CA1044398A - Light-sensitive compounds and photoresists containing the same - Google Patents
Light-sensitive compounds and photoresists containing the sameInfo
- Publication number
- CA1044398A CA1044398A CA219,615A CA219615A CA1044398A CA 1044398 A CA1044398 A CA 1044398A CA 219615 A CA219615 A CA 219615A CA 1044398 A CA1044398 A CA 1044398A
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- CA
- Canada
- Prior art keywords
- light
- sensitive
- acid
- mixture
- nitrobenzoic acid
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C247/00—Compounds containing azido groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
ABSTRACT
This invention relates to low molecular weight light-sensitive polymeric substances and their preparation in which, in the presence of a common solvent, a mixture of p-azidobenzoic acid or an esterifiable deriva-tive thereof and a p-nitrobenzoic acid which may be substituted in the ortho- and/or meta-positions with an alkyl group containing from 1 to 4 carbon atoms, or an esterifiable derivative thereof are reacted with an epoxide resin. The products obtained have improved properties such as radiation sensitivity, light resolution and edge definition.
This invention relates to low molecular weight light-sensitive polymeric substances and their preparation in which, in the presence of a common solvent, a mixture of p-azidobenzoic acid or an esterifiable deriva-tive thereof and a p-nitrobenzoic acid which may be substituted in the ortho- and/or meta-positions with an alkyl group containing from 1 to 4 carbon atoms, or an esterifiable derivative thereof are reacted with an epoxide resin. The products obtained have improved properties such as radiation sensitivity, light resolution and edge definition.
Description
~:']~1 B ~3 r,> ~1 0 ~EEN/l.~`VD
8 . 1 . 1 975 4~98 "Novel Light-sensitive Compounds and Photoresists -containing the same".
This invention relates to light-sensitive p~lymeric compounds and is concerned ~ith an improvement : :
to the invention of our United Kingdom Specificati.on No. 1,.330,263.
The said specification describes and claims a method of preparing low molecular weight light~
sensitive polymeric compounds, which method comprises -, reac~ing, in the presence of a common solvent, p-azidobenzoic ~:.
acid or an esterifiable derivative thereof with an ;~:
, .. .
epoxide resin as represented by the general. formula I:
./ O~ ~ ~ OE
CH2 CH - CH2- -O -. R - O - CH2 - CH - CH2- O - R - O
, ~ ., 0~ ~ ~
. ~ : CH2 CH~- CH2 tI]
~, . . .
in whioh ~ormula R represents hydroxypropylene or the ;
hydrocarbon nucleus of a dihydric phenol which lS free~
from functional groups other than phenolic hydroxy groups, : such as ~ -dihydroxydiphenyl~ ~p~-dihydroxy- .:
. . diphenyl methane, p,p~-dihydroxydlphenylmethylmethane, : p~-dihydroxydibenzyl, and p,~-dihydroxydiphenyl~
dimethyl methane; or a 1,2-propylene oxide derivative : .
~thereof; and n is 0, 1, 2 or 3. ~
!;~ ' : ` . ' . ' 3 3,~
8. 1 . 1975 - The present invention is particularly concerned with a new class of light-sensitive polymeric compounds which are derivatives of a reaction product obtained by reacting a mixture of p-azidobenzoic acid or an ~-esterifiable derivative thereof and a possib].y substituted ~-nitrobenzoic acid or an esterifiable derivative thereof with the aforementioned epoxide resin.
From said U.K. Specification No. 1,330,263 light-sensitive polymers are known which can be represented by the general formula:
, ` ''~
O OH OH
N3 ~ C-O-CH2-CH-CH~ -O-R'-O-CH2-lH-CH2 ~ ~~ 2 ~
- . n ~ .
- ' ' .: . ~ : '.
-CH-CH -O-C ~ N
¦ 2 11 ~ 3 II
OH
' or 1,2-propylene oxide or p-azidobenzoxy derivatives there~o~, in which formula R' represents hydroxypropylen~, or the hydrocarbon nucleus of a dihydric phenol which is free from functional groups other than phenolic hydroxy groups, and n is:0, 1,~2 or 3.
We have discov,ered that some of the p-azidobenzoxy groups present ln thë mixturë of polymers represent~d by ~ormula ~1 II may be replQced by ~-nitrobenzoxy groups and that, ~UD~ xpectedly, the propertiès, especlally~the light resolution and edge definition, of these polymeric coinpounds ,~.. . : : , -, l'HB 321~C)8 8.1.1975 ~ 4398 :: -are grreatly improved. The p-nitrobenzoxy-substituted polymers are also sensitive to relatively narrow ranges of wave-lengths of light, particularly in the short-wave or ultra-violet range. Thus, the polymeric compounds of the present invention have greatly , redhced defects due to aberration on exposure to light through masks with very fine apertures. Further- -more, the compounds of the invention have the . advantage that they can be processed under normal lighting conditions without, for example, use of special lights such as yellow lamps. ~ `
According to the present invention there - is provided a method of preparing low molecular weight light-sensitive polymeric compounds comprising reacting,~
in the presence of a common solvent, a mixture of p-azidobenzoic acid or an esterifiable derivative thereof and a p-nitrobenzoic acid ~hich may be substituted :
in the ortho- and/or meta-positions wlth an alky~
group containing from 1 to 4 carbon~atoms, or an esterifiable derivative thereof~ wlth an epoxide resin as represented by the general formula:
CM2 - CH - CE ~ 0 - R - 0 - CM2 - ~M - GH2 ~ - R
/\ - ' ` .i -0 - C~I2 - CH - CH2 in which formula R represents hydroxypropylene or the hydrocàrbon nuoleus of a dihydric phenol which is free - from functional groups o*her than phenollc hydroxy groups, .. ~ :
PHB 3~l08 8.1.1975 1~)44398 such as ~,p~:ihydroxydiphenyl, p,pl-dihydroxy-diphenyl methane, p,~'-dihydroxydiphenylmethylmethane, p,p~-dihydrox~dibenzyl, and p,p'-dihydroxydiphenyldimeth~Tl methane; or a 1,2-propylene oxide derivative thereor;
and n is 0, 1, 2 or 3.
An example of an epoxide resin according to the above formula whereby R represents a 1,2-propylene oxide derivative of the nucleus of a dihydric phenol and n = O, is represented by the formula CH2 - CH-CHz-O- ~
~ CH2 H
CH 2 - CH--CH 2- 0~ 0--CH2 -cH - CH2 :
- The molecular weight of such a epoxidised novol~k resin monomer is 645.
. When R has the above given meaning and n - 1 the molecular weight is 1063. At n = 2 the molecular weight amounts 1481.
Upon reaction of the epoxidised novolak resin represented above wlth a mixture Or p-azidobenzoic acid and p-nitrobenzoic acid the following compound will result:
O OH CH2-l OH O
ZO X-~-(~-O-CH2-CH-oH2-o-~ ~-o-CHz-CH-CH2-o-c-~3-x CH H
O OH ~2 ~ 2 OH O
X- ~ ~C-O-CH2-CH-CH2-0- ~ ~ -0-CH2-CH-CH2-0-C ~ ~ X
' :~ wherein X stands for a N3- or N02 group.
~. . : ' "
_, _ P11~3 3,~
8. 1. 19'75 1~4398 . .
The p-nitrobenzoic acid compounds or esterif`iable ~1erivatives thereof may be sub~tituted in the ortho- and/or meta-positions with one or more alkyl groups containing from 1 to 4 carbon atoms, ~or example, o-methyl p-nitrobenzoic acid, o-ethyl ~-nitro-benzoic acid, o-propyl ~-nitrobenzoic acid, o butyl p-nitrobenzoic acid, m-methyl p-nitrobenzoic acid, m-ethyl p-nitrobenzoic acid, m-propyl ~-nitrobenzoic -acid, m-butyl p-nitrobenzoic acid, o,~'-dimethyl p-nitroben~oic acid, o,o'-diethyl p-nitrobenzoic acid, o,o!_dipropyl p-nitrobenzoic acid, o,o'-dibutyl p-nitrobenzoic acid, m,m'-dimethyl p-nitrobenzoic acid, m,m'-diethyl p-nitrobenzoic acid, m,m'-dipropyl p-nitrobenzoic acid, m,m'-dibutyl P-nitrobenzoic acid, o~o',m,m'-tetramethyl ~-nitrobenzoic acid, o,o',m,m'-tetra-- -:
ethyl p-nitrobenzoic acid, o,o'-diethyl-m,m'-dimethyl ~-nitrobenzoic acid, o,o',m-trimethyl ~-nitrobenzoic acid, `
o,m,m'-triethyl p-nitrobenzoic acid.
Preferably, the mixture comprising P-azid~benzoic acid or an esterifiable derivative thereof and p-nitrobenzoic acid, if desired substituted in the ortho- and/or meta-positions with an alkyl group containing ! "
~rom 1 to 4 carbon atoms or an esterifiable derivative thereof~contains up to 75~ by weight ~-nitrobenzoic acid.
In an alternative embodiment the mixture contains ~-azidobenzoic acid and p-nitrobenzoic acid in the proportions of between 3 : 1 parts by weight to 1 : 2 parts by weight.
The epoxide resin may contain two reactive terminal epoxide groups and also may ha~e a molecular ...
... . -. :
Pll~ ~21Jo8 8.1.1975 ~044398 weight of between 340 - 1500, especially between 340 - 750. Wllen the epoxide resin is a novolak resin the molecular weight range is pre~erably between 600 - 1500.
Suitable ep,oxide resins may be prepared by reacting 2 to 4 moles of epichlorohydrin with one mole of bisphenol A under an'inert atrnosphere with the gradual addition of 2 moles of sodium hydroxide. The epoxide product may then be separated and reacted in the presence of a common solvent such as toluene with a mixture containing ~-azidobenzoic acid or an es~terifiable derivative thereof and ~-nitrobenzoic ac'id, if desired substituted in the ortho- and/or meta-positions with an alkyl group containing not more than 4 carbon atoms, or an esterifiable derivative thereof at a temperature of less than 200C and preferably between 130 - 150C.
A suitable novolak resin may be prepared by reacting one mole of phenol with o.8 moles~of .~ormaldehyde in the presence of an acid catalys* at ~' 100C, separating the product by removing the water produced when the desired degree of polymerisation ' is reached. The novolak resin may then be reacted wlth epichlorohydrin to form terminal reactive epoxide groups on the novolak resin nucleus. The reaction product '-' i9 separated and it is reacted in the presence of ~ , a common solvent such as toluene with a mixture o~
~-azidobenzo~c acid or an esterifiable derivative thereof and ~-nitrobenz'oic acid, if desired substituted ~ .
-7- ' 1?111~ ~ _108 8 . 1 . 1 97 5 ~44398 :
in the ortho- and/or meta-positions with an alkyl group contai~ing not more than 4 carbon atoms or an esterifiable derivative thereof, in the mole ratio of one mole of the resin to 3 to 4 moles of the mixture. :~
Preferably, the mixture contains 1 mole of p-azidobenzoic acid and from 2 to 3 moles of ~-nitrobenzoi.c acid, and the common solvent is an organic solvent such as 1,4-dioxane or toluene.
According to a further aspect of the present invention there is provided light-sensitive polymers as represented by the general formula:
X- ~ ~-0-CHz-CH-CH2~ o-R'-o-CH2-CH-CH73 0-R 0 CH2 . n ~, f 2 11 ~ -X . III
OH
a 1?2-propylene oxide, a p-azidobenzoxy or a ~-nitrobenzoxy :
derivative thereof, in which formula R' represents hydroxy-propylene or the hydrocarbon nucleus of a dihydric phenol -which is free from functional groups other than phenolic hydroxy groups, X represents a N3 or a N02 group, with the proviso that! a mixture of the polymers at least contain lone molecùle in which one X is a N3 group, and at least one :
molecule in which one X is a N02 group, and n is 0, 1, 2 or 3.
Light-sensitive polymeric compounds according to the invention preferably do not contain, on an averag~e, more than 75% N02 groups. Thus~ the distribution of the N02 groups -among the mo]ecules in a mixture of differing molecular ', :'' '.
~, 8 8.1.1975 1~44398 weights may range fro~ specific molecules wllich have ~ -three azido groups replaced by nitro groups, to specific moleculcs whicll have two, one or even no azido groups replaced by nitro groups. However, the majority of the molecules in a 66.6~ substitution have two a~ido groups replaced by nitro groups. Altsrnatively, the majority of the molecules may have only one azido group replaced by a nitro group in a 33.3~ substitution. If desired a homo~enous fraction of any one molecular species may be made by molecular separation techniques.
The light-sensitive polymeric cornpounds may have at least one terminal or cross-linked nitrilo radical per molecule. Particularly suitable polymeric compounds are represented by Formula III, in which formula R~ is the hydrocarbon nucleus of p,p~ -dihydroxy-diphenyldimethylmethane, where n is 0, 1, 2 or 3 and preferably n is 0.
Epoxide resins of th- type represented by Formula I may be prepared by reacting acetone and 2 mole equivalents of phenol to give bisphenol A, followed by reacting with epichlorohydrin in the manner described in specificatiorl No. 1,330,263. Alternatively, the epoxide resins prepared from glycerol, bisphenol F
or a long-chain bisphenol derived from cashew-nut oil may be used, followed by epoxidation with epichlorohydrin.
Similarly, the epoxide resins may be prepared from novolak reslns in the manner de~cribed in ~pecification No. 1,330,263.
The epoxide resin monomer may be dissolved separately in a solvent which is also a solvent common to both p-azidobenzoic acid or an esterifiable derivati~e ,.
~-- PT13 ~408 8.1.1975 lr~44398 thereof and p-nitrobenzoic acid or an esterifiable derivative thcreof. Preferably, a solution of the mixture of ~-azidobenzoic acid and p-nitrobenzoic acid is prepared and this solution is added to a solution ~
the epoxide resin and the reaction between the reagents is effected by refluxing the mixture for up~; to 8 hours. -The polymers produced according to the present invention ha~e a relatively low molecular weight which is controlled by the molar proportions of the reagents used and the degree to which the reaction is allowed to proceed, ~hese low molecular weight polymers may be dissolved in organic solvents to form solutions.
Preferablyf the solvents used for forming solutions of the polymers are ketones, such as cyclohexanone, acetone, ~ -methyl-ethyl ketone, 1,4-dioxane; esters, such as ethyl acetate, propyl acetate, butyl acetate, methyl glycoacetate; and mixtures of these and other solvents.
If desired, the solvents may be diluted with hydrocarbons, ;
suoh as xylene and/or dipolar aprotic solvents such as dimethyl formamide, dimethyl acetamide and N-methyl pyrrolidone.
In general, the solubility of the polymers in an organic solvent decreases with increasing molecular .
8 . 1 . 1 975 4~98 "Novel Light-sensitive Compounds and Photoresists -containing the same".
This invention relates to light-sensitive p~lymeric compounds and is concerned ~ith an improvement : :
to the invention of our United Kingdom Specificati.on No. 1,.330,263.
The said specification describes and claims a method of preparing low molecular weight light~
sensitive polymeric compounds, which method comprises -, reac~ing, in the presence of a common solvent, p-azidobenzoic ~:.
acid or an esterifiable derivative thereof with an ;~:
, .. .
epoxide resin as represented by the general. formula I:
./ O~ ~ ~ OE
CH2 CH - CH2- -O -. R - O - CH2 - CH - CH2- O - R - O
, ~ ., 0~ ~ ~
. ~ : CH2 CH~- CH2 tI]
~, . . .
in whioh ~ormula R represents hydroxypropylene or the ;
hydrocarbon nucleus of a dihydric phenol which lS free~
from functional groups other than phenolic hydroxy groups, : such as ~ -dihydroxydiphenyl~ ~p~-dihydroxy- .:
. . diphenyl methane, p,p~-dihydroxydlphenylmethylmethane, : p~-dihydroxydibenzyl, and p,~-dihydroxydiphenyl~
dimethyl methane; or a 1,2-propylene oxide derivative : .
~thereof; and n is 0, 1, 2 or 3. ~
!;~ ' : ` . ' . ' 3 3,~
8. 1 . 1975 - The present invention is particularly concerned with a new class of light-sensitive polymeric compounds which are derivatives of a reaction product obtained by reacting a mixture of p-azidobenzoic acid or an ~-esterifiable derivative thereof and a possib].y substituted ~-nitrobenzoic acid or an esterifiable derivative thereof with the aforementioned epoxide resin.
From said U.K. Specification No. 1,330,263 light-sensitive polymers are known which can be represented by the general formula:
, ` ''~
O OH OH
N3 ~ C-O-CH2-CH-CH~ -O-R'-O-CH2-lH-CH2 ~ ~~ 2 ~
- . n ~ .
- ' ' .: . ~ : '.
-CH-CH -O-C ~ N
¦ 2 11 ~ 3 II
OH
' or 1,2-propylene oxide or p-azidobenzoxy derivatives there~o~, in which formula R' represents hydroxypropylen~, or the hydrocarbon nucleus of a dihydric phenol which is free from functional groups other than phenolic hydroxy groups, and n is:0, 1,~2 or 3.
We have discov,ered that some of the p-azidobenzoxy groups present ln thë mixturë of polymers represent~d by ~ormula ~1 II may be replQced by ~-nitrobenzoxy groups and that, ~UD~ xpectedly, the propertiès, especlally~the light resolution and edge definition, of these polymeric coinpounds ,~.. . : : , -, l'HB 321~C)8 8.1.1975 ~ 4398 :: -are grreatly improved. The p-nitrobenzoxy-substituted polymers are also sensitive to relatively narrow ranges of wave-lengths of light, particularly in the short-wave or ultra-violet range. Thus, the polymeric compounds of the present invention have greatly , redhced defects due to aberration on exposure to light through masks with very fine apertures. Further- -more, the compounds of the invention have the . advantage that they can be processed under normal lighting conditions without, for example, use of special lights such as yellow lamps. ~ `
According to the present invention there - is provided a method of preparing low molecular weight light-sensitive polymeric compounds comprising reacting,~
in the presence of a common solvent, a mixture of p-azidobenzoic acid or an esterifiable derivative thereof and a p-nitrobenzoic acid ~hich may be substituted :
in the ortho- and/or meta-positions wlth an alky~
group containing from 1 to 4 carbon~atoms, or an esterifiable derivative thereof~ wlth an epoxide resin as represented by the general formula:
CM2 - CH - CE ~ 0 - R - 0 - CM2 - ~M - GH2 ~ - R
/\ - ' ` .i -0 - C~I2 - CH - CH2 in which formula R represents hydroxypropylene or the hydrocàrbon nuoleus of a dihydric phenol which is free - from functional groups o*her than phenollc hydroxy groups, .. ~ :
PHB 3~l08 8.1.1975 1~)44398 such as ~,p~:ihydroxydiphenyl, p,pl-dihydroxy-diphenyl methane, p,~'-dihydroxydiphenylmethylmethane, p,p~-dihydrox~dibenzyl, and p,p'-dihydroxydiphenyldimeth~Tl methane; or a 1,2-propylene oxide derivative thereor;
and n is 0, 1, 2 or 3.
An example of an epoxide resin according to the above formula whereby R represents a 1,2-propylene oxide derivative of the nucleus of a dihydric phenol and n = O, is represented by the formula CH2 - CH-CHz-O- ~
~ CH2 H
CH 2 - CH--CH 2- 0~ 0--CH2 -cH - CH2 :
- The molecular weight of such a epoxidised novol~k resin monomer is 645.
. When R has the above given meaning and n - 1 the molecular weight is 1063. At n = 2 the molecular weight amounts 1481.
Upon reaction of the epoxidised novolak resin represented above wlth a mixture Or p-azidobenzoic acid and p-nitrobenzoic acid the following compound will result:
O OH CH2-l OH O
ZO X-~-(~-O-CH2-CH-oH2-o-~ ~-o-CHz-CH-CH2-o-c-~3-x CH H
O OH ~2 ~ 2 OH O
X- ~ ~C-O-CH2-CH-CH2-0- ~ ~ -0-CH2-CH-CH2-0-C ~ ~ X
' :~ wherein X stands for a N3- or N02 group.
~. . : ' "
_, _ P11~3 3,~
8. 1. 19'75 1~4398 . .
The p-nitrobenzoic acid compounds or esterif`iable ~1erivatives thereof may be sub~tituted in the ortho- and/or meta-positions with one or more alkyl groups containing from 1 to 4 carbon atoms, ~or example, o-methyl p-nitrobenzoic acid, o-ethyl ~-nitro-benzoic acid, o-propyl ~-nitrobenzoic acid, o butyl p-nitrobenzoic acid, m-methyl p-nitrobenzoic acid, m-ethyl p-nitrobenzoic acid, m-propyl ~-nitrobenzoic -acid, m-butyl p-nitrobenzoic acid, o,~'-dimethyl p-nitroben~oic acid, o,o'-diethyl p-nitrobenzoic acid, o,o!_dipropyl p-nitrobenzoic acid, o,o'-dibutyl p-nitrobenzoic acid, m,m'-dimethyl p-nitrobenzoic acid, m,m'-diethyl p-nitrobenzoic acid, m,m'-dipropyl p-nitrobenzoic acid, m,m'-dibutyl P-nitrobenzoic acid, o~o',m,m'-tetramethyl ~-nitrobenzoic acid, o,o',m,m'-tetra-- -:
ethyl p-nitrobenzoic acid, o,o'-diethyl-m,m'-dimethyl ~-nitrobenzoic acid, o,o',m-trimethyl ~-nitrobenzoic acid, `
o,m,m'-triethyl p-nitrobenzoic acid.
Preferably, the mixture comprising P-azid~benzoic acid or an esterifiable derivative thereof and p-nitrobenzoic acid, if desired substituted in the ortho- and/or meta-positions with an alkyl group containing ! "
~rom 1 to 4 carbon atoms or an esterifiable derivative thereof~contains up to 75~ by weight ~-nitrobenzoic acid.
In an alternative embodiment the mixture contains ~-azidobenzoic acid and p-nitrobenzoic acid in the proportions of between 3 : 1 parts by weight to 1 : 2 parts by weight.
The epoxide resin may contain two reactive terminal epoxide groups and also may ha~e a molecular ...
... . -. :
Pll~ ~21Jo8 8.1.1975 ~044398 weight of between 340 - 1500, especially between 340 - 750. Wllen the epoxide resin is a novolak resin the molecular weight range is pre~erably between 600 - 1500.
Suitable ep,oxide resins may be prepared by reacting 2 to 4 moles of epichlorohydrin with one mole of bisphenol A under an'inert atrnosphere with the gradual addition of 2 moles of sodium hydroxide. The epoxide product may then be separated and reacted in the presence of a common solvent such as toluene with a mixture containing ~-azidobenzoic acid or an es~terifiable derivative thereof and ~-nitrobenzoic ac'id, if desired substituted in the ortho- and/or meta-positions with an alkyl group containing not more than 4 carbon atoms, or an esterifiable derivative thereof at a temperature of less than 200C and preferably between 130 - 150C.
A suitable novolak resin may be prepared by reacting one mole of phenol with o.8 moles~of .~ormaldehyde in the presence of an acid catalys* at ~' 100C, separating the product by removing the water produced when the desired degree of polymerisation ' is reached. The novolak resin may then be reacted wlth epichlorohydrin to form terminal reactive epoxide groups on the novolak resin nucleus. The reaction product '-' i9 separated and it is reacted in the presence of ~ , a common solvent such as toluene with a mixture o~
~-azidobenzo~c acid or an esterifiable derivative thereof and ~-nitrobenz'oic acid, if desired substituted ~ .
-7- ' 1?111~ ~ _108 8 . 1 . 1 97 5 ~44398 :
in the ortho- and/or meta-positions with an alkyl group contai~ing not more than 4 carbon atoms or an esterifiable derivative thereof, in the mole ratio of one mole of the resin to 3 to 4 moles of the mixture. :~
Preferably, the mixture contains 1 mole of p-azidobenzoic acid and from 2 to 3 moles of ~-nitrobenzoi.c acid, and the common solvent is an organic solvent such as 1,4-dioxane or toluene.
According to a further aspect of the present invention there is provided light-sensitive polymers as represented by the general formula:
X- ~ ~-0-CHz-CH-CH2~ o-R'-o-CH2-CH-CH73 0-R 0 CH2 . n ~, f 2 11 ~ -X . III
OH
a 1?2-propylene oxide, a p-azidobenzoxy or a ~-nitrobenzoxy :
derivative thereof, in which formula R' represents hydroxy-propylene or the hydrocarbon nucleus of a dihydric phenol -which is free from functional groups other than phenolic hydroxy groups, X represents a N3 or a N02 group, with the proviso that! a mixture of the polymers at least contain lone molecùle in which one X is a N3 group, and at least one :
molecule in which one X is a N02 group, and n is 0, 1, 2 or 3.
Light-sensitive polymeric compounds according to the invention preferably do not contain, on an averag~e, more than 75% N02 groups. Thus~ the distribution of the N02 groups -among the mo]ecules in a mixture of differing molecular ', :'' '.
~, 8 8.1.1975 1~44398 weights may range fro~ specific molecules wllich have ~ -three azido groups replaced by nitro groups, to specific moleculcs whicll have two, one or even no azido groups replaced by nitro groups. However, the majority of the molecules in a 66.6~ substitution have two a~ido groups replaced by nitro groups. Altsrnatively, the majority of the molecules may have only one azido group replaced by a nitro group in a 33.3~ substitution. If desired a homo~enous fraction of any one molecular species may be made by molecular separation techniques.
The light-sensitive polymeric cornpounds may have at least one terminal or cross-linked nitrilo radical per molecule. Particularly suitable polymeric compounds are represented by Formula III, in which formula R~ is the hydrocarbon nucleus of p,p~ -dihydroxy-diphenyldimethylmethane, where n is 0, 1, 2 or 3 and preferably n is 0.
Epoxide resins of th- type represented by Formula I may be prepared by reacting acetone and 2 mole equivalents of phenol to give bisphenol A, followed by reacting with epichlorohydrin in the manner described in specificatiorl No. 1,330,263. Alternatively, the epoxide resins prepared from glycerol, bisphenol F
or a long-chain bisphenol derived from cashew-nut oil may be used, followed by epoxidation with epichlorohydrin.
Similarly, the epoxide resins may be prepared from novolak reslns in the manner de~cribed in ~pecification No. 1,330,263.
The epoxide resin monomer may be dissolved separately in a solvent which is also a solvent common to both p-azidobenzoic acid or an esterifiable derivati~e ,.
~-- PT13 ~408 8.1.1975 lr~44398 thereof and p-nitrobenzoic acid or an esterifiable derivative thcreof. Preferably, a solution of the mixture of ~-azidobenzoic acid and p-nitrobenzoic acid is prepared and this solution is added to a solution ~
the epoxide resin and the reaction between the reagents is effected by refluxing the mixture for up~; to 8 hours. -The polymers produced according to the present invention ha~e a relatively low molecular weight which is controlled by the molar proportions of the reagents used and the degree to which the reaction is allowed to proceed, ~hese low molecular weight polymers may be dissolved in organic solvents to form solutions.
Preferablyf the solvents used for forming solutions of the polymers are ketones, such as cyclohexanone, acetone, ~ -methyl-ethyl ketone, 1,4-dioxane; esters, such as ethyl acetate, propyl acetate, butyl acetate, methyl glycoacetate; and mixtures of these and other solvents.
If desired, the solvents may be diluted with hydrocarbons, ;
suoh as xylene and/or dipolar aprotic solvents such as dimethyl formamide, dimethyl acetamide and N-methyl pyrrolidone.
In general, the solubility of the polymers in an organic solvent decreases with increasing molecular .
2~ weights. As the molecular weight of the -N3 group and the -N02 group are simllar, i.e. in the ratio of 42 : 46, nnd each group represent~ only a small proportion of the total molecular weight of the polymer, substitution Or -N3 groups by -N02 groups does not materially change the solubilities of the respective polymers.
:
l~rll3 3? '~
8.1.1975 ~044398' Light-sensitive compounds may be incorporated in-to compo9itions of the polymer:ic compound~ according to tlle invention. The light-sensitive compounds may be incorporated into the polymeric composition either during the prepara-tion of the polymer or a composition thereof, or subsequently, for example, when applyi~g a polymeric composition to the surface of a substrate.
One particularly suitable light-sensitive compound is 5-nitroacenaphthene. Other suitable light-sensitive compounds are Michler's ketone;~,p-tetraethyldiaminodiphenylketone; p,p-tetramethyl-diaminodiphenylketone; p,p-dimethylaminobenzophenone;
1,2-benzanthraquinone; ~-chloroanthraquinone; 9,10-anthra-quinone; 4-nitro-2-chloro aniline; 2,6-dichloro-4-nitro analine; 2,4,6-trinitro aniline; 5-nitro-2-amino toluene;
and P-nitrodiphenyl.
By way of illustration, certain preferred processes embodying the invention will now be described in more detail in the ensuing speoi~ic Examples:
EXAMPLE I
20.~ grams of epoxide-novolak resin, available as Bakelite resin ERR 0100 with a moleoular weight range ~ :
between 1000 and 2000, were placed in a 500 ml flask with -200 ml o~ dioxane and stood overnight to dissolve the resin. The following day, 5.6 g p-nitrobenzoic acid, 10.8 g p-a~ldobenzoic acid and 2 ml benzyl trimethyl ammonium hydroxide were added. The solution was then - refluxed (in a glyceiine bath at approximately 140C) ~or 7 hours; allowed to cool to room temperature; and . .
-~ . : . .
Tl3 ~,21l~)8 8.1.1975 1044398 :
..
poured into 6~o ml of methanol in a one-litre beaker, A brown resin precipitated and, after standing 2 hours to settle the precipitate, the l-iquid was decan-ted, leaving the resin at the bottom of the beaker. The resin weighed 28 grams and was dissolved in 70 ml of cyclohexanone.
EX~MPLE II
2.5 g of a sensitiserj 5-nitroacenaphthene, were dissolved in the cyclohexanone mixture obtained from Example I.
EXAMPLE III -The solution obtained from Examples I and II
were then applied to the silicon d~oxide oxidised surfaces of silicon slices by spinning at~600 r.p.m.
and the coated slices were heated at 70C for 20 minutes on a hot plate. Each coated slice was then exposed -through a photomask to ultra-violet light (intensity 5 milliwatts per sq.cm.) for various times, and developed for 2-3 minutes in cyclohexanone, followed by a 15-second rinse in methanol. The optimum exposure time-was found to be 10 seconds. In a comparative test, the optimum exposure time ~or a polymeric layer of equal thicknes~ of resist produced from p-azidobenzoic acid and epoxide-novolak resin without ~-nitro groups and sensitised by Michler's ketone was found to be 90 second~., showing that the addition of nitro-benzoic aoid to the reactlon mixture giv~s a llght-sensitive polymeric product nine times more sensitive. The addition of 5-nitroacenaphthene to the solution of the polymeric ': ' ~'' .
1~J
c3.1.1975 ~4439~
procluct obtained from p-azldobenzoic acid ancl epoxide-novolak resin did not give an optirl~um exposure time of less than 90 seconds.
. .
~ 13-
:
l~rll3 3? '~
8.1.1975 ~044398' Light-sensitive compounds may be incorporated in-to compo9itions of the polymer:ic compound~ according to tlle invention. The light-sensitive compounds may be incorporated into the polymeric composition either during the prepara-tion of the polymer or a composition thereof, or subsequently, for example, when applyi~g a polymeric composition to the surface of a substrate.
One particularly suitable light-sensitive compound is 5-nitroacenaphthene. Other suitable light-sensitive compounds are Michler's ketone;~,p-tetraethyldiaminodiphenylketone; p,p-tetramethyl-diaminodiphenylketone; p,p-dimethylaminobenzophenone;
1,2-benzanthraquinone; ~-chloroanthraquinone; 9,10-anthra-quinone; 4-nitro-2-chloro aniline; 2,6-dichloro-4-nitro analine; 2,4,6-trinitro aniline; 5-nitro-2-amino toluene;
and P-nitrodiphenyl.
By way of illustration, certain preferred processes embodying the invention will now be described in more detail in the ensuing speoi~ic Examples:
EXAMPLE I
20.~ grams of epoxide-novolak resin, available as Bakelite resin ERR 0100 with a moleoular weight range ~ :
between 1000 and 2000, were placed in a 500 ml flask with -200 ml o~ dioxane and stood overnight to dissolve the resin. The following day, 5.6 g p-nitrobenzoic acid, 10.8 g p-a~ldobenzoic acid and 2 ml benzyl trimethyl ammonium hydroxide were added. The solution was then - refluxed (in a glyceiine bath at approximately 140C) ~or 7 hours; allowed to cool to room temperature; and . .
-~ . : . .
Tl3 ~,21l~)8 8.1.1975 1044398 :
..
poured into 6~o ml of methanol in a one-litre beaker, A brown resin precipitated and, after standing 2 hours to settle the precipitate, the l-iquid was decan-ted, leaving the resin at the bottom of the beaker. The resin weighed 28 grams and was dissolved in 70 ml of cyclohexanone.
EX~MPLE II
2.5 g of a sensitiserj 5-nitroacenaphthene, were dissolved in the cyclohexanone mixture obtained from Example I.
EXAMPLE III -The solution obtained from Examples I and II
were then applied to the silicon d~oxide oxidised surfaces of silicon slices by spinning at~600 r.p.m.
and the coated slices were heated at 70C for 20 minutes on a hot plate. Each coated slice was then exposed -through a photomask to ultra-violet light (intensity 5 milliwatts per sq.cm.) for various times, and developed for 2-3 minutes in cyclohexanone, followed by a 15-second rinse in methanol. The optimum exposure time-was found to be 10 seconds. In a comparative test, the optimum exposure time ~or a polymeric layer of equal thicknes~ of resist produced from p-azidobenzoic acid and epoxide-novolak resin without ~-nitro groups and sensitised by Michler's ketone was found to be 90 second~., showing that the addition of nitro-benzoic aoid to the reactlon mixture giv~s a llght-sensitive polymeric product nine times more sensitive. The addition of 5-nitroacenaphthene to the solution of the polymeric ': ' ~'' .
1~J
c3.1.1975 ~4439~
procluct obtained from p-azldobenzoic acid ancl epoxide-novolak resin did not give an optirl~um exposure time of less than 90 seconds.
. .
~ 13-
Claims (22)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method of preparing low molecular weight light-sensitive polymeric compounds comprising reacting, in the presence of a common solvent, a mixture of p-azidobenzoic acid or an esterifiable derivative thereof and a p-nitrobenzoic acid which may be substituted in the ortho- and/or meta-positions with an alkyl group containing from 1 to 4 carbon atoms, or an esterifiable derivative thereof, with an epoxide resin as represented by the general formula:
(I) in which formula R represents hydroxypropylene or the hydrocarbon nucleus of a dihydric phenol which is free from functional groups other than phenolic hydroxy groups or a 1,2-propylene oxide derivative thereof; and n is 0, 1, 2 or 3.
(I) in which formula R represents hydroxypropylene or the hydrocarbon nucleus of a dihydric phenol which is free from functional groups other than phenolic hydroxy groups or a 1,2-propylene oxide derivative thereof; and n is 0, 1, 2 or 3.
2. A method according to claim 1 in which the mixture comprising p-azidobenzoic acid or an esterifiable derivative thereof and p-nitrobenzoic acid, if desired substituted in the ortho- and/or meta-positions with an alkyl group containing from 1 to 4 carbon atoms or an esterifiable derivative thereof, contains up to 75% by weight p-nitrobenzoic acid.
3. A method according to claim 2, in which the mixture contains p-azidobenzoic acid and p-nitrobenzoic acid in the proportions of between 3 : 1 parts by weight to 1 : 2 parts by weight.
4. A method according to claim 1, in which the epoxide resin has a molecular weight of between 340 - 1500.
5. A method according to claim 4, in which the epoxide resin has a molecular weight of between 340 - 750.
6. A method according to claim 4, in which the epoxide resin is a novolak resin with a molecular weight in the range of 600 - 1500.
7. A method according to claim 1, in which the epoxide resin is prepared by reacting 2 to 4 moles of epichlorohydrin with one mole of bisphenol A under an inert atmosphere with the gradual addition of 2 moles of sodium hydroxide, separating the epoxide product and reacting the epoxide, in the presence of a common solvent, with a mixture containing p-azidobenzoic acid or an esterifiable derivative thereof and p-nitrobenzoic acid, if desired substituted in the ortho- and/or meta-positions with an alkyl group containing not more than 4 carbon atoms, or an esterifiable derivative thereof at a temperature of less than 200°C.
8. h method according to claim 7, in which the reaction was carried out at a temperature of between 130 - 150°C.
9. A method according to claim 6, in which a novolak resin is prepared by reacting one mole of phenol with 0.8 mole of formaldehyde in the presence of an acid catalyst at 100 C, separating the product by removing the water produced when the desired degree of polymerization is reached ant reacting the novolak resin with epichlorohydrin to form terminal reactive epoxide groups on the novolak resin nucleus, separating the reaction product and reacting the product, in the presence of a common solvent, with a mixture of p-azidobenzoic acid or an esterifiable derivative thereof and p-nitrobenzoic acid, if desired substituted in the ortho- and/or meta-positions with an alkyl group containing not more than 4 carbon atoms or an esterifiable derivative thereof, in the mole ratio of one mole of the resin to 3 to 4 moles of the mixture.
10. A method according to claim 9, in which the mixture contains 1 mole of p-azidobenzoic acid and from 0.3 to 3 moles of p-nitrobenzoic acid.
11. A method according to claim 1, in which the common solvent is an organic solvent such as 1,4-dioxane or toluene.
12. A method according to claim 1 wherein R is selected from the group consisting of p,p'-dihydroxydiphenyl, p,p'-dihydroxydiphenyl methane, p,p'-dihydroxydiphenylmethylmethane, p,p'-dihydroxydibenzyl, and p,p'-di-hydroxydiphenyldimethyl methane.
13. Light-sensitive polymers as represented by the general formula:
(III) a 1,2-propylene oxide, a p-azidobenzoxy or a p-nitrobenzoxy derivative thereof, in which formula R1 represents hydroxypropylene or the hydrocarbon nucleus of a dihydric phenol which is free from functional groups other than phenolic hydroxy groups, X represents a N3 or a N02 group, with the proviso that the mixture of the polymers at least contain one molecule in which one X is a N2 group and at least one molecule in which one X is a N02 group, and n is 0, 1, 2 or 3,
(III) a 1,2-propylene oxide, a p-azidobenzoxy or a p-nitrobenzoxy derivative thereof, in which formula R1 represents hydroxypropylene or the hydrocarbon nucleus of a dihydric phenol which is free from functional groups other than phenolic hydroxy groups, X represents a N3 or a N02 group, with the proviso that the mixture of the polymers at least contain one molecule in which one X is a N2 group and at least one molecule in which one X is a N02 group, and n is 0, 1, 2 or 3,
14. Light-sensitive polymeric compounds according to claim 13 which contain an average of not more than 75% N02 groups.
15. Light-sensitve polymeric compounds according to claim 13 which contain at least one terminal or cross-linked nitrilo radical ?-N=) per molecule.
16. Light-sensitive polymeric compounds according to claim 13, in which R' is the hydrocarbon nucleus of p,p'-dihydroxydiphenyldimethyl methane.
17. Light-sensitive polymeric compounds according to claim 13, in which n is 0.
18. Light-sensitive compositions comprising a polymer according to claim 13 mixed with, dissolved or dispersed in an inert carrier.
19. Light-sensitive compositions according to claim 18 in which the composition is dissolved in a suitable organic solvent and, if desired, an inert carrier.
20. Light-sensitive compositions according to claim 18, comprising a light-sensitizing agent.
21. Light-sensitive coatings when coated on a substrate comprising a polymeric compound according to claim 13 or a light-sensitive composition according to claim 17.
22. Light-sensitive composition according to claim 20 in which the sensitizing agent is 5-nitroacenenaphthene.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB584674A GB1448332A (en) | 1974-02-08 | 1974-02-08 | Light-sensitive compoudns and photoresists containing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1044398A true CA1044398A (en) | 1978-12-12 |
Family
ID=9803731
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA219,615A Expired CA1044398A (en) | 1974-02-08 | 1975-02-07 | Light-sensitive compounds and photoresists containing the same |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS50114499A (en) |
| BE (1) | BE825326A (en) |
| CA (1) | CA1044398A (en) |
| DE (1) | DE2503969A1 (en) |
| FR (1) | FR2260603B1 (en) |
| GB (1) | GB1448332A (en) |
| NL (1) | NL7501274A (en) |
| SE (1) | SE7501269L (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100520163B1 (en) * | 2001-06-21 | 2005-10-10 | 주식회사 하이닉스반도체 | Novel photoresist polymer having nitro group and photoresist composition containing it |
| CN113101913B (en) * | 2021-03-19 | 2022-05-27 | 浙江恒逸石化研究院有限公司 | Preparation method of strip catalyst for regeneration of anthraquinone degradation product |
-
1974
- 1974-02-08 GB GB584674A patent/GB1448332A/en not_active Expired
-
1975
- 1975-01-31 DE DE19752503969 patent/DE2503969A1/en not_active Withdrawn
- 1975-02-04 NL NL7501274A patent/NL7501274A/en unknown
- 1975-02-05 SE SE7501269A patent/SE7501269L/xx unknown
- 1975-02-06 JP JP50014941A patent/JPS50114499A/ja active Pending
- 1975-02-07 CA CA219,615A patent/CA1044398A/en not_active Expired
- 1975-02-07 BE BE153188A patent/BE825326A/en unknown
- 1975-02-10 FR FR7504052A patent/FR2260603B1/fr not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2503969A1 (en) | 1975-08-14 |
| NL7501274A (en) | 1975-08-12 |
| JPS50114499A (en) | 1975-09-08 |
| GB1448332A (en) | 1976-09-02 |
| SE7501269L (en) | 1975-08-11 |
| FR2260603B1 (en) | 1980-05-16 |
| BE825326A (en) | 1975-08-07 |
| FR2260603A1 (en) | 1975-09-05 |
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