating the solution on the substrate. Additives such as non-ionic surface active agents can be added.

It is also possible to add pigments, softeners, wetting agents, polyglycols, cellulose ethers (taj' ethylcellulose) to the radiation-sensitive mixtures according to the invention to improve properties such as flexibility, adhesion, gloss, etc.

An example of a dye additive that can be used with the photoresist compositions of the present invention is Methyl Violet 2B (C0).
, /VL42535), Crystal Violet (C
, 1,42555), Malachite Green (C01 eyebrow 50040), Victoria Blue B (C', LA44
045) and Neutral Red (C, IJ65
0040), and these dyes are used at a level of 1 to 10% by weight based on the combined weight of resin and photosensitizer. Dye additives help provide increased resolution by blocking light scattering from the substrate. 5i based on the total weight of the resin and photosensitizer to prevent streak formation! It cannot be used at levels up to %. Examples of plasticizers used include tri(β-chloroethyl) phosphate: stearic acid; dicamphor; polypropylene;
There are acetal fats; phenoxy resins; and alkyl resins, which are used at a level of 1 to 10% by weight, t%, based on the total weight of resin and photosensitizer. Plasticizers improve the coverage of the material, allowing the application of smooth, uniform thickness films.

Adhesion promoters that can be used include, for example, β-(3,4-epoxy-cyclohexyl)-ethertrimethoxysilane: p-methyldisilane methyl methacrylate; vinyltrichlorosilane: and r-aminopropyl triethoxysilane. These are used at a level of up to 4 parts by weight based on the total weight of resin and photosensitizer.

Current retention speed enhancers that can be used include, for example, picric acid, nicotinic acid, or nitrocinnamic acid, which are used at levels up to 20% by weight based on the total Nf of resin and sensitizer. . These enhancers tend to increase the solubility of photoresist coatings in both exposed and unexposed areas, so they are used in applications where development speed is important even if some contrast is sacrificed. . That is, although exposed areas of photoresist coverage are more rapidly dissolved by the developer, the speed enhancer also causes greater loss of photoresist coverage from unexposed areas.

Free radical initiators such as di(trichloromethyl)
Stibenyl triazine and 1,1.1-)lichloro-t-butylacetophenone generate acid functionality upon exposure. They thus intensify the exposure and also provide free radicals for cross-linking of the image during subsequent printing.

Examples of nonionic surfactants that can be used in solutions containing the photosensitive compositions of the present invention include nonylphenoxy poly(oxyethylene) ethanol; octylphenoxy poly(oxyethylene) ethanol; and dinonylphenoxy poly(oxyethylene) ethanol. ) ethanol, which are used at levels up to 10% by weight, based on the combined weight of resin and photosensitizer.

The prepared photosensitive solution can be applied to a substrate to form a photoresist by conventional methods used in photoresist technology, including dip, spray, spin, and swirl coating techniques.

For example, during spin coating, the solid mold can be adjusted to provide the desired coating thickness depending on the spin equipment used and the time allowed for the spin process.

The support for making the photoresists of the present invention may be any support that can be electrochemically or mechanically roughened, such as metals such as aluminum and its associated niblast snack film, such as polyester or polyolefin. Films: wood; paper; semiconductor materials (ie, materials that are not t-conducting unless or until they are doped) such as silicon, gallium arsenide; ceramics: and textiles. Preferably, the support is a silicone-based sea urchin.

Any material that constitutes or can be made into capacitors, semiconductors, multilayer printed circuits, or integrated circuits is a candidate substrate. Particular candidates are pure silicon surfaces and surfaces of thermally oxidized and/or aluminum-coated silicon materials, which can also be doped. Other candidates include substrates commonly found in semiconductor technology such as silicon nitride, gallium arsenide, and indium phosphite. Other possible materials are those known from liquid crystal displays, such as glass 8 and indium stannic oxide; and metallic temporary and films made, for example, from aluminium, copper or zinc; bimetallic and trimetallic films: Nonconductor metallized film; aluminum coated e1
540. material and paper. These substrates can be subjected to thermal pretreatment, surface roughening, etching, or treatment with chemical agents to improve desired properties (eg, increase hydrophilicity).

In one particular embodiment, the radiation-sensitive mixture can include an adhesion promoter for better adhesion into the resist or between the resist and the substrate. Silicon or 2
In silicon oxide substrates, adhesion promoters of the aminosilane type can be used, such as 3-aminopropyltriethoxysilane or hexamethyldisilazane.

Examples of substrates that can be used to make opto-mechanical recording layers (e.g. letterpress, offset, screen print, and gravure relief copies) are aluminum plates (anodized, granulated and/or silicified aluminum). plate), zinc plate, copper plate (can also be treated with chrome), as well as plastic film or paper.

The photoresist coatings produced by the above method are particularly suitable for use in thermally treated silicon/silicon dioxide coated wafers, such as those used in the manufacture of microprocessors and other miniaturized integrated circuit components. It is.

The substrate can also be comprised of various polymeric resins, particularly transparent polymers such as polyesters. The substrate most preferably comprises doped silicon dioxide, silicon nitride, tantalum, copper, polysilicon, ceramics and aluminum/copper mixtures.

After applying the photosensitive composition bath to the substrate, this group 'J[
is baked at about 80-100° C. to evaporate substantially all the solvent, leaving only a thin coating of the photoresist composition on the substrate with a thickness on the order of microns. The coated substrate is then coated with a suitable optical mask, negative, stencil, template,
Exposure to actinic radiation, particularly ultraviolet radiation in the range of about 220% to about 450 ss, can be achieved by using a projector or the like. In the most preferred embodiment, ultraviolet (U, V, )
The exposure range is from about 248% to about 436%.

The recording material according to the invention is irradiated in an image pattern. Optical radiation sources are metal halide lamps, carbon/arc lamps, xenon lamps and mercury vapor lamps.

Irradiation with high energy radiation such as lasers, electrons or X-rays is preferred. The lasers are in particular helium/neon lasers, excimer lasers, argon lasers, chilibutton lasers, and helium/cadmium φ lasers.

The layer thickness will vary depending on the application. It is 0.1 to 10
0 micron, especially 0.3 to 10 micron. Application of the radiation-sensitive mixture to the substrate can be carried out by spraying, flow coating, rolling, centrifugal coating, and dip coating. Thereafter, the solvent is evaporated off leaving the radiation-sensitive layer on the surface of the substrate. However, this mixture can also first be applied to the intermediate substrate K as described above and then transferred to the final substrate under pressure and elevated temperature. Substantially any substrate suitable as a substrate can be used as the intermediate substrate described above. This layer is then irradiated in an image pattern. High energy radiation such as X-rays or electron beams is particularly preferred. High-energy synchrotron radiation or electron beam irradiation of leaves with 20 to 200 Jt1%/i
Recorder radiation is particularly preferred.

In the radiation-sensitive layer, an image pattern is developed by treating the layer with a developer solution that dissolves or removes the material in the irradiated areas.

The exposed resist-coated substrate is usually treated with an alkaline developer (
For example, AZ400, available from Hoechst Celanese Corporation, Anmerville, New Jersey, USA.
Developed by immersion in a potassium-based aqueous alkaline solution such as K. This solution preferably does not contain metal ions. In use, the developer solution is agitated, for example by nitrogen purge stirring. The substrate remains in the developer until all or substantially all of the resist coating is dissolved away from the exposed areas.

Solutions of alkaline agents such as silicates, metasilicates, hydroxides, phosphoric acid (-hydrogen or dihydrogen) salts, carbonates or bicarbonates, especially those containing alkali metal ions or ammonium ions, are used as developers. However, ammonia etc. can also be used. The f content of these substances in the developer is generally 0.1 to 15, based on the M amount of the developer.
% by weight, preferably 0.5-5M.

After removing the coated wafer from the developer solution, a late development heat treatment is used as described in British Patent No. 1,154,749 to increase the adhesion of the coating as well as its chemical resistance to etching solutions and other substances. You can also do that. This late development heat treatment can consist of oven baking the coating and substrate below the softening point of the coating. In industrial applications, in the manufacture of microcircuit units on substrates of the silicon/silicon dioxide type, the developed substrates can be treated with a buffered hydrofluoric acid etching solution. The resist compositions of the present invention are resistant to such etching solutions and provide effective protection to unexposed resist-coated areas of the substrate.

In a preferred embodiment, the developed resist structure can be cured by heating the resist structure on a hot plate to a point just below the flow temperature, followed by a xenon-mercury vapor lamp (200-250%). The entire surface can be exposed to ultraviolet light from This curing also bonds the resist structure so that it is flow resistant to temperatures in excess of 200'C. Curing is also
It can also be carried out simply by irradiating ultraviolet rays without using high temperatures.

This is especially true when using high energy radiation such as electron beams.

It is known in the art that photosensitive compositions of the above type are positive-working. However, the present invention is not subject to such limitations and is particularly suitable as a so-called image reversal photoresist which obtains a negative image by means of other suitable components or processing steps known in the art. For example, a suitable cross-linking agent can be incorporated into the photosensitive composition. Non-exclusive examples of cross-linking agents and methods are described in U.S. Pat. No. 4,581,321. Hexamethylol melamine ether such as: and U.S. Pat.
, No. 003, No. 4,576,096 and No. 4,
506,006; and dimethylol para-cresol and other types of cross-linking agents as described in US Patent No. 506,006. The substituted hydroxystyrene and substituted acetoxystyrene polymers of the present invention can be used in place of the alkali-soluble binder resins described in the above-referenced US patents. A cross-linking compound is a compound that is capable of cross-linking the diazide in the presence of the amount and strength of the acid generated when the diazide is exposed to light. This occurs when sufficient heat is applied to cause the acid to diffuse into the bonding components.
At less heat, diazide decomposes. A generally preferred class of such compounds are those that produce carbonium ions under the acid and heating conditions described above. Cross-linking agents suitable for use in the present invention include, non-exclusively, those having the general formula:

(R10-CUR8), -A-(CUR, -OR,)
□ [A has the formula B-Y-B, B is a substituted or non-trt substituted mononuclear or fused polynuclear aromatic hydrocarbon group, or an oxygen- or sulfur-containing heterocyclic group; Y is a single bond, 01-C4 alkylene/or alkylene/dioxy (oxygen atoms may be present in the chain),
-0-1-S-1-SO, -1-CO-1-CO2-1
-O-CO2-1-CONH=, or phenylenedioxy; R1 and R1 are H1C1-C6 alkyl, cycloalkyl, substituted or unsubstituted aryl, alkaryl or acyl; R5 and R4 are independently H , C, ~C-th alkyl, or 1α-substituted or unsubstituted phenyl; n is 1 to 3, m is 0 to 3, and n 10 m is thicker than l. The cross-linking agent is preferably present in the photographic composition at about 0.5% to 20%, more preferably about 1% to 10%. The scale is based on the solid components of the photographic composition. In the most preferred embodiment when image reversal is desired, 1,2-naphthoquinone-2-
Diazide-4-sulfonyl-containing isomers are used as photosensitizers. It has been found that the 4-isomer generates more acid than the corresponding 5-isomer and is therefore more desirable for image reversal techniques. In one embodiment of image reversal, the photosensitive composition is coated onto a suitable substrate as described above and dried (e.g., by heating at about 20-100<0>C for 30 seconds to 3 minutes) until tack-free. This is then exposed to the desired pattern/image energy in a manner well known to those skilled in the art. The resist is then subjected to a late exposure bake at about 95 DEG-160 DEG C., more preferably 112 DEG-120 DEG C., for about 10 seconds to the time required for resin cross bonding. This is about 10
It can range from seconds to about 90 seconds. After firing, a full flood exposure can optionally be performed. The exposed resist is then developed in a suitable developer until substantially all of the non-image areas of the resist are removed. Suitable developers include, nonexclusively, aqueous sodium hydroxide and aqueous tetramethylammonium hydroxide, as well as known in the art.

The developed resist can optionally be heat treated again.

〔Example〕

Although the following examples illustrate the present invention and demonstrate the advantages of the photosensitive compositions of the present invention as compared to conventional corresponding photosensitive compositions, it is understood that the present invention is not limited thereto. You should understand.

Example l.

Tetrahydrone 20. 3,5-dimethyl-4 in N
- Acetoxystyrene 5r (0.03 mol) is stirred at room temperature.

0.11 of azoinbutyronitrile is added and the reaction is carried out under nitrogen. The solution is then heated to reflux under nitrogen for 24 hours.

The resulting polymer is then isolated by precipitation in water and dried in a vacuum oven. Molecule t23,000
poly(3,5-dimethyl-4-acetoxystyrene)
A yield of 4.4r (88%) is obtained.

Example 2゜3,5-dimethyl- in 300 mj of tetrahydrofuran
4-acetoxystyrene 20? is added to a three-way flask equipped with a reflux condenser, thermometer, and nitrogen gas inlet. The solution is stirred under nitrogen for 30 minutes. 0.41 azoisobutyronitrile in 50ml of Tetrahydro7ran
is added little by little at room temperature and stirred under nitrogen. 2 solutions of C
Heat at reflux for 4 hours. The resulting polymer was separated by precipitation in water and dried to give poly(3,
5-dimethyl-4-acetoxystyrene) 17F (85
%).

EXAMPLE 3 The polymer reaction product of Example 2 was mixed with tetramethylammonium-hydroxide (2rILt, 2ml in methanol while stirring the polymer in tetrahydrofuran).
5%). Add methanol if necessary. C
The solution is refluxed under nitrogen for 36 hours. After separation, the reaction product is poly(3,5-dimethyl-4-hydroxystyrene).

Example 4゜Stere/) 10? of 4-acetoki-7-3,5-dipromostyrene was dissolved in 401 of propylene glycol monomethyl ether acetate, treated with azobisisobutyronitrile as a radical initiator, and dissolved in an airtight container at 70% of
Heat at 3°C while passing the glass through the container. Then, the same amount of azobisisobutyronitrile (AIBN) is added and heated at 80° C. for 3 hours. The polymer is precipitated from a 2=1 methanol:water solution, removed by suction, taken up in TIIF, and precipitated again with petroleum ether. After drying a white powder of 7.7-8.71 is obtained.

An “Ultra Styrogel” column (Watgrtt G
The molecular weight of the polymer is determined by gel permeation chromatography on mbH). The following values can be changed depending on the amount of radical disclosing agent added.

α)2X0.12r 25,300 0.88
9.4Pb) 2X0.5r 21,3
00 0.84 9.4rc) 2X0.7
5j' 13,000 0.89 8.7
5' Example 5゜ Poly(3,5-dibromo-4-acetoxy) by bulk polymerization 152 4-acetoxy-3,5-dipromostyrene was mixed with 700rn9 azobisisobutyronitrile and transferred to a vacuum ampoule. Seal under vacuum.Polymerization at 90%
℃ for 3 hours, after which time the initially melted material is allowed to solidify again.

The polymer is taken up in THF, reprecipitated twice (from methanol/water and from petroleum ether) and dried under vacuum. 10.15y of white powder is obtained. The molecular weight (Ak+) determined as in Example 4 is 31,000 and the non-uniformity (U') is 1,39.

EXAMPLE 6 109 3,5-Schifcomo-4-hydroxystyrene is dissolved in ICI's THF, treated with 0.4M azobisinbutyronitrile (AIBN) and heated to reflux under nitrogen. A sample taken after 4 hours yielded a sticky substance upon precipitation with methanol, which still contained large amounts of monomer as well as polymer. Furthermore 0.51 AI
After addition of BN and polymerization for a further 6 hours, the polymer is precipitated from petroleum ether. After drying, about 3.50
White powder with a molecular weight of 0 (41w) 4.2? get.

Example: 7゜52 3,5-dibromo-4-hydroxystyrene with 2
Bulk polymerization is carried out as in Example 4 by adding 50 μ of AIBN. After precipitation from petroleum ether, white crystals of ω1w of 3.41 (about 6,000) are obtained.

Example 8° A mixture of 8 parts of an acetoxy compound and 2 parts of a hydroxy compound ICl-Hα) in solution as in Example 4 and (b)
Bulk polymerization and separation as in Example 5. (α)
For (6), a white polymer with molecular weight (41w) 8,400 and (6), molecular weight (Afw)
6.22 of 21,000 white polymers are obtained respectively.

Example 9゜8.42 of 4-acetoxy-3,5-dipromostyrene was mixed with 42 of 4-acetoxystyrene, 600rn
9 of AIBN and placed in ampoules and sealed after degassing and vacuum. Polymerization is carried out at 90° C. for 3 hours. By the same operation as in Example 4, a white polymer (Jew approx.
0,700: Non-uniformity (of 1.38) 9.4 F
get.

Example 10゜Bulk polymerization of 4-acetoxy-3-bromo-5-methylstyrene 10? 4-acetoxy-3-bromo-5-methylstyrene was mixed with AIBN and polymerized for 3 hours at 90 DEG C. in a degassed and sealed ampoule as in Example 6. After treatment as in Example 4, the white polymer of 7.52 (
&w=30.300: Obtain non-uniformity U-1, 28).

Example 110 7.72 of the reaction product of Example 1 is suspended in 120 g of water,
7.31 with tetramethylammonium hydroxide hexahydrate. The mixture was heated to 70°C for 6 hours under nitrogen flow, then filtered and
Add gct. In this mixture, H is 2 and a white precipitate appears. This precipitate is removed by suction and reprecipitated twice from THF by dropping into water. 5.6
y white powder is changed.

Example 12 9.73F of the reaction product of Example 4 was dissolved in 50 g of THF, 251 g of methanol was added and the mixture was dissolved in 11.67 g.
Treat P with hydrazine hydrate (80% aqueous solution) and stir at room temperature for 2.5 hours. After addition of 20 m/HCl, a clear solution is obtained, which is brought to pH 2 with concentrated MCI. 1.
Separate the polymer by placing it in 56 water,
Aspirate, precipitate from THF in water and dry. 7.82 white powder is obtained.

Example 13° Styrene) Poly(4-acetoxy-3,5-dipromostyrene) 52 is dissolved in a cold saturated solution of hydrochloric acid in methanol (50 m??). Suspend in the liquid. The mixture was stirred at room temperature for 24 hours and then
00 m of water is added and the polymer is separated by suction and reprecipitated from THF in water. Hydrolyzed polymer 4
．． Get 82.

Example 14゜2.3.4-)dihydroxy-3'-methylbenzophenone 10% solids of 1,2-naphthoquino/Example 3
The photoresist is prepared from a homogeneous solution containing 90% solids of the resin produced by the above method in a sufficient amount of propylene glycol monomethyl ether acetate. Using this solution, 4. Coat with Q Q Of-rPLp and then gently bake in an evacuated convection oven at 90'C for 30 minutes. Actinic radiation exposure is performed through a glass optical mask containing the resolved test pattern using a Perkin-Elmer 200 Miclarin aligner.

Using hole #4, vary the scan rate by any energy unit between 200 and 400. These different scan detours (each scan rate is a typical experiment) are each 20 mJ/cry? measured with a radiometer for wavelengths between 365 nm and 436 nm. and 1
0 mJAcf. The optical mask consists of a resolution test pattern, revealing single lines, equal lines and intervals. These custom widths are 1.0μ and 3.0pm.
It changes in increments of 0.25μ between .

After exposure, the sea urchin 7a is optionally subsequently hard fired on an MTI Incorborated hot plate at a temperature in the range of 110-150°C for up to 60 seconds. 5 The wafer is a single color
201＠ Placed under the optical microscope of ina irradiation,
No L/IJ-7 image is observed.

The exposed and optionally hard-baked wafer is AZ433M.
After development by reconnaissance in a 0.33# solution of tetramethylammonium hydroxide available from the AZ Photoresist ψ Group, Hoechst Celanese Corporation, Zimmerville, New Chassis, USA). , wash the wafer with deionized water,
Swirl to dry.

When this wafer is calibrated using a 10,0000 magnification scanning electron microscope, the 1 .mu.m rate-spacing and larger geometries are clearly visible as fully open.

Example: 15° A coating solution is prepared from:

1) Kunzol with a softening point range of 105-120℃
Formaldehyde novolac resin 4 parts by weight + 1) Orthocarboxylic acid ester consisting of 2-phenoxyethanol and orthoformic acid (West German patent iP 3)
730787-3)
21 dispersion 111) Poly(3,5-dibromo-4=hydroxystyrene) according to example 6 or example 7
4-layer Tit Part 1v) Propylene Glycol Methyl Ether Acetate 301 Fluorescent Part This solution is spin coated at 30007 pm onto a silicon wafer treated with an adhesion promoter (hexamethyldisilizane). After drying for 30 minutes at 85° C. in a circulating air oven, a coating of 0.85 micron thickness is obtained. Irradiation in the image pattern through a gold mask on silicon 3
Cy/Kurodoro 77R shot with irradiation dose of 0m1/c1♂ (B aa ay in West Berlin: air space 112111
m). Setting the experimental conditions is A.

Hawbargmr, “X-Ray Lithogr.
apny”, kficro-alactronic E
nginagvitsg: L 535 556 (19
85) K is found. The wafer is developed with an alkaline developer having the following composition.

Sodium meta-silicate nonahydrate 5.3 parts by weight/trisodium acid dodecahydrate 3.41
Seibe sodium phosphate dihydrate 0.3
Part by weight: Completely deionized water 0.3N
After 30 seconds of development, sufficient to create a developer, an error-free image with all of the mask details is obtained. The edges of the resist are undercut in the negative and are at an angle of approximately 90° (scanning electron microscopy (SE
M) by photo). This does not change even when tempering is performed at 140° C. for 30 minutes. 0.85 micron'M,
The thickness of the cover is also kept constant within the experimental error range.

The same results are obtained when the same measurements are carried out after 4 weeks of storage at room temperature.

Example 16゜ A coating solution is prepared from:

1) Cresol with a softening point range of 105-120℃
Formaldehyde autonovolac tree n effect 4M parts 11
) Oligomeric acetal of cyclohexanone and triethylene glycol (Seidokuhosha 7P3730787.)
8) 2 parts by weight 111)
Poly(3,5-dibromo-4-hydroxystyrene) according to Example 6 or Example 7 4ftg+v)
7” Robylene glycol methyl ether aldehyde
30 parts by weight of this solution are spin coated at 3000 depm onto silicon wafers treated with an adhesion promoter (hexamethyldisilizane). After drying for 30 minutes at 85° C. in open circulating air, a coating with a thickness of 0.85 microns is obtained. Irradiation in an image pattern through a gold mask on silicon at 30 m
It is carried out using synchrotron radiation (Baaay: Air Gap 2, West Berlin) with a dose of 17 cm. Setting the experimental conditions is A.

Ra5her (Hr, “X-Ray Lithogr
aphy”, Mieroelac-tronic E
%ginamrtng 3,535 556 (19
85). Develop the sea urchin 7er with an alkaline developer having the following composition.

Sodium metasilicate nonahydrate 5.3 parts by weight Trisodium phosphate dodecahydrate 3.4 parts by weight Sodium dihydrogen phosphate 0.3
Part by weight: Completely deionized water 0.3N
After 30 seconds of development, sufficient to create a developer solution, an error-free image with all of the mask details is obtained. The edges of the resist are undercut in the negative and are at an angle of approximately 90° (scanning electron microscopy (5E
M) by photo). This does not change even when tempering is performed at 140° C. for 30 minutes. The coating thickness of 0.85 microns also remains constant within experimental error.

The same results are obtained when the same measurements are carried out after 4 weeks of storage at room temperature.

Example 17. (Comparative example) A coating solution is prepared from:

1) Cresol with a softening point range of 105-120℃
Formaldehyde e-novolac resin 4 parts by weight II)
Orthocarboxylic acid ester produced from 2-phenoxyethanol and ortho-formic acid (West German patent application P3)
According to 730787.8 > 2iit part 1
11) Brominated poly(p) with bromine content of 50 wt.
4 parts by weight +
v) Flopylene glycol methyl ether aldehyde 30 M parts This solution is spin coated onto a substrate according to Example 15, dried, irradiated in an image pattern and developed. Image reproduction is good, but removal of dark areas at 250 microns/min is more than desired. Due to the high removal rate of the dark areas and the high development rate, differential images are no longer possible after one week's storage at 40°C.

Example 18゜ A solution for G is prepared from the following:

1) Silenol ether of 72 parts of cyclopentano and 1 part of dichloromethylphenylsilane (West German patent application P37
30783.5) 2 parts by weight11)
Poly(3-bromo-4-hydroxy-5-methylstyrene 8 parts +++)
7” Robylene glycol methyl ether aldehyde
30 parts by weight of this solution was spin-coated onto a substrate according to Example 15 and after drying 60 parts by weight
%J/at? f) Irradiate at a dose. Development is carried out in the developer of Example 15, the concentration of which is set at 0.3N.

After 13.5 seconds of development, an error-free image comparable to Example 15 is obtained. When the initial coating thickness is 1.08 microns, only 0.3 microns of dark areas are removed. Storage stability is also similar to that described in Example 15.

Procedural amendment November 2, 1988 Commissioner of the Japan Patent Office Yoshi 1) Takeshi Moon 1 Display of the case 1988 Permanent Application No. 232132 2 Name of the invention 3 Person making the amendment Relationship with the case Name of patent applicant Hexist Akchengesell shaft (outer 1)
Name) 4 Agent Name Patent Attorney (7175) Takehiko Saito ゛,
", -'- 5. Engraving of the handwritten specification attached to the application subject to amendment

Claims (1)

[Scope of Claims] 1. Alkyl or alkoxy, primary or secondary amino, having a molecular weight in the range of about 1,000 to about 800,000, in which 3 and 5 substituents are independently C_1 to C_1_0;
or the compound poly(3,5-disubstituted-4-acetoxystyrene) which is halo. 2. The compound of claim 1 having a molecular weight in the range of about 5,000 to about 15,000. 3,3,5-disubstituted-4-acetoxystyrene monomer (wherein the 3,5 substituents are independently C_1 to C_1_0 alkyl or alkoxy, primary or secondary amino, or halo) to about 1, 000~about 800,0
free radical polymerization until a molecular weight of 0.00 is reached;
The polymer thus produced is then hydrolyzed with a sufficient amount of a suitable hydrolyzing agent to obtain a poly(
3,5-disubstituted 4-hydroxystyrene). 4. The method according to claim 3, wherein the hydrolyzing agent is a base. 5. The method according to claim 3, wherein the hydrolyzing agent is tetramethylammonium hydroxide. 6. The method according to claim 3, wherein the free radical polymerization is initiated using azo-isobutyronitrile. 7. Alkyl or alkoxy, primary or secondary amino, having a molecular weight in the range of about 1,000 to about 800,000, in which the 3 and 5 substituents are independently C_1 to C_1_0;
or halo; an o-quinone diazide photosensitizer; and a suitable solvent, the polymer being a binder of the composition. the diazide is present in an amount sufficient to provide a differentiated image when the composition is coated on a substrate and imagewise exposed to actinic radiation, and the solvent is A photosensitive composition present in an amount sufficient to create a homogeneous solution of the components. 8. Poly(3,5-disubstituted-4-hydroxystyrene)
8. The composition of claim 7, wherein has a molecular weight of about 5,000 to about 15,000. 9. The photosensitizer is naphthoquinone-(1,2)-diazide-(
8. The composition according to claim 7, which is a condensate of 2)-4 or 5-sulfonyl compound and hydroxybenzophenone. 10. The composition according to claim 7, wherein the solvent is propylene glycol monomethyl ether and/or propylene glycol monomethyl ether acetate. 11. The composition of claim 7, wherein the weight ratio of said polymer to said photosensitizer ranges from about 1:1 to about 20:1. 12. Colorants, dyes, anti-string agents, plasticizers, adhesion promoters,
Claim 7 further comprising one or more additives selected from the group consisting of speed enhancers, solvents and surfactants.
Compositions as described. 13. The composition according to claim 7, further comprising a cross-linking agent. 14. The composition according to claim 13, wherein the cross-linking agent is dimethylol para-cresol. 15. A photographic element comprising a support coated with the dry composition of claim 7. 16. A photographic element comprising a support coated with the dry composition of claim 13. 17. The photographic element of claim 15, wherein the support comprises one or more materials selected from the group consisting of semiconductor materials, metals, plastic films, wood, paper, ceramics, and textiles. 18. The support is selected from the group consisting of polyester, polyolefin, silicon, gallium arsenide, silicon/silicon dioxide, doped silicon dioxide, silicon nitride, aluminum/copper mixture, tantalum, copper, polysilicon, and aluminum. 16. A photographic element as claimed in claim 15, consisting of or more than one material. 19. Coating the photosensitive composition of claim 7 onto a support; drying the composition until it is substantially tack-free; exposing the composition to sufficient actinic radiation, electron beam or x-ray radiation; A method of forming a photographic image comprising: exposing the composition to radiation to provide a differentially distinguishing image; and removing the non-image portions of the composition with a developer. 20. Claim 19, wherein the developer comprises an aqueous alkaline solution.
Method described. 21. The method of claim 20, wherein the developer does not contain metal ions. 22. Coating the photosensitive composition of claim 13 onto a support; drying the composition until substantially tack-free; subjecting the composition to sufficient actinic radiation, electron beam or X-ray radiation; Exposure to radiation to provide a differentially distinguishing image;
heating to a temperature of from about 160<0>C to cross-link the polymer; and removing the non-image portions of the composition with a developer;
A method of forming a photographic image consisting of: 23, poly(3) containing units with the following general formula (I)
-mono- and 3,5 di-halogenated 4-hydroxy-
and 4-acetoxy-styrene) and their copolymers. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [R is hydrogen or acetyl; Hal is chlorine or bromine; R_1 is hydrogen, alkyl, or halogen; and R_2 and R_3 are independently hydrogen, allyl , alkoxy or halogen, but when R_1 is alkyl, R_1 and R_2 together particularly represent 6 to 1
A two-membered alicyclic group can also be formed. ] 24, Hal is bromine, R_1 is (C_1 to C_3
) alkyl, R_2 and R_3 are hydrogen,
24. The polymer of claim 23, wherein R is hydrogen. 25. The polymer of claim 23, wherein the polymer contains at least 50% of units having the general formula (I). 24. The polymer of claim 23, comprising up to about 50% comonomers that are 26, styrene, 4-acetoxystyrene, 4-hydroxystyrene, or 3,5-disubstituted-acetoxystyrene and -hydroxystyrene. 27. The polymer of claim 23 having a molecular weight of about 1,000 to 500,000. 28. A positive-acting radiation-sensitive mixture comprising an initiator compound that generates an acid under the action of actinic radiation and a compound cleavable by the acid, the acid-generating compound having the general formula (I ) is a positive-working, radiation-sensitive mixture that is a polymer having units of ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [R is hydrogen or acetyl; Hal is chlorine or bromine; R_1 is hydrogen, alkyl, or halogen; and R_2 and R_3 are independently hydrogen, allyl , alkoxy or halogen, but when R_1 is alkyl, R_1 and R_2 together particularly represent 6 to 1
A two-membered alicyclic group can also be formed. 29. The positive-working radiation-sensitive mixture of claim 28, wherein the polymeric starter is included in the radiation-sensitive mixture in an amount of about 2 to 60% by weight, based on the weight of the mixture. 30. The positive-working radiation-sensitive mixture of claim 28, wherein said mixture comprises a binder that is insoluble in water but at least swellable in aqueous alkaline and organic solvents. 31. A positive-working, radiation-sensitive mixture according to claim 30, wherein the binder is a novolac resin. 32. The positive-working radiation-sensitive mixture of claim 28, wherein the polymer starter and binder in the mixture are present in substantially equal proportions by weight. 33. Positive-working for the production of printed circuits and for the production of offset printing plates, consisting of a substrate and a radiation-sensitive layer on said substrate, said photosensitive layer consisting of a radiation-sensitive mixture according to claim 28. Recording materials. 34. coating a substrate (optionally coated with an adhesion promoter) with the radiation-sensitive mixture of claim 28, drying the material, and then subjecting the material to actinic radiation in an image pattern. 1. A process for producing a positive-working recording material, which comprises irradiating and then developing the imaging material with an alkaline developer. 35. Before development, the resist structure is heated and exposed to UV light.
35. The method according to claim 34, wherein the method is cured by radiation. The 36,3,5-disubstituted-4-acetoxystyrene monomer is hydrolyzed with a sufficient amount of a suitable hydrolyzing agent to give the unprotected monomer so produced a
,000 (with the proviso that the 3,5-substituents are independently C
_1 to C_1_0 alkyl or alkoxy, primary or secondary amino, or halo) poly(3,5-disubstituted-4-hydroxystyrene)
manufacturing method. 37. The method according to claim 36, wherein the hydrolyzing agent is a base. 38. Claim 36, wherein the hydrolyzing agent is hydrazine hydrate.
Method described.