JPH032142A - 3-substituted 4-acetoxystyrene, production thereof, homo- and co-polymers and use thereof - Google Patents

Abstract

PURPOSE: To obtain the title compd. useful for a monomer of a polymer easily used in a photoresist by using 2-substd. phenol as a starting raw material to acylate the same in the presence of a catalyst and esterifying the obtained compd. before hydrogenating and dehydrating the same.

CONSTITUTION: 2-substd. phenol (a substitutuent is 1-10C alkyl, Br, I, Cl, NO₂ or SO₃H) is acylated in the presence of a proper catalyst such as acetic anhydride to form 3-substd.-4-hydroxyacetophenone which is, in turn, esterified by acetic anhydride to obtain 3-substd.-4-acetoxyacetophenone. This compd. is hydrogenated in the presence of a catalyst such as Pd/C to form 1-(3'-substd.-4'- acetoxyphenyl) ethanol which is, in turn, dehydrated in the presence of a dehydration agent and a polymn. inhibitor to obtain the objective compd. useful for producing a polymer such as poly(3-methyl-4-acetoxystyrene) or poly(3- methyl-4-hydroxystyrene).

COPYRIGHT: (C)1991,JPO

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to 3-substituted-4-acetoxystyrene (3-substituted is c, to c, alkyl, Br5I, CL%NO, or So, H ), its preparation, homo- and copolymers prepared therefrom and their use, particularly in photoresists.

[Conventional technology]

It is well known to those skilled in the art to produce monomers, homopolymers and copolymers of 4-acetoxystyrene and their hydrolysis to produce 4-hydroxystyrene derivatives or polyvinylphenols. These are photoresists,
Used in the production of adhesives, coating compositions, etc.

The compounds of the invention may be used in polymers such as poly(3-methyl-4-
acetoxystyrene) and poly(3-methyl-4-hydroxystyrene). These latter compounds are useful as improved bonding resins for photoresists that have more favorable dissolution rates in commercially used photoresist developers.

Alpha-acetoxystyrene and beta-acetoxystyrene are described in U.S. Pat. No. 4,144, (363) and acetoxymethylstyrene is described in U.S. Pat.
No. 963,495. U.S. Pat. No. 4,075,237 describes 1,4-dimethyl-2-
describes hydroxystyrene, while U.S. Patent No. 4.56
No. 5,846 Blue teaches the use of poly(3,5-dimethyl-4-hydroxystyrene). Japanese Unexamined Patent Publication 1983
No. 23,747 describes antistatic compounds using poly-acetoxymethylstyrene and U.S. Pat. No. 4,221,700 uses poly(alkylated alkenylphenols) containing 2-methylparavinylphenol. A stabilized synthetic polymer composition is described. U.S. Pat. No. 4,600,683 and U.S. Pat. No. 4.543
No. 397 describes poly(alpha methylvinylphenol). 4.517.028 for U.S. Patent
; 4.460°770 and 4,539,051 describe dimethylvinylphenol. U.S. Patent Application No. 097,809; 097.810 and 097,8
No. 15 (all filed on September 16, 1987, and the references and (cited) are, respectively, 3,5-disubstituted-4-acetoxystyrene:poly(3,5-disubstituted-4
-hydroxystyrene/N-substituted maleimide) and the polymerization, hydrolysis, and use of 3,5-disubstituted-4-acetoxystyrene.

Positive photoresist formulation e.g. US patent 3.666.4
75; 4.115,128 and 4,173,470 are well known to those skilled in the art. These are photosensitive materials, usually substituted naphthoquinonediazide compounds as well as alkali-soluble phenols and
Contains formaldehyde and novolak resin. The resin and sensitizer are dissolved in an organic solvent or mixture of solvents and applied as a thin film or coating to a substrate suitable for the particular application desired. Although the resin components of these photoresist formulations are soluble in aqueous alkaline solutions, naphthoquinone sensitizers generally are not. Upon exposing selected areas of the coated substrate to actinic radiation, however, the sensitizer becomes more soluble than in the unexposed areas. This difference in dissolution rate causes the exposed areas of the photoresist coating to dissolve when the substrate is immersed in an alkaline imaging bath solution, but
On the other hand, the unexposed areas are largely unaffected and therefore produce a pattern of positive relief on the substrate.

In many cases, the substrate that is exposed and developed is subjected to treatment with a substrate etchant. A photoresist coating captures the coated neck of the substrate from the etchant and therefore the etchant can only etch the uncoated areas of the substrate, which in the case of a positive photoresist is the area exposed to actinic radiation. corresponds to An etched pattern is thus created on the substrate, which corresponds to the pattern on the mask, stencil, template, etc. used to create the selectively exposed pattern on the coated substrate prior to development.

Patterns of photoresist relief on substrates produced by the methods described above are useful in a variety of applications including photosensitive masses or patterns such as those used in the manufacture of miniaturized integrated electronic components. Properties of photoresist compositions necessary for commercial implementation include resist photosensitivity, development contrast, resist degradation, and resist adhesion.

In many industrial applications, especially in the production of miniaturized electronic components, photoresists are used to create very small lines and spacings (
It is required to provide a high degree of resolution (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 the fabrication of large scale integrated circuits in silicon chips and similar components.

The circuit density in such chips will only increase, taking advantage of photolithographic techniques by increasing the resolution capability of the resist. Photoresists are generally classified as either negative-working or positive-working. In negative-working resist compositions, the areas of the image that are hit by the light harden and the developer removes the unexposed areas. After forming the image area of the resist.

Works positively (in resist, the exposed area is the area other than the image. The exposed area is treated with an alkaline aqueous developer.)
Becomes soluble. Although negative resists are most widely used in industrial manufacturing of printed circuit boards, positive resists produce very fine resolution and smaller image structures. Therefore, positive resists are chosen for the production of densely packed integrated circuits.

[Summary of the invention]

The present invention provides novel polymers and photographic compositions using these polymers. In one important embodiment of the present invention, photoresists employing the above-described polymers as bonding resins exhibit development and dissolution properties similar to phenol formaldehyde novolac resins, but polyvinyl phenol, which is also known for this purpose. It was found to exhibit an advantageously lower dissolution rate than 2. Polyvinylphenol has the disadvantage of faster dissolution, which makes image differentiation more difficult to achieve. But they are about 20
It can withstand much higher processing temperatures than novolak, on the order of 0°C. Preferred polymers of the invention exhibit dissolution rates comparable to novolacs and can resist processing temperatures comparable to polyvinylphenol. It is also an improvement over poly(4-hydroxystyrene), which is generally produced only in low molecular weight, poor color, impure form.

The present invention provides a method for preparing 3-substituted-4-acetoxystyrene, which comprises (5) acylating a 2-substituted phenol, preferably with acetic anhydride under suitable catalysis to produce a 3-substituted-4-hydroxyacetophenone. bring, then (
b) Esterifying 3-tit-substituted-4-hydroxyacetophenone, preferably with acetic anhydride, to form 3-substituted-4
-acetoxyacetopheno/ and then (c) 3
-tri-substituted-4-acetoxyacetophenone is hydrogenated to form 1-(3'-substituted-47-acetoxyphenyl)ethanol and then (d) 1-(3'-substituted-4'-acetoxyphenyl)ethanol to form 3[%-4-acetoxystyrene, each of the above substitutions being C8-C1° alkyl, E
r, 1. C.L.

NO7 or So, H. The present invention also provides a method for making poly(3-substituted-4-acetoxystyrene), which comprises adding previously prepared 3-substituted-4-acetoxystyrene until a molecular weight of about 1,000 to about 300,000 is obtained. Consists of free radical polymerization. The present invention also provides a method for preparing poly(3-substituted-4-hydroxystyrene), which comprises pre-prepared poly(3-substituted-4-acetoxystyrene).
It consists of hydrolyzing. The present invention also provides 3-substituted-4
A copolymer of -hydroxystyrene and 3°5-disubstituted-4-hydroxystyrene is provided. The present invention further provides three
-substituted acetoxystyrene and 4-acetoxystyrene,
3.5-disubstituted acetoxystyrene, maleic anhydride,
Copolymers and terpolymers of maleimide, styrene, methacrylic V-), methyl methacrylic V-) and butyl acrylate are provided. The present invention further provides a photosensitive composition comprising a mixture of any of the aforementioned polymers with a photosensitizer such as O-quinonediazide.

In preferred embodiments, the preferred 3-substitution is methyl and preferred embodiments will be described in detail. Other permutations can be obtained in a similar manner. The process for making 3-methyl-4-acetoxystyrene starts with readily available 0-cresol, which is preferably esterified with acetic anhydride to produce 2-methyl-4-phenylacetate. This is then converted to 3-methyl-4-hydroxyacetophenone by Fries rearrangement. O-cresol can also be converted to 3-methyl-4 by Friedel-Krauch catalysis.
-converted to hydroxyacetophenone. This is then preferably esterified with acetic anhydride to give 3-methyl-
Forms 4-acetoxyacetophenone. The latter is then hydrogenated to form 1-(3'-methyl-4'-acetoxyphenyl)ethanol.

This is then dehydrated to form 3-methyl-4-acetoxystyrene monomer. These first two reaction steps proceed almost simultaneously. That is, a reactor is charged with 0-cresol, a slight excess of anhydrous vinegar, and a Friedel-Krach catalyst such as hydrogen fluoride. Acylation is carried out at a temperature of about 10°C to about 100°C, or more preferably from about 0°C to about 80°C.

The most preferred temperature is about 50°C. The reaction is about 1 to about 5
Proceed at a preferred pressure of about 700 saH2 to about 780 wtHt for an hour. Esterification of the hydroxyl group for its protection is preferably achieved with acetyl chloride or acetic anhydride. However, any reagent known to protect hydroxyl functionality may be used. These include in particular ethers such as methyl, methoxymethyl, 2-methoxyethoxymethyl, methylthiomethyl, tetrahydropyranyl, cyclopropylmethyl, allyl, isopropyl, cyclohexyl, tert-butyl, benzyl, 0-nitrobenzyl, 9-anthrylmethyl and 4-picolyl ether, also silyl ethers such as trimethylsilyl and t-j methyldimethylsilyl ether, esters such as acetate, pivaloate, benzoate and 9-fluorene carboxylate, carbonates such as methyl, 2,2.2-1-lichloroethyl, including the formation of vinyl and benzyl carbonates, aryl carbamates and sulfonates such as methanesulfonate and toluenesulfonate. This type of protecting group is described by Thaodora W., Gram
s) [Brotective Glue 7's in Organic Synthesis ()rotaetivaGro%
ps js Organic 5 synthesis)
” John 1 Wiley & Sons (Jo7Ls W
It-y & 5ons) (1981). However, acetoxy groups are particularly preferred. Hydrogen fluoride is the preferred catalyst, but other Lewis acids such as AtC65,
HClO4, BP, , H, PO, and S9Ct.

is also used. Acylation, on the other hand, is carried out in a manner well known to those skilled in the art, using a 7-liase arrangement. 3 which is a reaction product
-Methyl-4-hydroxyacetophenone is then esterified with butyric anhydride. In this method, 3-methyl-4-hydroxyacetophenone is refluxed with excess acetic anhydride for about 1 to about 20 hours. Excess acetic anhydride and generated acetic acid are removed by vacuum distillation (for example, approximately 1
The 3-methyl-4-acetoxyacetophenone obtained is then preferably flash distilled at a pressure of about 10 to about 40 m5+Hr and at a temperature of about 100 to about 125 °C. The 3-methyl-4-acetoxyacetophenone is then catalytically hydrogenated.
For example, if you first save 30 inches HNO and then KOH/Improper Tools! Forms a film. 3-Methyl-4-acetoxyacetophenone, excess hydrogen gas under pressure, an amount of a suitable catalyst and a suitable solvent sufficient to drive the reaction are then charged. One preferred catalyst is 3-methyl-4
- Pd/C of about 1 to about 4 weight i% of acetoxyacetophenone. Other suitable catalysts are generally CaCO5,
Ni/A4 boron hydride) IJium and Pt, Pd
and a reduced metal salt of Ni. A preferred solvent is ethanol and is present in an amount of about 3 to about 5 parts by weight of 3-methyl-4-acetoxyacetophenone. The reaction is carried out at a preferred temperature of about 25°C to about 40°C, about 100 to about 250°C.
Proceed at a preferred hydrogen gas pressure of mHt psig. The reaction is allowed to run for about 1 to about 5 hours. The product obtained 4'! ,1
-(3'-methyl-4'-acetoxyphenyl)
/-. This compound is then dehydrated. Dehydration is preferably carried out under vacuum by heating the compound in the presence of a polymerization inhibitor and a dehydrating agent. In one preferred embodiment, 1-(3'-methyl-47-acetoxyphenyl)ethanol is mixed with KIISO4R water solution and t-butylcatechol (polymerization inhibitor). Other useful dehydrating agents are generally bases, CsSO4, C5r(1'4 and At
, O, is included. Other polymerization inhibitors are generally hydroquinone,
Contains tetrachloroquinone and di-t-butyl-p-cresol. The dehydrating agent is present in an amount of about 0.25% to about 2.0% by weight of the compound. The polymerization inhibitor is preferably present in an amount of about 1% to about 5% based on the weight of the oil. About 1.0 to about 15 wnHf, preferably 1.5 to 2.0 m at about 60°C to about 210°C, preferably from 185°C to about 190°C
H? Heat at a pressure of The product is then distilled and then redistilled after addition of additional polymerization inhibitor.

The 3-methyl-4-acetoxystyrene monomer is then polymerized by free radical initiation to produce poly(3-methyl-4-acetoxystyrene), which has a polymerization rate of about 1,000 to about s.
o cxoo.

Preferably it has a molecular weight ranging from 5.000 to 50.000 or more preferably from about s,ooo to about 15,000. This intermediate is then hydrolyzed with base or acid to form poly(3-methyl-4-hydroxystyrene), which has a molecular weight ranging from about 1.000 to about 500.000. One preferred free radical initiator is azoin butyronitrile.

Other azo type initiators are also suitable. Still others commonly include peroxides such as benzoyl peroxide and di-t-butyl peroxide. It is expected that almost all free radical initiation systems will operate in the same manner. One preferred hydrolyzing agent is tetramethyl ammonium hydroxide.

Other hydrolyzing agents are generally aqueous NH3, NaOH and KO.
Contains H. The aforementioned 3-methyl-4-acetoxystyrene may also contain one or more additional monomers (4-acetoxystyrene, 3,5-disubstituted acetoxystyrene, maleic anhydride, maleimide, styrene, methacrylate, methyl methacrylate). and butyl acrylate) under the aforementioned polymerization conditions. 3-substituted-4-acetoxystyrene is also 3,
Copolymerized with 5-disubstituted-4-acetoxystyrene and then hydrolyzed with acid or base to form poly(3-11-substituted-4
-hydroxystyrene/3,5-disubstituted-4-hydroxystyrene). Any of the foregoing copolymers and terpolymers may be used in combination with a photosensitizer to form a photographic element, such as a photosensitizer.

In preparing the photosensitive compositions and photographic elements of this invention, the above-prepared binding resin is mixed with an O-quinonediazide photosensitizer and a suitable solvent until a homogeneous solution is formed.

The solution is then coated onto a suitable substrate and dried until it is no longer tacky.

The use of 0-quinonediazide is well known to those skilled in the art;
It is called “Light Sensitive Systems”.
tSg*tttiva Systemg Tsukikosa-(Ko
aar) J, C John - Wiley & Sons, Niney York, 1965) Chapter 7.4, which is also cited as a reference. These sensitizers that are components of the resist compositions of the present invention are preferably selected from the group of substituted naphthoquinone diazide sensitizers (conventionally used by those skilled in the art in photoresist formulations).

This type of sensitizing compound is described in US Pat. No. 2,797, for example.
．． 213; 3.1 (36,465; 3,148,983
;3.130.047;3,201,329;3
, 785, 825; 3.802, 885), which are cited by reference.

The photosensitizer is preferably a 1,2 quinone diazide-4 or 5-sulfonic acid ester of a phenolic derivative. It currently appears that the number of fused rings is not important to the invention, but rather the position of the sulfonyl group. That is, the oxygen is in the 1st position, the diazo is in the 2nd position, and the sulfonyl group is in the 4th position.
Alternatively, penzoginone, naphthoquinone or anthraquinone is used as long as it is in the 5th position. Similarly, the number of phenols to which it is attached does not seem to be important. For example, it is a cumylphenol derivative as taught in U.S. Pat. No. 3,640,992, or it is a mono-, as shown in U.S. Pat. No. 4,499,171.
It can be a di- or trihydroxyphenylalkyl ketone or a benzophenone.

Both of these patents are cited as references.

Useful photosensitizers include phenolic compounds such as hydroxybenzophenone, especially trihydroxybenzophenone, more especially 2,3,4-trihydroxybenzophenone condensed with (1.2) naphthoquinonediazide-4-sulfonyl chloride; 2. 3.4-trihydroxyphenylpentylketone 1.2-Natsutaquinone-2-diazide-4-sulfonic acid trisester or other alkylphenone; 2,3°4-trihydroxy-3'-methoxybenzophenone 1.2-st 7 taquinone-2-diazido-4-sulfone tris ester; 2,3.4-)dihydroxy-3-fumethylbenzophenone 1.2-7 taquinone-2-diazido-4-sulfone tris ester; and 2,3 .4-) Lyhydroxybenzophenone 1.
Contains 2-natsutaquinonediazide-4-sulfonic acid tris ester.

The photosensitive m-parabolite is formed by mixing the ingredients in a suitable solvent composition. In preferred embodiments, the resin is present in the total composition in an amount of about 75% to about 99%, based on the weight of the non-solvent portion of the preferably solid composition.

A more preferred range of resin is from about 80 to 80% of the solid composition.
It will be about 90% by weight and most preferably about 82 to about 85% by weight.

The diazide is preferably present in an amount ranging from about 1% to about 25% solids, based on the weight of the non-solvent portions of the composition. A more preferred range of diazide is about 1 part of the solid composition.
~ about 20% by weight and more preferably about 10 to about 18%
It would be % by weight.

To prepare the composition, the resin and diazide are mixed with solvents such as propylene glycol alkyl ether acetate, bufk acetate, xylene, ethylene glycol, monoethyl ether acetate, propylene gellicol monomethyl ether, and propylene glycol monomethyl ether acetate. Mix.

Additives such as colorants, dyes, anti-striking agents, plasticizers, adhesion promoters, sensitivity enhancers, solvents and surfactants such as nonionic surfactants are added to the solution of the resin, sensitizer and solvent. can be added until the substrate is coated.

An example of a dye additive that may be used with the photoresist compositions of the present invention is Methyl Violet 2B (c, 1,142
535 people Crystal Violet CC, 1,4255
5), malachite green (c, LA42000),
Victoria Blue B (c, 1, B 44045) and Neutral Red (c, 1, A 30040),
1 to 10 weight i based on the combined weight of resin and sensitizer
Chiru at the level of chi. Dye additives help increase degradation by preventing back scattering of light from the substrate. The anti-striking agent is 5i based on the total weight of resin and sensitizer.
! (Used at levels within 41%.

Plasticizers that can be used are, for example, phosphoric acid tri(beta-chloroethyl)-ester: stearic acid; dicamphor;
Contains polypropylene; acetal resins; phenoxy resins; and alkyl resins at levels of 1 to 10% by weight based on the combined weight of resin and sensitizer. Plasticizer additives improve the coatability of the material and allow the application of smooth and even thickness films.

Adhesion promoters that can be used include, for example, beta(3,4-epoxy-cyclohexyl)-ethyltrimethoxysilane; p-methyl-disilane-methyl methacrylate; vinyltrichlorosilane; and gamma-amino-propyltriethoxysilane; and a level within 4% by weight based on the total weight of sensitizer.

Development sensitivity enhancers that may be used include, for example, picric acid, nicotinic acid or nitrocinnamic acid, at weight levels up to 20% based on the combined weight of resin and sensitizer. These enhancers tend to increase the solubility of photoresist coatings in both exposed and unexposed areas, and therefore they make development sensitivity the most important issue, even at the expense of some degree of contrast. Used when. That is, while the exposed areas of the photoresist coating are more quickly dissolved by the developer, the sensitivity enhancer also causes greater loss of the photoresist coating from the unexposed areas. Free radical initiators such as di(trichloromethyl)stibenyltriazine and 1,1,1-trichloro-t-butylacetophenone generate acid functionality upon exposure to light. In addition to increasing photosensitivity, they therefore provide free radicals that cross-link the image when subsequently printed.

Nonionic surfactants that can be used in solutions containing the photosensitive compositions of the invention include, for example, nonylphenoxypoly(oxyethylene)ethanol; octylphenoxypoly(oxyethylene)ethanol;
oxyethylene) ethanol; and dinonylphenoxy poly(oxyethylene) ethanol, at a level within 10 parts per ton based on the total weight of resin and sensitizer.

The prepared photosensitive solution may be applied to a substrate to form a photoresist by any conventional method used in the original resist technology, including dipping, spraying, centrifugal deburring, and spin coating. For example, during spin coating, the resist solution is
The solids content is adjusted to provide a coating of desired thickness.

The support for producing the photoresist of the invention may be any suitable support such as metals (which may be electrochemically or mechanically roughened) such as aluminum and its alloys; plastic films such as polyester. or polyolefins; wood; paper; semiconductor materials (ie, materials that are not electrically conductive unless they are doped) such as silicon, gallium arsenide; ceramics; and textiles. Preferably the support is a silicon-based wafer.

Photoresist coatings produced in the manner described above find particular application in thermally grown silicon/silicon dioxide coated wafers, such as those utilized in the manufacture of microprocessors and other miniaturized integrated circuit components. suitable for

The substrate may be made of various polymeric resins, especially transparent polymers such as polyester. The substrate may also be comprised of doped silicon oxide, silicon nitride, tantalum, copper, polysilicon, ceramic and aluminum/copper mixtures.

After the solution of the photosensitive composition is coated on the substrate, the substrate is coated with a
Bake at about 80° C. to 100° C. at 1, at which substantially all of the solvent evaporates and a thin coating of photoresist composition on the order of microns in thickness remains on the substrate. The coated substrate is then exposed to actinic radiation, particularly ultraviolet radiation (in the range of about 250° to about 45°), produced by the use of a suitable photomask, negative mask, stencil, template, projection means, or the like. In a more preferred embodiment, the UV sensitivity range is from about 254 nm to about 436% fi. The sensitized resist-coated substrate is then immersed in an alkaline developer solution such as a potassium pace alkaline aqueous solution such as Az4Ooxc (obtained from Hoechst Celanese Corporation, Somerville, New Jersey). The solution is preferably free of metal ions. In use, the developer is agitated, for example, by nitrogen pressure and agitation.

The substrate is left in the developer until all or substantially all of the resist coating has dissolved from the exposed areas. After removal of the coating material from the developer solution, a post-development heat treatment or baking is performed as described in British Patent No. 1,154,749.
It can be used to increase the adhesion and chemical resistance of coatings to etching solutions and other substances as taught in the '999 patent. Post-development heat treatment consists of baking the coating and substrate in an oven below the softening point of the coating. In industrial applications, particularly in the manufacture of microcircuit units on silicon/silicon dioxide type substrates, the developed substrates can be treated with a buffered hydrophobic acid etching solution. The resist compositions of the present invention resist such etching M solutions and provide effective protection for unexposed V cyst coated areas of the substrate.

It is well known to those skilled in the art that photosensitive compositions of the above-mentioned type are of the positive working type. However, the invention is not limited thereto and in particular may be used in so-called reversal image photoresists (other suitable ones known to those skilled in the art). For example, a suitable crosslinking agent is included in the photosensitive composition. Non-limiting examples of crosslinking agents and methods are described in U.S. Pat. No. 4,581,321. Hexamethylol melamine ether as taught in US Pat. No. 4,104,070; 4,196.
003; 4,576.901 and 4.5 (36.0
(Crosslinking agents and methods taught in U.S. Pat. No. 36/895,609; All of these are cited as references. The substituted hydroxystyrene and acetoxystyrene polymers of the present invention can be used in place of the alkali-soluble binding resins taught in these documents. A compound that can cross-link polymers in the presence of an amount and strength of acid that is generated when exposed to light; this is sufficient heat to disperse the acid in the cross-linking component, but not enough heat to decompose the diazide. A generally preferred group of this sophisticated compound is those capable of forming carbonium ions under the aforementioned acid and heat conditions. Particularly suitable cross-linking agents for use in the present invention include , but not limited to, general formula % formula %) [wherein A is 2B-Y-E (wherein B is a substituted or unsubstituted mononuclear or condensed polynuclear aromatic hydrocarbon or oxygen- or sulfur-containing complex It is a cyclic compound, Y is a single bond, C1 to C number-
alkylene or alkylenedioxy (the chain may contain an oxygen atom), -o --s --5o2-
-co --CO, -1-Q -Co, --CONH-
or phenylenedioxy); RI and R
1 is H, C, -C6-alkyl, cycloalkyl, substituted or unsubstituted aryl, alkaryl or acyl;
R,,E are independently H,C,~C4-alkyl or substituted or unsubstituted phenyl, and dew is 1-3
and false ranges from O to 3, with the proviso that arithmetical + 惟 is greater than 1]. The crosslinking agent is preferably present in the photographic composition in an amount of about 0.5% to about 20%, more preferably about 1% to about 10%, based on the solids content of the photographic composition. When image reversal is desired in the most preferred embodiment 1
．． 2-naphthoquinone-2-diazide-4-sulfonyl-containing isomers are used as photosensitizers. The 4-isomer is known to generate more acid than the corresponding 5-isomer and is therefore more desirable for image reversal techniques. In one image reversal mode, the photosensitive composition is coated onto a suitable substrate as described above and heated at about 20°C for, for example, 30 seconds to about 3 minutes.
Dry by heating to ~100°C until it loses its tackiness. It is then exposed to image energy in any desired pattern in a manner well known to those skilled in the art. The resist is heated from about 25°C to about 160°C or more preferably at 112°C for about 10 seconds to the time necessary to cross-bond the resin.
℃~about 120℃ post-exposure baking.

This ranges from about 10 to about 90 seconds. After exposure, perform optional whole flood exposure. The exposed resist is then developed in a suitable developer until substantially all non-image areas of the resist are removed. Suitable developers include, but are not limited to, aqueous solutions of sodium hydroxide and tetramethylammonium hydroxide, as is well known to those skilled in the art. The developed resist may optionally be heat treated again.

〔Example〕

The following non-limiting examples serve to illustrate the invention.

Example 1 3-Methyl-4-hydroxyacetophenone: 0-cresol (10,8r, 0.1 mol) and acetic anhydride (15
,3? . Anhydrous HF (80f, 40
mol) into an autoclave and heat the autoclave at 50 U for 2 hours.

The autoclave is cooled and much of the HF is removed by evaporation. The remaining traces of HF are neutralized with KOH and the product is extracted with ethyl acetate (2×100 t/). Concentrate to give a brown product (15,3f). Recrystallize to obtain pure 3-methyl-4-hydroxyacetophenone.

3-Methyl-4-acetoxyacetophenone: 3-Methyl-4-hydroxyacetophenone (25, Of.

0.17 mol), acetic anhydride (50.0d) and acetic acid)
Put IJum (0.5f) into a 1001 volume flask 1
Heat to reflux overnight.

Unreacted acetic anhydride and acetic acid are removed by distillation. 3-Methyl-4-acetoxyacetophenone as a colorless liquid 1
It solidifies when distilled at 03'C (LOmH9) and cooled (
32. (1,97% yield.

1-(3'-Mefk-4'7cetoxyphenyl)ethanol: 3-methyl-4-acetoxyacetophenone (
32f.

0.17 mol) at 5% in a stainless steel autoclave.
Mix with Pd/C (catalyst) and absolute ethanol (120 ml). Pour hydrogen into the autoclave at a pressure of about 1 g.
7.5 A? / on” (250 pa4y). Hydrogenation is carried out for 5 hours at 40° C. The catalyst is removed and the solvent is removed on a rotary evaporator to form a viscous oil C.
1-(3/-Methyl-4'-acetoxyphenyl)ethanol is obtained as (32,45f, 98% yield).

3-Methyl-4-acetoxystyrene: 1- (3'-
Methyl-47-acetoxyphenyl)ethanol (32
, 4sr, 0.17 mol), KIIS (hc O, 32
? ) and t-butylcatechol (0.65f) are combined in a flask. Equip the flask with a fractionator and attach it to a vacuum pump. Dehydration was performed under vacuum (0.5-1.0++ onH)
? ) 160'C~1901. Do it.

3-Methyl-4-acetoxystyrene as a colorless liquid (21,8'l, 74% yield) that solidifies on cooling.
Distilled at 22° C. (0.5 rmHt).

Example 2゜Homopolymerization 11' of 3-methyl-4-acetoxystyrene, 0.4
The azoinbutyronitrile of F is dissolved in degassed tetrahydrofuran in a reaction flask and refluxed overnight. A sample is taken, precipitated in water, and filtered to obtain poly(3-methyl-4-acetoxystyrene).

Example 3 Hydrolyzed Ma, 20% solution of NOH in methanol is added to the reaction flask described above and reflux is continued under nitrogen. Hydrolysis is complete after 18 hours. The polymer is isolated by precipitation in water. The polymer is in the form of a gum and placed in a vacuum oven at 50°C to yield 72 poly(3-methyl-4-hydroxystyrene).

Example 4 Copolymerization of 10.83r 3-methyl-4-acetoxystyrene with maleic anhydride,
601 t of maleic anhydride and 0.43F azoisobutyronitrile! l! of degassed N-methylpyrrolidone and heated to 70°C under N2 for 15 hours.

A portion of the polymer is submerged in water. The polymer is then filtered and dried.

Example 5 Imidization 6.2v of cyclohexylamine is added to the above polymer solution and heated to 75°C for 1 hour and then to 150°C for 15 hours.

The polymer is isolated by precipitation in water and filtration. C”NM
Complete imidization determined by R is observed.

Example 6 A photoV cyst composition was prepared in a solvent solution of propylene glycol monomethyl ether acetate with poly(3-methyl-
4-hydroxystyrene) (PMH8), 15%, t%
2,3゜4-)! J Hydroxy-3'-methylbenzophenone 1,2-natsutaquinone-2-diazide-4
- Sulfone-dispersed triester polymer photosensitizer, 5% by weight
2,6-dimethylol-p-cresol and a striation inhibitor. Similarly, a control photoresist is formulated by substituting the standard cresol formaldehyde resin.

The PMH8 and control resists were coated onto silicon wafers, treated with adhesion promoters and incubated in a circulating oven for 30 minutes.
Bake at 90°C for minutes and quartz optoline (O
Exposure to broad-spectrum UV light [Oriel (Or<sJ)] through a p to Liyu ) mask. Hot plate top 120
After exposure for 60 seconds at ℃, it was baked to 2 mJ using the same equipment.
/ cm" 7 rad exposure. The test resist was developed for 2 minutes with 0.16N tetramethylammonium hydroxide, and the control resist was developed with 0.22N tetramethylammonium hydroxide at 45N.
Develop for seconds. Test resist is 27.5 each
tnJ/cpn” and a nominal photosensitivity and contrast value of 6.0.

The control resist result was 9.1 mJ/ltn
χ and 2.9.

Example 7: Example 60 PMH8 and control resists were spin coated onto adhesion promoter treated silicon wafers and baked for 30 minutes at 90°C in a circulating oven.
Next, broad-spectrum UV light is applied through a quartz optoline mask.
Sensitive to light (oriel). Development of the PMH3 resist in 0.113 N tetramethylammonium hydroxide solution for 60 seconds shows a calculated sensitivity of 300 m J/crn'' and a contrast of 2.3.

Development of the control resist with 0.30#tetramethylammonium hydroxide shows a sensitivity of 100 mJ/as'' and a contrast of 2.5.

Claims (1)

Claims: (1) (a) Acylation of a 2-substituted phenol under appropriate catalysis to yield a 3-substituted-4-hydroxyacetophenone, and then (b) a 3-substituted-4-hydroxy Esterification of acetophenone to produce 3-substituted-4-acetoxyacetophenone, followed by (c) 3-substituted-4-
Acetoxyacetophenone is hydrogenated to form 1-(3'-substituted-4'-acetoxyphenyl)ethanol and then (d) 1-(3'-substituted-4'-acetoxyphenyl)ethanol is dehydrated to form 3 -substituted-4-acetoxystyrene, each of the above substitutions being C_1~
C_1_0 alkyl, Br, I, Cl, NO_2 or S
A method for producing 3-substituted-4-acetoxystyrene which is O_3H. 2. The method according to claim 1, wherein step (a) is carried out by the Fries rearrangement method. (3) The method according to claim 1, wherein step (1) is carried out by Friedel-Crafts acylation method. 4. The method of claim 1, wherein step (a) is carried out with acetic anhydride and a hydrogen fluoride catalyst. (5) Step (c) is carried out by heating under hydrogen as a positive pressure in the presence of a catalyst, and the pressure of the hydrogen gas is from about 100 to about 2
50 mmHgpsig and the heating is approximately 2
2. The method of claim 1, wherein the method is carried out at a temperature of 5<0>C to about 40<0>C. (6) The method according to claim 5, wherein the catalyst in step (c) is Pd/C. (7) The method according to claim 1, wherein step (d) is carried out in the presence of a dehydrating agent and a polymerization inhibitor. (8) The method according to claim 1, wherein the trisubstitution is methyl. (9) (a) Acylation of 2-substituted phenols under suitable catalysis to yield 3-substituted-4-hydroxyacetophenones, and (b) esterification of 3-substituted-4-hydroxyacetophenones to yield 3-substituted phenones. -substituted-4-acetoxyacetophenone and then (c) 3-substituted-4-
Hydrogenating acetoxyacetophenone to form 1-(3'-substituted-4'-acetoxyphenyl)ethanol and then (d) dehydrating the 1-(3'-substituted-4'-acetoxyphenyl)ethanol. to form 3-substituted-4-acetoxystyrene, each of the above substitutions being C_1~
C_1_0 alkyl, Br, I, Cl, NO_2 or S
O_3H and then (e) about 1,000 to about 80
Poly(3
-substituted-4-acetoxystyrene). (10) The method of claim 9, wherein said free radical polymerization is carried out with azoisobutyronitrile. (11) (a) Acylation of 2-substituted phenol under appropriate catalytic action to produce 3-substituted phenol.
(b) esterification of the 3-substituted-4-hydroxyacetophenone to produce a 3-substituted-4-acetoxyacetophenone, and then (c) 3-substituted-4-acetophenone. Acetophenone is hydrogenated to form 1-(3'monosubstituted-4'-acetoxyphenyl)ethanol and then (d) 1-
(3'-Substituted-4'-acetoxyphenyl)ethanol is dehydrated to form 3-substituted-4-acetoxystyrene, each of the above substitutions being C_1-C_1_0 alkyl, Br, I, Cl, NO_2 or SO_3H. and then (e) free radical polymerization of 3-substituted-4-acetoxystyrene until a molecular weight of about 1,000 to about 800,000 is obtained, and then (f) poly(3-substituted-4-acetoxystyrene). ) A method for producing poly(3-substituted-4-hydroxystyrene). (12) The method according to claim 11, wherein the hydrolyzing agent is a base. (13) The method according to claim 11, wherein the hydrolyzing agent is tetramethyl ammonium hydroxide. (14) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X is C_1 to C_1_0 alkyl, Br, I, C
selected from the group consisting of l, NO_2 and SO_3H;
and Y is 4-acetoxystyrene; styrene acrylate or methacrylate; 3,5-di-X-substituted-4
-acetoxystyrene; maleic anhydride; and N-substituted maleimide, where the N-substitution is selected from the group consisting of aliphatic, alicyclic or heterocyclic groups; and Z is absent; or 4-acetoxystyrene; styrene; acrylate or methacrylate; 3,5-di-X-substituted-4-acetoxystyrene; maleic anhydride; and N
- substituted maleimides, wherein the N-substitution is selected from the group consisting of aliphatic, cycloaliphatic, or heterocyclic groups; 800
copolymers or terpolymers having an average molecular weight in the range of ,000. (15) The copolymer according to claim 14, wherein X is methyl. (16) The copolymer according to claim 14, wherein X is bromine. (17) The copolymer of claim 15, wherein Y is an N-alkyl substituted maleimide and Z is absent. (18) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, X is C_1 to C_1_0 alkyl, Br, I, C
1,000 to about 800,0
having an average molecular weight in the range of 0.00. (19) The copolymer of claim 18 having an average molecular weight ranging from about 5,000 to about 15,000. (20) The copolymer according to claim 18, wherein each X is methyl. (21) The copolymer according to claim 18, wherein each X is bromine. (22) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X is C_1 to C_1_0 alkyl, Br, I, C
1, NO_2 and SO_3H; and Y is 4-acetoxystyrene; styrene; acrylate or methacrylate; 3,5-di-X-substituted-4-acetoxystyrene; maleic anhydride; and N-substituted maleimide. (said N-substitution is selected from the group consisting of aliphatic, alicyclic or heterocyclic groups); and Z is absent or 4-acetoxystyrene; styrene;
acrylate or methacrylate; 3,5-di-X-substituted-4-acetoxystyrene; maleic anhydride; selected from the group consisting of; and Z is selected from the group consisting of:
- substituted maleimides, wherein the N-substitution is selected from the group consisting of aliphatic, cycloaliphatic, or heterocyclic groups; 800
and an o-quinonediazide photosensitizer; and a suitable solvent; the composition is coated onto a substrate. and the copolymer or terpolymer is present in an amount sufficient to act as a binder for the composition and the diazide is present in an amount sufficient to produce image distinction when imagewise exposed to actinic radiation. and the solvent is present in an amount sufficient to form a homogeneous solution of the components of the composition. (23) The copolymer or terpolymer has a molecular weight of about 5,000 to
23. The composition of claim 22 having a molecular weight of about 15,000. (24) The composition according to claim 22, wherein the photosensitizer is a condensation product of a naphthoquinone-(1,2)-diazide-(2)-4 or 5-sulfonyl compound and hydroxybenzophenone. (25) The composition according to claim 22, wherein the solvent is propylene glycol monomethyl ether and/or propylene glycol monomethyl ether acetate. 26. The composition of claim 22, wherein the weight ratio of said polymer to said photosensitizer ranges from about 1:1 to about 20:1. (27) The method according to claim 22, further comprising one or more additives selected from the group consisting of colorants, dyes, anti-striation agents, plasticizers, adhesion promoters, sensitivity enhancers, solvents, and surfactants. Composition. (28) The composition according to claim 22, further comprising a crosslinking agent. (29) The composition according to claim 28, wherein the crosslinking agent is dimethylol para-cresol. (30) A photographic element comprising the dry composition of claim 22 coated onto a support. (31) A photographic element comprising the dry composition of claim 28 coated onto a support. 32. The photographic element of claim 30, wherein said support comprises one or more materials selected from the group consisting of semiconductor materials, metals, plastic films, wood, paper, ceramics, and textiles. (33) 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. 31. The photographic element of claim 30, comprising more than one material. (34) coating the photographic composition of claim 22 on a support and drying the composition until it is substantially tack-free; A method of forming photographic images comprising imagewise exposing a composition to radiation with X-rays and removing non-image portions of the composition with a developer. (35) The method according to claim 34, wherein the developer contains an alkaline aqueous solution. (36) The method according to claim 34, wherein the developer does not contain metal ions. (37) coating the photographic composition of claim 28 on a support, drying the composition until it is substantially tack-free, and applying sufficient actinic radiation, electron beam, or imagewise exposing the composition to radiation, heating the composition to a temperature of about 95° to about 160°C to cross-bond the polymers, and removing the non-image portions of the composition with a developer. A method of forming different photographic images. (38) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, X is C_1 to C_1_0 alkyl, Br, I, C
an o-quinonediazide photosensitizer; and an o-quinonediazide photosensitizer; A photosensitive composition comprising a suitable solvent in an amount sufficient for the copolymer to act as a binder for the composition when the composition is coated on a substrate and imagewise exposed to actinic radiation. and the diazide is present in an amount sufficient to provide image differentiation; and the solvent is present in an amount sufficient to form a homogeneous solution of the composition components. 39. The composition of claim 38, wherein said copolymer has a molecular weight of about 5,000 to about 15,000. (40) The composition according to claim 38, wherein the photosensitizer is a condensation product of a naphthoquinone-(1,2)-diazide-(2)-4 or 5-sulfonyl compound and hydroxybenzophenone. (41) The composition according to claim 38, wherein the solvent is propylene glycol monomethyl ether and/or propylene glycol monomethyl ether acetate. 42. The composition of claim 38, wherein the weight ratio of said polymer to said photosensitizer ranges from about 1:1 to about 20:1. (43) The composition according to claim 38, further comprising one or more additives selected from the group consisting of colorants, dyes, anti-striation agents, plasticizers, adhesion promoters, sensitivity enhancers, solvents, and surfactants. thing. (44) The composition according to claim 38, further comprising a crosslinking agent. (45) The composition according to claim 44, wherein the crosslinking agent is dimethylol para-cresol. (46) A photographic element comprising the dry composition of claim 38 coated onto a support. (47) A photographic element comprising the dry composition of claim 44 coated onto a support. (48) The photographic element of claim 46, wherein said support is comprised of one or more materials selected from the group consisting of semiconductor materials, metals, plastic films, wood, paper, ceramics, and textiles. (49) The support is one 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. 47. A photographic element according to claim 46, comprising a material as defined above. (50) coating the photographic composition of claim 38 on a support, drying the composition until it is substantially tack-free, and applying sufficient actinic radiation, electron beam or - A method of forming a photographic image comprising imagewise exposing a composition to radiation and removing the non-image parts of the composition with a developer. (51) The method according to claim 50, wherein the developer contains an alkaline aqueous solution. (52) The method according to claim 50, wherein the developer does not contain metal ions. (53) coating the photographic composition of claim 44 on a support, drying the composition until it is substantially tack-free, and applying sufficient actinic radiation, electron beam, or - imagewise exposing the composition to radiation, heating the composition to a temperature of about 95° to about 160°C to cross-bond the polymers, and removing the non-image parts of the composition with a developer; A method of forming different photographic images.