CA1041346A - Photosensitive composition - Google Patents
Photosensitive compositionInfo
- Publication number
- CA1041346A CA1041346A CA205,472A CA205472A CA1041346A CA 1041346 A CA1041346 A CA 1041346A CA 205472 A CA205472 A CA 205472A CA 1041346 A CA1041346 A CA 1041346A
- Authority
- CA
- Canada
- Prior art keywords
- diazo
- photosensitive composition
- polymer
- methyl
- methacrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/016—Diazonium salts or compounds
- G03F7/021—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders
- G03F7/0212—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders characterised by the polymeric binder or the macromolecular additives other than the diazo resins or the polymeric diazonium compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/106—Binder containing
- Y10S430/111—Polymer of unsaturated acid or ester
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/128—Radiation-activated cross-linking agent containing
Abstract
ABSTRACT OF THE DISCLOSURE
A photosensitive composition is prepared comprising a diazo-aromatic compound and a polymer containing 50 to 100%
by weight of the recurring unit represented by the following general formula (I):
A photosensitive composition is prepared comprising a diazo-aromatic compound and a polymer containing 50 to 100%
by weight of the recurring unit represented by the following general formula (I):
Description
:~04~346 This invention relates to a photosensitive composition and, particularly, to a photosensitive composition used for the preparation of a photosensitive or presensitized planographic plate. The great majority of photosensitive substances which have been used as a photosensitive layer of a presensitized printing plate are diazonium compounds. The most commonly used are diazo resins represented, for example, by a condensate of ?
p-diazodiphenylamine with formaldehyde. Such diazo resins are commercially available, e.g., under the trade marks "DIAZOLYS #l"
10 (Ringwood Chemical Corp.) and "DIAZO RESIN #4" ~Fairmount Chemical Corp.). When such a diazo resin is applied to a paper, , plastic film, metallic sheet or like appropriate support and , . -j , exposed to actinic light through a negative transparency, the exposed part o~ the diazo resin is insolubilized due to the decomposition of the diazo resin. On the other hand, the un-exposed area is washed off with water, whereupon the surface of the support is revealed. In case there is used a support having a surface pretreated to render it hydrophilic, the unexposed ~ area reveals this hydrophilic surface upon development. Thus, ., :
20 on an off-set printing press, this area attracts water and repels an ink, while the decomposed diazo resin in the exposed area exhibits oleophilic properties and attracts ink and repels ~; water. Namely, such printing materials provide so called .
negative-working printing plates.
Photosensitive compositions used in this type o~ ;
.. ( ': ' ~ .photosensitive printing material may be divided into two groups~
one comprising a diazo resin alone and containing no ' ' ;~' .,. ,., ' ' .
.. . ~ , ':' :~' ' 1:04~L3~16 .
carrier as disclosed in United States Patent No. 2,714,066 and : the other comprising a blend of a diazo r~,sin and a carrier as disclosed in United 5tates Patent No. 2,826,5~1 and British ~ : Patent No. 1,074,392. In the former case, since no carrier,ls 5 ;. used, the thickness of the photosensitive layer is abou~ 20 to : , ~ about 100 mg/mZ, so that it is necessary to reinforce the image : ~ :
. ~ area to enhance it~ a~rasion resistance and printing durability.
. . . ;~ .
Usually, concurrently with or subsequently to the developing ; step, an emulsified lac~uer is applied to the image area to ..
deposit thereon a resinous proteative film khereby to make the printing plate able to endure various ~rictional and peeling-.
o~f forces encountered during the printing of numerous sheets .; of printed matter. A lacquer to be used for this purpose ; must have excellent abrasion resistance, firmly adhere to the . }
i: : .15.;~ image area o~ a plate and never yield scums and dregs. Many . .
. proposals for such lacquers have been made as disclosed, for ..example in United States Patent No. 2,754,279. However, the ,, . .. ~ .
application o~ a laaquer, which is usually done by the users o~ printing material~, re~uires aonsiderable skill because 20 ....the ~uality o~ a printing plate depends greatly on whether the lacquer is applied well or poorly. To eliminate the afore-said drawbacks, it was previously proposed to incorporate a resin having good abrasion resistance into a photosensitive layer together with a photosensitive substance and to harden t, ~
~: the incorporated resin with a photodecomposed diaæonium compound, as disclosed, for example, in United States Patent No. 2,826,501 and British Patent No. 1,074,392. Specifically, .: . .~ , ~ ~ :
4~346 . ~ , . , a resin corresponding to the'aforesaid lacquer is blended with a diazo resin, the blend is applied to a ~support in the ,; ;,, . I
~ ' `'necessary thickness, usually about 0.5 to about 5 g/m2 as ., ,, t ' ~ the coated amount, and, in the developing step,,the unnecessary '' 5, area, i.e. f unhardened area, is removed by taking advantage t'~` of the difference in solubility or degree of swelling between "'S1'the hardened area and the hardened area from the surface of the `;'support to obtain a printing plate which is equal to or 8uperior in quality to a printing plate prepared in the afore-~10 ~'said way.~
'` ` ' The re8in to be incorpoxated with a diazo resin should be such that it has a ~ood compatibility with the diazo resin and can be dissolved in an inexpensive common solvent f with the diazo resin. Furthermore, the resin incorporated should ' ~ ",' ,'t, ~ ,' ., "~"~ _ _ "
'i~,'-'15~' be completely hardened ~y the photodecomposed product of the ' '~j'''-,t~ .diazo resin into the insoluble state or yield a clear difference 'in solubility or swellability between the exposed area and i ~ih ~ ~,s k"" ,, ~ ; " !''` ~he unexposed area. In addition, the resin used as a carrier "' should not have the property of deteriorating the storage ~:~ .; . 20 i.; stability of a blend with the diazo photosensitive'substance.
~''''` ''s~ 'A certain water-soluble colloid forms, when used as ia carrier ?~, for a diazo resin, a photoresist of a very good quality, but ;the resist is deteriorated after a few days to lose its photo-' ~ j'; sensitivity by dark reaction. In the prior art, some proposals 25'- have been made with respect to carrier materials which satisfy the aforesaid requirements, though none of them fulfills all ' ~ 'lo''~''~' the requirements of hardening rate, printing durability, oleophilic "
J''G'~ "y~' properties and storage stability.
""~, "~
~0~346 In accordance with the present invention there is provided a photosensitive composition, comprising (a) a diazo-aromatic compound which has been reacted with at least one coupling agent to form a reaction product which is at least partially soluble in organic solvents, has a light sensitivity not substantially less than the initial diazo-aromatic compound ~, and is, at the most, slightly water soluble, and (b) a polymer containing 50 to 100% by weight of the recurring unit represented by the following general formula (I): Rl ~, 10 Coo(cH2cHo)n-H (I) :- , R2 , wherein Rl represents a hydrogen atom or methyl group, R2 re-i presents a hydrogen atom or a methyl, ethyl or chloromethyl group and n is an integer of from 1 to 10, the balance of the units of said polymer consisting essentially of units of a monoethyleni- -cally unsaturated compound which is selected from the group con- `
sisting of organic acrylates or methacrylates, acrylamide or ;~
methacrylamide, mono or di-N-alkyl-, cycloalkyl- or aryl- ;
acrylamide or methacrylamide, hydroxyalkyl or hydroxyaryl acrylamide or methacrylamide, allyl esters and ethers, vinyl ethers, vinyl esters, styrene, alkylstyrenes, halostyrenes, halomethyl styrenes, alkoxyalkyl styrenes, alkyl crotonates, dialkyl itaconates, dialkyl maleates, dialkyl fumarates, acrylonitrile and methacrylonitrile, said diazo-aromatic compound , . . . ,~
being present in an amount of about 5 to about 50% by weight based on the total weight of diazo-aromatic compound and polymer.
; . . . .
The photosensitive compositions of this invention meet the requirements outlined above.
:, , .
The monomers employed to form the recurring units of formula I include hydroxyethyl acrylate, hydroxyethyl methacrylate, , ~2 ' .; ,: : . . : . ,~ . . : : . . .
~ ~L041~6 hydroxypropyl acryla-te, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxy-2-chloropropyl acrylate, hydroxy-2-chloropropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, tri-ethylene glycol monoacrylate, triethylene glycol monomethacrylate, tetraethylene glycol monoacrylate, tetraethylene glycol monomethacrylate, pentaethylene glycol monomethacrylate, decaethylene glycol monoacrylate, decaethylene glycol~mono methacrylate, dipropylene glycol mono acrylate, dipropylene glycol monomethacrylat~, tripropylene glycol monoacrylate, tripropylene glycol monomethacrylate, dibutylene glycol monoacrylate, dibutylene glycol monomethacrylate, di(2-chloro-~, propylene glycol) acrylate, di~2-chloropropylene glycol) methacrylate.
~ The preferred monomer is hydroxyetllyl methacrylate.
; Negative-acting diazo compounds, broadly, are diazo-:; ~ . .
aromatics, and more particular~y are diazo-arylamines that can be substituted on the aromatic nucleus or on the amino-nitrogen, preferably p-diazo-diphenylamine and derivatives thereof, for example, condensation products thereof with or-ganic condensing agents containing reactive carbonyl groups ~.,, ~s such as aldehydes and acetals, particularly condensates with . . .
compounds such as formaldehyde, zinc chloride and paraformal-, i~ dehyde. The preparation of such eminently suitable condensation ~ products is disclosed in U.S.Pat. Nos. 2,992,715 and 2,946,683.
;: .
: .:
, :
'.''''.' ,, , -.~; '' ., ' ' .
., ~ . .
13g6 ., The foregoing diazo compounds are reacted with suitable . -:
~ - couplin~ agents to prepare recs9ction products that are at least .. ..
partially soluble in organic solvents, preferably well soluble and that have light-sensitivity not substantial~y less 7,. ~
~ ` 5 ~ than the starting diazo. The reaction products are only ~, ~
~ ~- slightly water-soluble, if at all. Suitable coupling agents , . ~ , .
h-~ broadly are essentially organic compounds that react with the `; ~ water-soluble diazo compounds to reduce its ionic character : i ~,.. .-and make it more covalent, do not reduce significantly its 10 ` light-sensitivity, and produce a reaction product that is i soluble in organic solvents but no more than only sli~htly ,, .., ..~. " . ... . . . .
`""';' ~`~' ';' ;'~!'~' water-soluble. Such coupling agents in general presently ;~;appear to be acidic aromatic compounds, for example, the ; phosphinic, phosphonic, sulfonic and carboxylic acids of ;15 ~ benzene, toluene and naphthalene and their derivatives, for example, the alkali metal salts thereof; hydroxyl-containing ' aromatic compounds,~e.g., phenolics such as diphenolic acid, benzophencsne, substituted benzophenones, naphthols, naphthalene diols and alizarins, including sulfonic acids and alkali 20 -~ metal sulfonic acid salts thereof; and acidic aliphatic compounds such as stearic acid and ethylenediamine tetra acetic acid.
Particularly suitable couplin~ compounds of the type described ~ 9~
`;include toluene suIfonic acid, ben~ene phosphinic acid, ` 2,5-dimethyl-benzene sulfonic acid, benzene sulfonic ascid s ~ ~25~ sodium salt, nitrobenzen~isiisi acetic acid, diphenolic acicl, j ` ~2,3-naphthalene diol, naphthalene-2-sulfonic acld, 1-naphthol-2-9~
::
:~t)4~3~
~or 4-)sulfonic acid, 2,4-dinit.ro-l-naphthol-7-sulfonic acid,
p-diazodiphenylamine with formaldehyde. Such diazo resins are commercially available, e.g., under the trade marks "DIAZOLYS #l"
10 (Ringwood Chemical Corp.) and "DIAZO RESIN #4" ~Fairmount Chemical Corp.). When such a diazo resin is applied to a paper, , plastic film, metallic sheet or like appropriate support and , . -j , exposed to actinic light through a negative transparency, the exposed part o~ the diazo resin is insolubilized due to the decomposition of the diazo resin. On the other hand, the un-exposed area is washed off with water, whereupon the surface of the support is revealed. In case there is used a support having a surface pretreated to render it hydrophilic, the unexposed ~ area reveals this hydrophilic surface upon development. Thus, ., :
20 on an off-set printing press, this area attracts water and repels an ink, while the decomposed diazo resin in the exposed area exhibits oleophilic properties and attracts ink and repels ~; water. Namely, such printing materials provide so called .
negative-working printing plates.
Photosensitive compositions used in this type o~ ;
.. ( ': ' ~ .photosensitive printing material may be divided into two groups~
one comprising a diazo resin alone and containing no ' ' ;~' .,. ,., ' ' .
.. . ~ , ':' :~' ' 1:04~L3~16 .
carrier as disclosed in United States Patent No. 2,714,066 and : the other comprising a blend of a diazo r~,sin and a carrier as disclosed in United 5tates Patent No. 2,826,5~1 and British ~ : Patent No. 1,074,392. In the former case, since no carrier,ls 5 ;. used, the thickness of the photosensitive layer is abou~ 20 to : , ~ about 100 mg/mZ, so that it is necessary to reinforce the image : ~ :
. ~ area to enhance it~ a~rasion resistance and printing durability.
. . . ;~ .
Usually, concurrently with or subsequently to the developing ; step, an emulsified lac~uer is applied to the image area to ..
deposit thereon a resinous proteative film khereby to make the printing plate able to endure various ~rictional and peeling-.
o~f forces encountered during the printing of numerous sheets .; of printed matter. A lacquer to be used for this purpose ; must have excellent abrasion resistance, firmly adhere to the . }
i: : .15.;~ image area o~ a plate and never yield scums and dregs. Many . .
. proposals for such lacquers have been made as disclosed, for ..example in United States Patent No. 2,754,279. However, the ,, . .. ~ .
application o~ a laaquer, which is usually done by the users o~ printing material~, re~uires aonsiderable skill because 20 ....the ~uality o~ a printing plate depends greatly on whether the lacquer is applied well or poorly. To eliminate the afore-said drawbacks, it was previously proposed to incorporate a resin having good abrasion resistance into a photosensitive layer together with a photosensitive substance and to harden t, ~
~: the incorporated resin with a photodecomposed diaæonium compound, as disclosed, for example, in United States Patent No. 2,826,501 and British Patent No. 1,074,392. Specifically, .: . .~ , ~ ~ :
4~346 . ~ , . , a resin corresponding to the'aforesaid lacquer is blended with a diazo resin, the blend is applied to a ~support in the ,; ;,, . I
~ ' `'necessary thickness, usually about 0.5 to about 5 g/m2 as ., ,, t ' ~ the coated amount, and, in the developing step,,the unnecessary '' 5, area, i.e. f unhardened area, is removed by taking advantage t'~` of the difference in solubility or degree of swelling between "'S1'the hardened area and the hardened area from the surface of the `;'support to obtain a printing plate which is equal to or 8uperior in quality to a printing plate prepared in the afore-~10 ~'said way.~
'` ` ' The re8in to be incorpoxated with a diazo resin should be such that it has a ~ood compatibility with the diazo resin and can be dissolved in an inexpensive common solvent f with the diazo resin. Furthermore, the resin incorporated should ' ~ ",' ,'t, ~ ,' ., "~"~ _ _ "
'i~,'-'15~' be completely hardened ~y the photodecomposed product of the ' '~j'''-,t~ .diazo resin into the insoluble state or yield a clear difference 'in solubility or swellability between the exposed area and i ~ih ~ ~,s k"" ,, ~ ; " !''` ~he unexposed area. In addition, the resin used as a carrier "' should not have the property of deteriorating the storage ~:~ .; . 20 i.; stability of a blend with the diazo photosensitive'substance.
~''''` ''s~ 'A certain water-soluble colloid forms, when used as ia carrier ?~, for a diazo resin, a photoresist of a very good quality, but ;the resist is deteriorated after a few days to lose its photo-' ~ j'; sensitivity by dark reaction. In the prior art, some proposals 25'- have been made with respect to carrier materials which satisfy the aforesaid requirements, though none of them fulfills all ' ~ 'lo''~''~' the requirements of hardening rate, printing durability, oleophilic "
J''G'~ "y~' properties and storage stability.
""~, "~
~0~346 In accordance with the present invention there is provided a photosensitive composition, comprising (a) a diazo-aromatic compound which has been reacted with at least one coupling agent to form a reaction product which is at least partially soluble in organic solvents, has a light sensitivity not substantially less than the initial diazo-aromatic compound ~, and is, at the most, slightly water soluble, and (b) a polymer containing 50 to 100% by weight of the recurring unit represented by the following general formula (I): Rl ~, 10 Coo(cH2cHo)n-H (I) :- , R2 , wherein Rl represents a hydrogen atom or methyl group, R2 re-i presents a hydrogen atom or a methyl, ethyl or chloromethyl group and n is an integer of from 1 to 10, the balance of the units of said polymer consisting essentially of units of a monoethyleni- -cally unsaturated compound which is selected from the group con- `
sisting of organic acrylates or methacrylates, acrylamide or ;~
methacrylamide, mono or di-N-alkyl-, cycloalkyl- or aryl- ;
acrylamide or methacrylamide, hydroxyalkyl or hydroxyaryl acrylamide or methacrylamide, allyl esters and ethers, vinyl ethers, vinyl esters, styrene, alkylstyrenes, halostyrenes, halomethyl styrenes, alkoxyalkyl styrenes, alkyl crotonates, dialkyl itaconates, dialkyl maleates, dialkyl fumarates, acrylonitrile and methacrylonitrile, said diazo-aromatic compound , . . . ,~
being present in an amount of about 5 to about 50% by weight based on the total weight of diazo-aromatic compound and polymer.
; . . . .
The photosensitive compositions of this invention meet the requirements outlined above.
:, , .
The monomers employed to form the recurring units of formula I include hydroxyethyl acrylate, hydroxyethyl methacrylate, , ~2 ' .; ,: : . . : . ,~ . . : : . . .
~ ~L041~6 hydroxypropyl acryla-te, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxy-2-chloropropyl acrylate, hydroxy-2-chloropropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, tri-ethylene glycol monoacrylate, triethylene glycol monomethacrylate, tetraethylene glycol monoacrylate, tetraethylene glycol monomethacrylate, pentaethylene glycol monomethacrylate, decaethylene glycol monoacrylate, decaethylene glycol~mono methacrylate, dipropylene glycol mono acrylate, dipropylene glycol monomethacrylat~, tripropylene glycol monoacrylate, tripropylene glycol monomethacrylate, dibutylene glycol monoacrylate, dibutylene glycol monomethacrylate, di(2-chloro-~, propylene glycol) acrylate, di~2-chloropropylene glycol) methacrylate.
~ The preferred monomer is hydroxyetllyl methacrylate.
; Negative-acting diazo compounds, broadly, are diazo-:; ~ . .
aromatics, and more particular~y are diazo-arylamines that can be substituted on the aromatic nucleus or on the amino-nitrogen, preferably p-diazo-diphenylamine and derivatives thereof, for example, condensation products thereof with or-ganic condensing agents containing reactive carbonyl groups ~.,, ~s such as aldehydes and acetals, particularly condensates with . . .
compounds such as formaldehyde, zinc chloride and paraformal-, i~ dehyde. The preparation of such eminently suitable condensation ~ products is disclosed in U.S.Pat. Nos. 2,992,715 and 2,946,683.
;: .
: .:
, :
'.''''.' ,, , -.~; '' ., ' ' .
., ~ . .
13g6 ., The foregoing diazo compounds are reacted with suitable . -:
~ - couplin~ agents to prepare recs9ction products that are at least .. ..
partially soluble in organic solvents, preferably well soluble and that have light-sensitivity not substantial~y less 7,. ~
~ ` 5 ~ than the starting diazo. The reaction products are only ~, ~
~ ~- slightly water-soluble, if at all. Suitable coupling agents , . ~ , .
h-~ broadly are essentially organic compounds that react with the `; ~ water-soluble diazo compounds to reduce its ionic character : i ~,.. .-and make it more covalent, do not reduce significantly its 10 ` light-sensitivity, and produce a reaction product that is i soluble in organic solvents but no more than only sli~htly ,, .., ..~. " . ... . . . .
`""';' ~`~' ';' ;'~!'~' water-soluble. Such coupling agents in general presently ;~;appear to be acidic aromatic compounds, for example, the ; phosphinic, phosphonic, sulfonic and carboxylic acids of ;15 ~ benzene, toluene and naphthalene and their derivatives, for example, the alkali metal salts thereof; hydroxyl-containing ' aromatic compounds,~e.g., phenolics such as diphenolic acid, benzophencsne, substituted benzophenones, naphthols, naphthalene diols and alizarins, including sulfonic acids and alkali 20 -~ metal sulfonic acid salts thereof; and acidic aliphatic compounds such as stearic acid and ethylenediamine tetra acetic acid.
Particularly suitable couplin~ compounds of the type described ~ 9~
`;include toluene suIfonic acid, ben~ene phosphinic acid, ` 2,5-dimethyl-benzene sulfonic acid, benzene sulfonic ascid s ~ ~25~ sodium salt, nitrobenzen~isiisi acetic acid, diphenolic acicl, j ` ~2,3-naphthalene diol, naphthalene-2-sulfonic acld, 1-naphthol-2-9~
::
:~t)4~3~
~or 4-)sulfonic acid, 2,4-dinit.ro-l-naphthol-7-sulfonic acid,
2,4-dihydroxy-benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone, 2,2', 4,4'-tetra-hydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone-S-sulfonic acid, m-(pl-anilino-phenylazo)- .
benzene sulfonic acid sodium salt, p-morpholino-benzene diazonium flucborate, alizarin sodium-monosulfonate and o-toluidine-m-sulfonic acid. Some of these coupling agents and the preparation of coupled products thereof with light-sensitive diazo compounds are disclosed in U.S. Patent No. 3,300,309 and U.S. Patent :~
benzene sulfonic acid sodium salt, p-morpholino-benzene diazonium flucborate, alizarin sodium-monosulfonate and o-toluidine-m-sulfonic acid. Some of these coupling agents and the preparation of coupled products thereof with light-sensitive diazo compounds are disclosed in U.S. Patent No. 3,300,309 and U.S. Patent :~
3,591,575. :`
~i The diazo component and the coupling agent preferably ~.
;. ~ e~ u~nnol~r are reacted together in approximately~ e~ uantities.
Other examples of suitable diazo compounds include reaction products of the coupl.ing agents described above with .~
diazo resins such as condensates of 2,5-dimethoxy-4-p-tolylmer- ~ ;
captobenzenediazonium with formaldehyde and condensates of 2,5-; dimethoxy-4-morpholinobenzenediazonium with formaldehyde or acetaldehyde, and compounds represented by the following general . formula:
,:' .~ 20 ` ~
:. .
'.. "", ' ' ':
.:
''~'' ' `" , ', ~,'' : , ' 'i . `~
.,. I
~'': i l'. . ' .
`.~ .' ~.,, .
',,, ~;'. _ 9 _ f',, ,.' , ' ~' ': ,, `, ' ' ' ' ' ~C~4~L346 -~ R \ ~ ~4 J
i ,., -.
; wherein: :
:; .:
Rl, R2, R3 and R4 each represent an alkyl groupcontaining 1 to 4 carbon atoms, such as methyl, ethyl, propyl or butyl;
,~ ~
. X represents a substituted amino group, such as ;: N-(beta-Hydroxyethyl)amino, N,N-di(beta-hydroxyethyl)amino or like hydroxyalkylarnino group; and ,: Y represents an anion of the coupling agent as -~; 10 described above; examples are: 2-methoxy-4-hydroxy-5- : :
benzoyl benzenesulfonate of 2,6-bis(4-diazo-2,5-dimethoxyphenyl-.: amino)-4-N,N-(di-beta-hydroxyethyl)amino-1,3,5-triazine; ~ :
~"," ., ~ 2-methoxy-4-hydroxy-5-benzoylbenzene-sulfonate of 2,6-bis(4-., .
diazo-2,5-dimethoxyphenylamino)-4-N-(beta-hydroxyethyl)amino- .
~ 1,3,5-triazine, and 2-methoxy-4-hydroxy-5-benzoylbenzene-.~ sulfonate of 2,6-bis(4-diazo-2,5-diethoxy-phenylamino)-4- ;. .
~; N-(beta-hydroxyethyl)-amino-1,3,5-triazine.
Still other suitable diazo compounds are those as disclosed in United States Patent Specification No. 2,649,373.
The most preferred diazo compound is 2-methoxy-4-.: hydroxy-5-benzoylbenzene sulfonic acid salt of the condensate of .:
p-diazo-diphenylamine with formaldehyde. ;:
.'f, .'.~ :
''' ' ., ~' - 10 -;:~.,.
... ~.'':' '~
:~.~ . . . . . - . , .
~ .
The polymer containing at least about 5Q~, by weight o the recurring units represented by the aforesaid general : ~ . .
formula (I), to be used in the present invention, includes homopolymers as well as copolymers with other addition~
~5 - polymerizable uni,aturated compounds (e.g., ethylenically , .: :
` unsaturated compounds). The units of general formula I
result from polymerizing compounds represented by the following . . ....
~ general formula (II): ~
" , . j i, ~ .. " ! ~
CH = C
; 2 COO~C~2CHOtnH ~ ~ (II) ' ~Z, ;-; ` wherein: R , R2, and n have the same meanings as designated with respect to the general formula (I).
The adaition-polymerizable unsaturated compounds which can be compolymerized with the compounds of formula II
. Z, ~ include compounds containing a single addition-polymerizable :. : ".
unsaturated bond, such as organic acrylates, acrylamides, organic methacrylates, methacrylamides, allyl compounds,~
vinyl ethers r vinyl esters, organic crotonates, styrenes and the like. Examples are: organic acrylates, such as alkyl ; acrylates, e.g., methyl acrylatej, ethyl acrylater propyl ~20 `ll acrylate, butyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert.-octyl acrylate, chloroethyl acxylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, ! "` glycidyl acrylate, benzyl acrylate, methoxybenzyl acry:Late, 25-~ i; urfuryl acrylate and tetrahydrofuxfuryl acrylate, and aryl ~ acrylates, e.gO, phenyl acrylates; organic methacrylates, such -- l L
as alkyl methacrylate, e.g., methylmethacrylate, ethylmethacrylate, propyl methacrylate, isopropyl methacrylate, b~yl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, ~ benzyl methacrylate, chlorobenzyl methacrylate" octyl ; 5 methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl .
-- methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, tri-` methylolpropane monomethacrylate, pentaerythritol methacrylate, glycidyl methacrylate, furfury~: methacrylate and tetrahydrofur-` furyl methacrylate, and aryl methacrylates, e.g., phenyl !,~ .
10 ; methacrylate, cresyl methacryalte and naphthyl methacrylate~
; acrylamides, such as acxylamide itself, N-alkylaarylamides wherein the alkyl is, e.gA, methyl ethyl, propyl, butyl, t-butyl, heptyl, octyl, cyclohexyl, benzyl, or pentyl, ~-hydroxyalkyl acrylamides, e.g., hydroxyethyl acrylamide, i~ N-arylacrylamides wherein the aryl, e~g., phenyl or tolyl or naphthyl and N-hydroxyaryl acrylamides, e.y., hydroxyphenyl, ' ~ p-nitrophenyl, N,N-dialkylacrylamides wherein the alkyl is i.!- ;.~ .
e.g., methyl, ethyl such as~dimethyl acrylamide, ethyl propyl acrylamide, diebutyl acrylamide, butyl, isobutyl, 2-ethylhexyl ,. ~
~; 20 ~ or cyclohexyl, N,N-diarylacrylamides wherein the aryl is, e.g., ~ ; phenyl, e.gO, N-methyl-N-phenylacrylamide, N-2-acetamidethyl-N-3 ~ acetylacrylamide and the like, methacrylamides, such as methacrylamide itself, N-alkylmethacrylamides wherein the alkyl is, e.g., methyl, ethyl, tert-butyl, 2-ethylhexyl, hydroxyethyl .~ . ....
~ 25~ ~ and cyclohexyl, N-arylmethacrylamides wherein the aryl is, ., . .~ :
e.g., phenyl, N,N-dialkylmethacrylamides wherein the alkyl ~s, ?.'. "..` ;~ e-~., methyl, ethyl, propyl and/or butyl, e.g., dimethyl ~ methacrylamlde, dibutyl methacrylamide, N,N-diarylmethacrylamides ~ . .
.
I
~0~ 346 wherein aryl is, e.g., phenyl, N-hydroxyethyl-N-methylmethacryl-amide, N-methyl-N-phenylmethacryiamide and N-ethyl-N-phenyl-methacrylamide; allyl compounds, such as allyl esters, e.g., ` ' ~ allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoàte, ailyl aceto-- . , acetate and allyl lactate, and allyoxyethanol; vinyl ethers, such as alkyl vinyl ethers, e.g., hexyl vinyl ether, octyl , ~ .
~ vinyl ether, decyl vinyl ether, 2-ethylhexyl vinyl ether, .
; ~ methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethyl-.
butyl vinyl ether, hydroxyethyl vinyl either, vinyl methyl ether, diethyleneglycol vinyl ether, dimethylaminoethyl vinyl ether, , , butylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, benzyL vinyl ether and tetrahydrofurfuryl vinyl ether, and ,I; lS ; vinyl aryl ethers and vinyl halvaryl ethers, e.g., vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl 2,4-dichlorophenyl ether, vinyl naphthyl ether and vinyl anthranyl ether; vinyl esters, e.g., vinyl acetate, vinyl ~; butyrate, vinyl iso~utyrate, vinyl trimethylacetate, vinyl ~diethylacetate, vinyl valerate, vinyl caproate, vinyl chloro-acetat~e, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl phenylacetate, vinyl acetoacetate, vinyl lactate, vinyl propionate, vinyl beta-phenylbutylate, vinyl ~; ~ ; cyclohexanecarboxylate, vinyl benzoate, vinyl salicylate, , :~ ,. . .
vinyl chlorobenzoate, vinyl tetrachlorobenzoate and vinyl naphthoate; styrenes, such as styrnee itself, alkylstyrenes, ; e.g., p-methylstyrene, o-methylstyrene, 2,4-dimethylstyrene, . .
~ trimethylstyrene, p-ethylstyrene, ~,4-diethylstyrene, o-isopropyl-. , ~ , ~ . .
~ styrene, p-butylstyrene, p-hexylstyrene, alpha methyl styrene, ' ' , ,: ' . ! , ~ ~ , .
: :
~ 4~;~46 p-cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethyl-styrene, trifluoromethylstyrene, ethoxymethylstyrene and acetoxymethylstyrene, alkoxystyrenes, e.g., p-methoxystyrene,
~i The diazo component and the coupling agent preferably ~.
;. ~ e~ u~nnol~r are reacted together in approximately~ e~ uantities.
Other examples of suitable diazo compounds include reaction products of the coupl.ing agents described above with .~
diazo resins such as condensates of 2,5-dimethoxy-4-p-tolylmer- ~ ;
captobenzenediazonium with formaldehyde and condensates of 2,5-; dimethoxy-4-morpholinobenzenediazonium with formaldehyde or acetaldehyde, and compounds represented by the following general . formula:
,:' .~ 20 ` ~
:. .
'.. "", ' ' ':
.:
''~'' ' `" , ', ~,'' : , ' 'i . `~
.,. I
~'': i l'. . ' .
`.~ .' ~.,, .
',,, ~;'. _ 9 _ f',, ,.' , ' ~' ': ,, `, ' ' ' ' ' ~C~4~L346 -~ R \ ~ ~4 J
i ,., -.
; wherein: :
:; .:
Rl, R2, R3 and R4 each represent an alkyl groupcontaining 1 to 4 carbon atoms, such as methyl, ethyl, propyl or butyl;
,~ ~
. X represents a substituted amino group, such as ;: N-(beta-Hydroxyethyl)amino, N,N-di(beta-hydroxyethyl)amino or like hydroxyalkylarnino group; and ,: Y represents an anion of the coupling agent as -~; 10 described above; examples are: 2-methoxy-4-hydroxy-5- : :
benzoyl benzenesulfonate of 2,6-bis(4-diazo-2,5-dimethoxyphenyl-.: amino)-4-N,N-(di-beta-hydroxyethyl)amino-1,3,5-triazine; ~ :
~"," ., ~ 2-methoxy-4-hydroxy-5-benzoylbenzene-sulfonate of 2,6-bis(4-., .
diazo-2,5-dimethoxyphenylamino)-4-N-(beta-hydroxyethyl)amino- .
~ 1,3,5-triazine, and 2-methoxy-4-hydroxy-5-benzoylbenzene-.~ sulfonate of 2,6-bis(4-diazo-2,5-diethoxy-phenylamino)-4- ;. .
~; N-(beta-hydroxyethyl)-amino-1,3,5-triazine.
Still other suitable diazo compounds are those as disclosed in United States Patent Specification No. 2,649,373.
The most preferred diazo compound is 2-methoxy-4-.: hydroxy-5-benzoylbenzene sulfonic acid salt of the condensate of .:
p-diazo-diphenylamine with formaldehyde. ;:
.'f, .'.~ :
''' ' ., ~' - 10 -;:~.,.
... ~.'':' '~
:~.~ . . . . . - . , .
~ .
The polymer containing at least about 5Q~, by weight o the recurring units represented by the aforesaid general : ~ . .
formula (I), to be used in the present invention, includes homopolymers as well as copolymers with other addition~
~5 - polymerizable uni,aturated compounds (e.g., ethylenically , .: :
` unsaturated compounds). The units of general formula I
result from polymerizing compounds represented by the following . . ....
~ general formula (II): ~
" , . j i, ~ .. " ! ~
CH = C
; 2 COO~C~2CHOtnH ~ ~ (II) ' ~Z, ;-; ` wherein: R , R2, and n have the same meanings as designated with respect to the general formula (I).
The adaition-polymerizable unsaturated compounds which can be compolymerized with the compounds of formula II
. Z, ~ include compounds containing a single addition-polymerizable :. : ".
unsaturated bond, such as organic acrylates, acrylamides, organic methacrylates, methacrylamides, allyl compounds,~
vinyl ethers r vinyl esters, organic crotonates, styrenes and the like. Examples are: organic acrylates, such as alkyl ; acrylates, e.g., methyl acrylatej, ethyl acrylater propyl ~20 `ll acrylate, butyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert.-octyl acrylate, chloroethyl acxylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, ! "` glycidyl acrylate, benzyl acrylate, methoxybenzyl acry:Late, 25-~ i; urfuryl acrylate and tetrahydrofuxfuryl acrylate, and aryl ~ acrylates, e.gO, phenyl acrylates; organic methacrylates, such -- l L
as alkyl methacrylate, e.g., methylmethacrylate, ethylmethacrylate, propyl methacrylate, isopropyl methacrylate, b~yl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, ~ benzyl methacrylate, chlorobenzyl methacrylate" octyl ; 5 methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl .
-- methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, tri-` methylolpropane monomethacrylate, pentaerythritol methacrylate, glycidyl methacrylate, furfury~: methacrylate and tetrahydrofur-` furyl methacrylate, and aryl methacrylates, e.g., phenyl !,~ .
10 ; methacrylate, cresyl methacryalte and naphthyl methacrylate~
; acrylamides, such as acxylamide itself, N-alkylaarylamides wherein the alkyl is, e.gA, methyl ethyl, propyl, butyl, t-butyl, heptyl, octyl, cyclohexyl, benzyl, or pentyl, ~-hydroxyalkyl acrylamides, e.g., hydroxyethyl acrylamide, i~ N-arylacrylamides wherein the aryl, e~g., phenyl or tolyl or naphthyl and N-hydroxyaryl acrylamides, e.y., hydroxyphenyl, ' ~ p-nitrophenyl, N,N-dialkylacrylamides wherein the alkyl is i.!- ;.~ .
e.g., methyl, ethyl such as~dimethyl acrylamide, ethyl propyl acrylamide, diebutyl acrylamide, butyl, isobutyl, 2-ethylhexyl ,. ~
~; 20 ~ or cyclohexyl, N,N-diarylacrylamides wherein the aryl is, e.g., ~ ; phenyl, e.gO, N-methyl-N-phenylacrylamide, N-2-acetamidethyl-N-3 ~ acetylacrylamide and the like, methacrylamides, such as methacrylamide itself, N-alkylmethacrylamides wherein the alkyl is, e.g., methyl, ethyl, tert-butyl, 2-ethylhexyl, hydroxyethyl .~ . ....
~ 25~ ~ and cyclohexyl, N-arylmethacrylamides wherein the aryl is, ., . .~ :
e.g., phenyl, N,N-dialkylmethacrylamides wherein the alkyl ~s, ?.'. "..` ;~ e-~., methyl, ethyl, propyl and/or butyl, e.g., dimethyl ~ methacrylamlde, dibutyl methacrylamide, N,N-diarylmethacrylamides ~ . .
.
I
~0~ 346 wherein aryl is, e.g., phenyl, N-hydroxyethyl-N-methylmethacryl-amide, N-methyl-N-phenylmethacryiamide and N-ethyl-N-phenyl-methacrylamide; allyl compounds, such as allyl esters, e.g., ` ' ~ allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoàte, ailyl aceto-- . , acetate and allyl lactate, and allyoxyethanol; vinyl ethers, such as alkyl vinyl ethers, e.g., hexyl vinyl ether, octyl , ~ .
~ vinyl ether, decyl vinyl ether, 2-ethylhexyl vinyl ether, .
; ~ methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethyl-.
butyl vinyl ether, hydroxyethyl vinyl either, vinyl methyl ether, diethyleneglycol vinyl ether, dimethylaminoethyl vinyl ether, , , butylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, benzyL vinyl ether and tetrahydrofurfuryl vinyl ether, and ,I; lS ; vinyl aryl ethers and vinyl halvaryl ethers, e.g., vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl 2,4-dichlorophenyl ether, vinyl naphthyl ether and vinyl anthranyl ether; vinyl esters, e.g., vinyl acetate, vinyl ~; butyrate, vinyl iso~utyrate, vinyl trimethylacetate, vinyl ~diethylacetate, vinyl valerate, vinyl caproate, vinyl chloro-acetat~e, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl phenylacetate, vinyl acetoacetate, vinyl lactate, vinyl propionate, vinyl beta-phenylbutylate, vinyl ~; ~ ; cyclohexanecarboxylate, vinyl benzoate, vinyl salicylate, , :~ ,. . .
vinyl chlorobenzoate, vinyl tetrachlorobenzoate and vinyl naphthoate; styrenes, such as styrnee itself, alkylstyrenes, ; e.g., p-methylstyrene, o-methylstyrene, 2,4-dimethylstyrene, . .
~ trimethylstyrene, p-ethylstyrene, ~,4-diethylstyrene, o-isopropyl-. , ~ , ~ . .
~ styrene, p-butylstyrene, p-hexylstyrene, alpha methyl styrene, ' ' , ,: ' . ! , ~ ~ , .
: :
~ 4~;~46 p-cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethyl-styrene, trifluoromethylstyrene, ethoxymethylstyrene and acetoxymethylstyrene, alkoxystyrenes, e.g., p-methoxystyrene,
4-methoxy-3-methylstyrene and dimethoxystyrene, and halogeno-~ ~ ~i . . 7' ~' ' ~5 ~ styrenes, e.g., p-chlorostyrene, 2,4-dichlorostyrene, tri-chlorostyrene, tetrachlorostyrene, pentachlorostyrene, ` ~ p-bromostyrene, 2,4-dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2 bromo-4-trifluoromethylstyrene and 4-fluoro-.
3-trifluoromethylstyrene; organla crotonates, such as alkyl ., ~ lO ~ crotonates, e.g., butyl crotonate, hexyl crotonate and glycerol .. . . .. . .
~ monocrotonate; dialkyl itaconates, e.g., dimethyl itaconate, . .
diethyl itaconate and dibutyl itaconate; dialkyl maleates and ` ~ ~ fumarates, e.g., dimethyl maleate, diethyl maleate, diethyl i~ fumarate and dibutyl fumarate; acrylonitrile; methacrylonitrile;
15~ ~and the like. In addition, there can be used any addition-polymerizable u~saturated compounds capable of copolymerizing ~with the compound represented by ~he above general formula ~II).
However, addition-polymerizable unsaturated compounds having a functional group capable of reacting with the hydroxyl ~20 ~ ~ group of beta-hydroxyalkyl acrylates or methacrylates and ,, ~ polyfunctional addition-polymerizable unsaturated compounds ,, . ': : "': , !
having 2 or more polymerizable vinyl groups in the molecule are not preferred. A compound represented by the above general formula ; (II) is copolymerized with one or more of such addition-polymer-. ;,.. .. .
-`~ 25 ~izable unsatura~ed compounds as mentioned above to obtain the i ` ~;- copolymerizates of the present invention. Among the comonomers ... .~. ~ . . ~
to be copolymerized with a compound represented by the above ~;'.'': ', ~
::. :., , . ~ , .
.
.
~L 0 413 9L 6 ~ ~ general formula (II), those of relatively low oleophilic , properties bring about a better result than those of relatively high oleophilic properties. Methyl methacrylate and acrylo-nitrile bring about the best results. Al~hough a water-soluble ,. , , ~ i, ~ ; i ~
~addition-polymerizable unsaturated compound, such as acrylic acid, methacrylic acid, acrylamide or methacrylamide, is not preferred, it can be used in a small amount as the third component in combination with an other addition-polymerizable ~ unsaturated compound to form a terpolymer. Addition-polymer-^~lO~ ~ izable unsaturated compounds having amino group are not preferred because their copolymers with a compound of the general formula ~!~
II) have a tendency to deaompose diazo compounds.
The pol prepared in the usual ways although the compounds of the general ~ formula (II) preferably have a higher purity than the normally commercially available purity. Most commercial compounds contain , . ., .~,~ , . . .up to about 1% by weight of polyfunctional addition-polymerizable unsaturated compounds, e.g.; 0.1 - 0.3~ of ethylene glycol di- ~
methacrylate and about 0.5%, e.g., 0.05 - 0.2% by weight of free ~ -20~ ` acrylic acid or methacrylic acid. The former impurity often 9~`~':','''''`~,'',~ causes gelation of the polymerization mixture and the latter has an ad~erse effect on the characteristics of a photosensitive pla~e prepared from the polymer and a diazo compound.
` ~ }~ The content of the compound of the above general ;25 ~; ~ formulà (II) in~the polymer of the present invention may vary within the range of from 100% by weight to about 50~ by weight, preferably from about 80% by weight to about 65~
by weight.~ The polymer des1rably has a molecular weight within 30 ~ the range of from about 10,000 to about 100,000, preferably from about 30,000 to about 70,000, as determined by gel-permeation , . . . . .
L3~6 ' chroma ography. However, this can be varied.
i '' The polymer used in thb present invention is .
insoluble'in water but swollen by a solution of a water and wetting agent or'water and alcohol or even water alone. When ' a combination of the polymerizate with a diazo'compound~'is contacted with a developing solution comprising water and a ~ -wetting agent, the polymer is swollen in the developing solution to exude an unhardened diazo compound, and as a result, the ' combination in the unexposed area is removed to develop a ~10 relief image.
A polymer in which the content o the recurring units '' ` represented by the above general ormula ~1) is less than about 50% by weight gives a photosensitive plate which is difficult ~ to be developed by a solution of water and wetting agent. In-f~ s ~i~ crease of the amount of a diazo compound for improving the developing property causes a decrease of photosensitivity.
The diazo compound is p~Lff~a~y used in an amount '''' ' ;~;~of about 5 to about 50% by weight based on the total weight ., :,,..: ~ ~: . .
;''' '' ` o the pol~mer and diazo compound. As the amount o a diazo .' " : ' 'I ' ~ ! ~ .
~20 ~ 'compound decreases, the photosensitivity is enhanced but the . 1 ` ,~.' ..~ : . ~
developing property by a mixture including a water and wetting agent is degraded~ The optimum amount of a ~iazo compound is about~lO to about 30~ by weight.
' In the photosensitive composition of the present 25~ - invention there can be'incorporated another resin in an amount of up to about 50~ by weight of the` aforesaid polymer. As ''the other resin'suitably there are used those having, e.g., hydroxyl, amide or urethane groups in the molecule and 'I' i ~ , '~ ~-; compatible with the aforesaid polymerizate,' such as polyamide ; ~-6_10 co~olvmerJ
' 30~ resins, e.g., nylo~ fn ~ -6, epoxy resin, e.g., bisphenol l6 -. .. .....
.. . . . . ~ .: .. .
34~
, ''' A-epichlorhydrin, polyurethane resins, e.g., polyethylene : glycol Mol. Wt. 2000 - toluene diisocyanate r~action product, - and polyvinyl formal resin. By incorporation of such a resin " ' there is obtainable some improvement in abrasion resistance.
~ ~ .r~ . * ~
Improvements in some properties may be obtained by addition of ' ~ dye, pigment, stabilizer, filler and other additives. Dyes .
; which will be discolored during development or react with a diazo compound are unsuitable for use as a dye for enhancing i, ~ ~ ,,-; ,~
,' ' " the visual con~ras~ between a support surface and an image : l ' ';' ' ''i' 10~'" area o a developed plate. Examples o the dyes which are ., j, , .;'.,1; ,,':~,~ suitable include oil-soluble dyes isuch as, e-g-, Oil Blue l'"" '-; ~ ~ h'ki Ka'shal sen splron ue GN an isen Spiron Red 2BH supplied by Hodogaya Kagaku Kogyo Kabushiki Kaisha, Zapon Fast airly Red B supplied by Badische Anilin & Soda Fabrik A.G., I5-~ Oil Orange (C.I. 12,055), Oil Black 2HB ~C.I. 50,415), ,' r~;~ Oil BIue G Extra~(C.I. 61,525), Oil Orange SS ~C. I. 12,100), Oil Red ~C. I. 26,105), Oil Red AS ~C. I. 26,100), Oil Red XO
' (C~ I. 12,140), Oil Violet (C. I. 26,050), Oil Yellow OB
' ';'~ (C.I. 11,3g0), Oil Yellow BB (C. I. 11,020), Nigrosine -l'.20 '~Solvent Blue (C. I. 864), Spirit Blue CR (C.I. 689~, Oil Blue N, Oil Red 4B, Oil Bordeaux (Solvent Red 4), Oil Red B
(Solvent Red 24), Indirubin ~olvent Blue 7), Oil Brown BB
'(Solvent Brown 5), Spirit Black (Solvent Black 5). A compound ~ having the following general formula is preferable:
i~ . i,`. 2 5 , ': ', ~ ' 4~L346 ~ ~ R2 - C --N(R3)2 l ~ /> ~ ~
~-- ~ N(R3)2(OH) ,. ~ , .
,`': ': ~ ~, ~;, ,,. ~,,- ......
~ wherein Rl represents hydrogen atom, an alkyl group, preferably, i~ e.g., methyl group, or an alkoxy group, preferably, e.g., ~, methoxy group, and R2 and R3 represent hydrogen atom or an ` 5 ~ alkyl group, preferably, e.g., a methyl or ethyl group. These oil soluble dyes may be incorporated with the composition usually in an amount of about 0.5 to about 10%, preferably abou~ 2 tio ; about 5% by weight based on the polymer. Thus, if these oil~
soluble dyes aré incorporated with the composition, these dyes may be faded by exposure to actinic light.
~.; 1 , -:: . . ;.
~ The photosensitive composition of the present invention "~, ., , ~
;~ ; , is suitable for use as a photosensitive layer of a photo- -sensitive planographic plate. The suitable support includes, e.g~, paper and sheets or foils of plastic such as polyvinyl 15~ acetate, zinc, copper, aluminum, stainless steel, surface-~ = treated steel and like metals, and glass. The surface of a :':i' !`~,'!~`~'',''.'','`'"~'.'-"' support is usually passivated to hinder a harmful interaction ~,/ ','5~ ' between the surface and a diazo compound prior to application 'J~,'`"~'~', `'.'"~'. thereto of a coating composition- The passivation treatment ~; aids a firm bonding between the support and the exposed area of ' ' i ' ': ': ' ' : ' . ' :. ' . ' ,' ~ , .,,, ,, , . , : : : : .
~ . ~ . , ~ , .. . . .
~(~4~346 a coating and enhances the naked surface of the support during printing. The silicate treatment as disclosed in United States Patent No. 2,714,066, is a suitable passivation process for metallic supports. Other passivating processes are treatment by an aqueous potassium fluorozirconate as disclosed in United States Patent No. 2,946,683, phosphomolybdate treatment as disclosed in United States Patent No. 3,201,247, and silicate electro-deposition as disclosed in United States Patent No.
3,658,662. Still another process is a silicate treatment following an anodic oxidation in phosphoric or sulphuric acid as described in United States Patent No. 3,181,461.
The amount of the photosensitive composition applied to a support can range from about 0.5 to 5 g/m2, preferably from about 0.5 to about 2.5 g/m2 and most preferably about 0.7 to ` about 1.5 g/m2.
A photosensitive planographic plate in which there is used the photosensitive composition of the present invention, when exposed through a negative transparency to actinic light, changes the solubility of the photosensitive layer in the exposed area and results in a difference in degree of swelling by a developing solution. Development is performed by contacting the photosensitive layer with a developing solution comprising - an aqueous solution of a wetting agentO A preferred developingsolution is an aqueous solution of sodium lauryl sulfate of industrial grade sole under the trademark "MONOGEN" Y-lQ0 by ., ~ Dai-ichi Kogyo Seiyaku Kabushiki Kaisha, Japan. Examples of : ., .
other useful wetting agents are sodium-lauryl, lauryl '' :
.
.
., benzene sulfonate, sodium octyl sulfate, ammonium lauryl . . .
' sulfate, sodium xylenesulfonate, monosodium N~,N-dihydroxy-glycine and the like. As the concentration of the wetting agent increases the developing time'decreases. ,The wetting' ' k~
agent is used in a concentration of about 0.005 to about ' ~ 30%, preferably about 0.5 to about 10%, more desirably about 2 to about 6% by weight. The a~ueous wetting agent developing i solution can remove the photosensitive composition in the '~ unexposed area without 'xemoval in the exposed area or with ' ;~ 10 only slight rf~moval in the exposed area. To the wet~ing agent ; solution there can be added sodium silicate, magnesium sulfate, ~' magnesium nitrate or like compound in an amount of about 0.1 ' to about 10%, preferably about 0.5 to about 2% by weight based on the total weight of the developing solution to keep .. l . ;
S-~, .
r" j '.:;~ '15 ' the blanket of a press clean during printing. Developing latitude in development can be broadened by addition to the t; ~
'i'"'';'~"' developing solution of a small amount of a water-misci~le oryanic solvent such as benzyl alcohol.
'' The photosensitive composition of the present ; 20 invention can be used in the preparation of photoresist materials ., . :
f~ and photo masks, too.
-. ~ ~, .
~ ; Hereinafter, some embodiments of the present inventi~n . " ~
~ will be 'illustrated in more'detail by the following examples, in :f f , ~
' which all percents are by weight.
~ 25 ~
Ç`'." ;``' ~ 20 , ,. .: .: . . ~ . ..
., . .
' '' .: ' - ;. . ' .
'~ ' ' ' :" ' ' ' . ~:; , , . 1, .
1~41346 ~ EXAMPLE 1: ~
. .
~ 180 g of 2 methoxyethanol was heate~ in a stream ., I - .
~ ; of nitrogen gas at 100C. and a mixture of 100 g of beta-i ~ hydroxyethyl methacrylate and 0.75 g of benzoy peroxide was
3-trifluoromethylstyrene; organla crotonates, such as alkyl ., ~ lO ~ crotonates, e.g., butyl crotonate, hexyl crotonate and glycerol .. . . .. . .
~ monocrotonate; dialkyl itaconates, e.g., dimethyl itaconate, . .
diethyl itaconate and dibutyl itaconate; dialkyl maleates and ` ~ ~ fumarates, e.g., dimethyl maleate, diethyl maleate, diethyl i~ fumarate and dibutyl fumarate; acrylonitrile; methacrylonitrile;
15~ ~and the like. In addition, there can be used any addition-polymerizable u~saturated compounds capable of copolymerizing ~with the compound represented by ~he above general formula ~II).
However, addition-polymerizable unsaturated compounds having a functional group capable of reacting with the hydroxyl ~20 ~ ~ group of beta-hydroxyalkyl acrylates or methacrylates and ,, ~ polyfunctional addition-polymerizable unsaturated compounds ,, . ': : "': , !
having 2 or more polymerizable vinyl groups in the molecule are not preferred. A compound represented by the above general formula ; (II) is copolymerized with one or more of such addition-polymer-. ;,.. .. .
-`~ 25 ~izable unsatura~ed compounds as mentioned above to obtain the i ` ~;- copolymerizates of the present invention. Among the comonomers ... .~. ~ . . ~
to be copolymerized with a compound represented by the above ~;'.'': ', ~
::. :., , . ~ , .
.
.
~L 0 413 9L 6 ~ ~ general formula (II), those of relatively low oleophilic , properties bring about a better result than those of relatively high oleophilic properties. Methyl methacrylate and acrylo-nitrile bring about the best results. Al~hough a water-soluble ,. , , ~ i, ~ ; i ~
~addition-polymerizable unsaturated compound, such as acrylic acid, methacrylic acid, acrylamide or methacrylamide, is not preferred, it can be used in a small amount as the third component in combination with an other addition-polymerizable ~ unsaturated compound to form a terpolymer. Addition-polymer-^~lO~ ~ izable unsaturated compounds having amino group are not preferred because their copolymers with a compound of the general formula ~!~
II) have a tendency to deaompose diazo compounds.
The pol prepared in the usual ways although the compounds of the general ~ formula (II) preferably have a higher purity than the normally commercially available purity. Most commercial compounds contain , . ., .~,~ , . . .up to about 1% by weight of polyfunctional addition-polymerizable unsaturated compounds, e.g.; 0.1 - 0.3~ of ethylene glycol di- ~
methacrylate and about 0.5%, e.g., 0.05 - 0.2% by weight of free ~ -20~ ` acrylic acid or methacrylic acid. The former impurity often 9~`~':','''''`~,'',~ causes gelation of the polymerization mixture and the latter has an ad~erse effect on the characteristics of a photosensitive pla~e prepared from the polymer and a diazo compound.
` ~ }~ The content of the compound of the above general ;25 ~; ~ formulà (II) in~the polymer of the present invention may vary within the range of from 100% by weight to about 50~ by weight, preferably from about 80% by weight to about 65~
by weight.~ The polymer des1rably has a molecular weight within 30 ~ the range of from about 10,000 to about 100,000, preferably from about 30,000 to about 70,000, as determined by gel-permeation , . . . . .
L3~6 ' chroma ography. However, this can be varied.
i '' The polymer used in thb present invention is .
insoluble'in water but swollen by a solution of a water and wetting agent or'water and alcohol or even water alone. When ' a combination of the polymerizate with a diazo'compound~'is contacted with a developing solution comprising water and a ~ -wetting agent, the polymer is swollen in the developing solution to exude an unhardened diazo compound, and as a result, the ' combination in the unexposed area is removed to develop a ~10 relief image.
A polymer in which the content o the recurring units '' ` represented by the above general ormula ~1) is less than about 50% by weight gives a photosensitive plate which is difficult ~ to be developed by a solution of water and wetting agent. In-f~ s ~i~ crease of the amount of a diazo compound for improving the developing property causes a decrease of photosensitivity.
The diazo compound is p~Lff~a~y used in an amount '''' ' ;~;~of about 5 to about 50% by weight based on the total weight ., :,,..: ~ ~: . .
;''' '' ` o the pol~mer and diazo compound. As the amount o a diazo .' " : ' 'I ' ~ ! ~ .
~20 ~ 'compound decreases, the photosensitivity is enhanced but the . 1 ` ,~.' ..~ : . ~
developing property by a mixture including a water and wetting agent is degraded~ The optimum amount of a ~iazo compound is about~lO to about 30~ by weight.
' In the photosensitive composition of the present 25~ - invention there can be'incorporated another resin in an amount of up to about 50~ by weight of the` aforesaid polymer. As ''the other resin'suitably there are used those having, e.g., hydroxyl, amide or urethane groups in the molecule and 'I' i ~ , '~ ~-; compatible with the aforesaid polymerizate,' such as polyamide ; ~-6_10 co~olvmerJ
' 30~ resins, e.g., nylo~ fn ~ -6, epoxy resin, e.g., bisphenol l6 -. .. .....
.. . . . . ~ .: .. .
34~
, ''' A-epichlorhydrin, polyurethane resins, e.g., polyethylene : glycol Mol. Wt. 2000 - toluene diisocyanate r~action product, - and polyvinyl formal resin. By incorporation of such a resin " ' there is obtainable some improvement in abrasion resistance.
~ ~ .r~ . * ~
Improvements in some properties may be obtained by addition of ' ~ dye, pigment, stabilizer, filler and other additives. Dyes .
; which will be discolored during development or react with a diazo compound are unsuitable for use as a dye for enhancing i, ~ ~ ,,-; ,~
,' ' " the visual con~ras~ between a support surface and an image : l ' ';' ' ''i' 10~'" area o a developed plate. Examples o the dyes which are ., j, , .;'.,1; ,,':~,~ suitable include oil-soluble dyes isuch as, e-g-, Oil Blue l'"" '-; ~ ~ h'ki Ka'shal sen splron ue GN an isen Spiron Red 2BH supplied by Hodogaya Kagaku Kogyo Kabushiki Kaisha, Zapon Fast airly Red B supplied by Badische Anilin & Soda Fabrik A.G., I5-~ Oil Orange (C.I. 12,055), Oil Black 2HB ~C.I. 50,415), ,' r~;~ Oil BIue G Extra~(C.I. 61,525), Oil Orange SS ~C. I. 12,100), Oil Red ~C. I. 26,105), Oil Red AS ~C. I. 26,100), Oil Red XO
' (C~ I. 12,140), Oil Violet (C. I. 26,050), Oil Yellow OB
' ';'~ (C.I. 11,3g0), Oil Yellow BB (C. I. 11,020), Nigrosine -l'.20 '~Solvent Blue (C. I. 864), Spirit Blue CR (C.I. 689~, Oil Blue N, Oil Red 4B, Oil Bordeaux (Solvent Red 4), Oil Red B
(Solvent Red 24), Indirubin ~olvent Blue 7), Oil Brown BB
'(Solvent Brown 5), Spirit Black (Solvent Black 5). A compound ~ having the following general formula is preferable:
i~ . i,`. 2 5 , ': ', ~ ' 4~L346 ~ ~ R2 - C --N(R3)2 l ~ /> ~ ~
~-- ~ N(R3)2(OH) ,. ~ , .
,`': ': ~ ~, ~;, ,,. ~,,- ......
~ wherein Rl represents hydrogen atom, an alkyl group, preferably, i~ e.g., methyl group, or an alkoxy group, preferably, e.g., ~, methoxy group, and R2 and R3 represent hydrogen atom or an ` 5 ~ alkyl group, preferably, e.g., a methyl or ethyl group. These oil soluble dyes may be incorporated with the composition usually in an amount of about 0.5 to about 10%, preferably abou~ 2 tio ; about 5% by weight based on the polymer. Thus, if these oil~
soluble dyes aré incorporated with the composition, these dyes may be faded by exposure to actinic light.
~.; 1 , -:: . . ;.
~ The photosensitive composition of the present invention "~, ., , ~
;~ ; , is suitable for use as a photosensitive layer of a photo- -sensitive planographic plate. The suitable support includes, e.g~, paper and sheets or foils of plastic such as polyvinyl 15~ acetate, zinc, copper, aluminum, stainless steel, surface-~ = treated steel and like metals, and glass. The surface of a :':i' !`~,'!~`~'',''.'','`'"~'.'-"' support is usually passivated to hinder a harmful interaction ~,/ ','5~ ' between the surface and a diazo compound prior to application 'J~,'`"~'~', `'.'"~'. thereto of a coating composition- The passivation treatment ~; aids a firm bonding between the support and the exposed area of ' ' i ' ': ': ' ' : ' . ' :. ' . ' ,' ~ , .,,, ,, , . , : : : : .
~ . ~ . , ~ , .. . . .
~(~4~346 a coating and enhances the naked surface of the support during printing. The silicate treatment as disclosed in United States Patent No. 2,714,066, is a suitable passivation process for metallic supports. Other passivating processes are treatment by an aqueous potassium fluorozirconate as disclosed in United States Patent No. 2,946,683, phosphomolybdate treatment as disclosed in United States Patent No. 3,201,247, and silicate electro-deposition as disclosed in United States Patent No.
3,658,662. Still another process is a silicate treatment following an anodic oxidation in phosphoric or sulphuric acid as described in United States Patent No. 3,181,461.
The amount of the photosensitive composition applied to a support can range from about 0.5 to 5 g/m2, preferably from about 0.5 to about 2.5 g/m2 and most preferably about 0.7 to ` about 1.5 g/m2.
A photosensitive planographic plate in which there is used the photosensitive composition of the present invention, when exposed through a negative transparency to actinic light, changes the solubility of the photosensitive layer in the exposed area and results in a difference in degree of swelling by a developing solution. Development is performed by contacting the photosensitive layer with a developing solution comprising - an aqueous solution of a wetting agentO A preferred developingsolution is an aqueous solution of sodium lauryl sulfate of industrial grade sole under the trademark "MONOGEN" Y-lQ0 by ., ~ Dai-ichi Kogyo Seiyaku Kabushiki Kaisha, Japan. Examples of : ., .
other useful wetting agents are sodium-lauryl, lauryl '' :
.
.
., benzene sulfonate, sodium octyl sulfate, ammonium lauryl . . .
' sulfate, sodium xylenesulfonate, monosodium N~,N-dihydroxy-glycine and the like. As the concentration of the wetting agent increases the developing time'decreases. ,The wetting' ' k~
agent is used in a concentration of about 0.005 to about ' ~ 30%, preferably about 0.5 to about 10%, more desirably about 2 to about 6% by weight. The a~ueous wetting agent developing i solution can remove the photosensitive composition in the '~ unexposed area without 'xemoval in the exposed area or with ' ;~ 10 only slight rf~moval in the exposed area. To the wet~ing agent ; solution there can be added sodium silicate, magnesium sulfate, ~' magnesium nitrate or like compound in an amount of about 0.1 ' to about 10%, preferably about 0.5 to about 2% by weight based on the total weight of the developing solution to keep .. l . ;
S-~, .
r" j '.:;~ '15 ' the blanket of a press clean during printing. Developing latitude in development can be broadened by addition to the t; ~
'i'"'';'~"' developing solution of a small amount of a water-misci~le oryanic solvent such as benzyl alcohol.
'' The photosensitive composition of the present ; 20 invention can be used in the preparation of photoresist materials ., . :
f~ and photo masks, too.
-. ~ ~, .
~ ; Hereinafter, some embodiments of the present inventi~n . " ~
~ will be 'illustrated in more'detail by the following examples, in :f f , ~
' which all percents are by weight.
~ 25 ~
Ç`'." ;``' ~ 20 , ,. .: .: . . ~ . ..
., . .
' '' .: ' - ;. . ' .
'~ ' ' ' :" ' ' ' . ~:; , , . 1, .
1~41346 ~ EXAMPLE 1: ~
. .
~ 180 g of 2 methoxyethanol was heate~ in a stream ., I - .
~ ; of nitrogen gas at 100C. and a mixture of 100 g of beta-i ~ hydroxyethyl methacrylate and 0.75 g of benzoy peroxide was
5;~ added dropwise thereto over 2 hours. To the reaction mixture ` ~ there was then added dropwise a mixture of 20 g of 2-methoxy-~ ~ , ethanol and 0.25 g of benzoyl peroxide over 15 minutes. The reaction was continued at 100C. for an additional 3 hours to obtain a methoxyethanol solution of poly(beta-hydroxyethyl ~ ~ methacrylat) having a non-volatile matter content of 32%.
; The viscosity of this solution was 1,500 cps.
; A 2S aluminum sheet was immersed for 3 minutes in a 10% aqueous solution of tertiary sodium phosphate maintained `at 80C. to degrease it, washed with water, and then desmutted ~ by means of a 70% aqueous nitric acid, washed with water, immersed for 1 minute in a 3~ aqueous solution of sodium silicate maintained at 70C. washed with water and dried. A photosen-sitive solution of the following composition was applied to the ; smooth-surfaced aluminum sheet thus pretrea~ed by means of a ~ ~ wire and dried at 100C. for 2 minutes.
~, ~
h, .,. ~ . .
~L0~13~f~
32% Solution in 2-methoxyethanol of poly ~beta-hydroxyethyl methacrylate). 2.40 g An acrylic urethane compound prepared by reacting "CORONATE L" (trade mark for an adduct of 3 moles of 2,4-toluene diisocyanate to one mole of tri-methylol-propane, supplied by Nippon Polyurethane Xogyo Kabushiki Kaisha, with beta-hydroxyethyl acrylate in the equal proportions with respect to functional groups, i.e., NCO:OH = 1:1. 0.20 g 10 2-Methoxy-4-hydroxy-5-benzoylbenzene-sulfonate of a condensate of p-diazodi-` phenylamine with para formaldehyde. 0.20 g Oil Blue #603 (Orient Kagaku Kogyo Kabushiki Kaisha~. 0.03 g 2-Methoxyethanol 20.00 g Methanol 5-00 g -. The weight of dried coating was 0.98 g/m2. The p.hoto-sensitive planographic plate was exposed for 30 seconds to a carbon arc lamp of 30 Amp. located 70 cm apart from the plate, . 20 immersed at room temperature for 1 minute in a developing .
solution of the following composition and the unexposea area removed by lightly rubbing it with an absorbent cotton to .:
obtain a planographic plate.
Benzyl alcohol 20.00 g ~.
40% aqueous solution of sodium silicate 10.00 g Monogen Y - 100 30.00 g :
~ Water 940 00 g : . .
''' ' ':
"',:
. ' :'`' ~, ~
~. . .
.
: ~ - 22 -: . ..: . , : . -., : ., . .: , . , -~)413~
. ~r.;len printing was carried out using the plate mounted on a press, the plate ex~ibited good olephilic properties - ~` in the image area and gave printed matter`with a very good ~:
reproducibility. . . ~~
;
, . ..
T~: 5. EXAMPLE 2:
.. . ._ - A conical flask was charged with 70 g of beta-hydroxyethyl methacrylate, 30 g of methyl methacrylate, 0.5 - ~ g of benzoin ethyl ether and 200 g of dioxane and exposed for .:4 hours to outdoor sunlight to synthesize a beta-hydroxy- ., ethyl methacrylate/methyl methacrylate copolymer. The copol~mier solution thus obtained had a non-volatile matter content of 31~ and the average molecular weight of the copolymer determined by gel permeation chromatography was 55,000.
To the same silicate-treated smooth-surfaced aluminum ,~, 15~ sheet as used in Example 1 and to an aluminum sheet which had been subjected to silicate treatment under the same condition as in Example l.and to an aluminum sheet which had been subjected to silicate treatment under the same condition as in Example 1, after sandblasting there was applied a ,;,~20 .photosensitive solution of the following composition.
` 31% Dioxane solution of beta-hydroxyethyl methacrylate ~ methyl methacrylate =70/
30 copolymer ~ 3.00 g .,`.1'"~'~ '~,.. ! '~:'~ ',' '~ " The same diaæo resin as used in Example 1 :0.20 g ,.~5 ~ Oil Blue.#6.03 0.03 g ; 2-Methoxyethanol ~ . 20.00 g Methanol 5 00 g Ethylene dichloride 5.00 g 134~
The weight of dried coating after coating at 100C
for 2 minutes of the photosensitive layer thus fo~med was 1.02 g/m in case of the smooth-surfaced aluminum sheet support and 1.20 g/m2 in case of the sand matted aluminum sheet support.
The photosensitive planographic plates were exposed for 40 seconds to a carbon arc lamp of 30 Amp. located 70 cm apart from the plate and developed at room temperature for 1 minute by immersing them in a developing solution of the following ~
composit on: ~ ;
Benzyl alcohol 5.00 g ~ ~
. . . j Magnesium sulfate heptahydrate 15.00 g Citric acid 5.00 g `~
Monogen Y - 10030.00 g Water 945.00 g After development, the plates were lightly rubbed with absorbent cotton to remove unexposed areas. The printing plate just developed and washed with water was mounted on a "ROTA" ~Trademark~ press (Nippon Jimuki Kabushiki Kaishal and printing was carried out. On this occasion, there were obtained .. ~ .
fine prints except for the initial S or 6 sheets. In the case of the smooth-surfaced support the printing durability was 18,000 and in the case of the sand matted support it was 47,000 sheets. It was found that the printing durability could be enhanced by about 50% by drying the developed and washed plate ;~
: .i at 100C for 5 minutes.
.
,,',''"' ' ' ~
. .
., .
;, ' ~
. j .
':
39L~;
In another test, developing was carried out using, in place of'the aforesaid acidic developing solution, an alkaline - ~ developing solution of the following composition.
.
.. . ..
40% Aqueous sodium silicate ~ lO.OOig ` 5 - Monogen Y - 100 20.00 y ! Water ' g .
~ ' The printing durability of the printing plate thus obtained .. . .
'' and having a smooth-surfaced aluminum sheet support was 15,000 , ;~ ' ' sheets and thus was lower than that of a printing plate developed by the aoresaid acidic developing solution.
I ..j ' ~ However, a blanket on the non-image area was less soiled by the plate developed by the alkaline developing solution ' containing sodium-silicate than by the plate developed by the alkaline developing solution.
... . . .
~15 ~ EXAMPLE 3-~" ' A beta-hydroxyethyl methacrylate ' methyl methacrylate=S0/so , ' " ~ copolymer was synthesized in a similar manner to that in ~' Example 2. The non-volatile'matter content of the copolymer ~-~ solution was 31% and the average molecular wei'ght as determined ~;~ ? ~ by a gel permeation chromatography of the copolymer was 30,000.
' To the same'silicate-treated smooth-surfaced aluminum sheet as in Example 2 there was applied a photosensitive :¢,~
solution of the following composition.
t ' - 2 5 -. . ~ . ~ . ..
~ '' ~' '; ' ~;":
,,~; ~.
., . ~ .
~i ~!~
31% Dioxane solution of beta-hydroxyethyl methac.ylate/methyl 3.00 g methacrylate=50/50 copolymer ; Diazo resin as used in Example l 0.40 g -~ 2-Methoxyethanol 2.00 g -. 5 Methanol -5.00,g Ethylene dichloride ' ' ' ~;OO g , The coated aluminum sheet was dried at 100C. for 2 minutes to obtain a photosensitive planographic plate having a photosensitive layer having a weight o~ dried coating of 0~79 g/m2.
: The photosensiti~e plate was exposed through a transparency ~or 100 seconds to a aarbon arc lamp of 30 Amp.
. .
located 70 cm apart from the plate and immersed at room tempera-. ~ . ture for 1 minute in the following developing solution to obtain 15 ~ a printing plate.
Benzyl alcohol 30.00 g n-Propyl alcohol 20.00 g ,,, . .:,. ~
; - 85% Phosphoric acid . 10.00 g i ;, .
Magnesium sulfate heptahydrate . . . 10.00 g .~ 20 . ~. Monogen Y-100 20.00 g Water ~ ~910.00 g The printing plate exhibited improved oleophilic properties in the image area compared to the printing plate of ~ Example 2, through the sensitivity of the photosensitive plate /~^',~ 25 ~ of this example was one half or less that of the photosensitive plate of Example 2.
: ~ . .
. . .
." .
EXAMPLE 4: 10~1346 To the same silicate-treated smooth-surfaced aluminum sheet as in Example 2 there was applied the following photo-sensitive solution: ~;
31% Dioxane solution of beta-hydroxyethyl 2.00 g methacrylate/methyl methacrylate = 70/30 Copolymer of Example 2 "ULTRAMIDE"(Trademark) IC àlcoholic solu~ 0.20 g ble polyamide, supplied by Badishe Aniline und Soda Fabrik., A.G., West Germany Diazo resin as used in Example 10.20 g 2-methoxyethanol 10.00 g ; Methanol 10.00 g Ethylene dichloride 10.00 g Oil Blue #603 0.04 g The coated sheet was dried at 100C or 2 minutes to obtain a photosensitive planographic plate having a photosen-sitive layer with a dried coating weight of 0.82 g/m2 The photosensitive plate was exposed to a carbon arc lamp of 30 Amp. located 70 cm apart from the plate for 40 seconds and developed by immersing at room temperature for 1 minute 1 in the following developing solution: ;
Benzyl alcohol 5.00 g 40~ Aqueous sodium silicate 10.00 g , .
Monogen Y - 100 30.00 g Water 995.00 g :
: .
~' .
i :, ~ .
;. . .
~ . .
`` ~ 27 -.. . .
: ~)4~46 :
... .
The printing plate thus obtained was superior in toughness o~ the resist in the image area and in the olephilic properties to the printing plate from the smooth-surfaced aluminum sheet in Example 2 and exhibited a printing durability on a R ot a press vf 18,000 sheets or more.
.~ .
; EXAMPLE 5:_ ;. . In this example, there was eMployed, in place of the diazo resin of Example 2, a diazo compound of the following . structural formula:
Complex salt of:
' .: ~: , . .
;.: , ~ .
~ SOH4C2H - C C - N~ ~ N2C1 '`~ I \C~ IC330-~-CO~~
. I . OC2H5 OH
¦ ;
. ~ : H5C2 ~ N2Cl ~ L
, ! : ' 1` ~ ' : ~ ' :
''' ,, ~,' ,~' ' ' ' : i ` , ~ . : ' ' '' " ' .~' i ' ~ i :
. ~,, ' ~, .~ ' .'' ~ . ' 1 i ~
. . ~ : _, . ..
" ~ ~
1. ', ~ .
'.,~' ' ' :
".. '.'~' ' ' ' . - 28 - ~
-~4~6 ' The same procedure as in Example 2 was followed :::
: except for the diazo compound employed to obtain a printing ~; material having a photosensitive layer with a dry coating weight of 0.96 g/m2.
S The printing material was exposed for' 40 secoh'ds''to : a carbon arc lamp of 30 Amp. located 70 cm apart therefrom - and developed by immersing it at room temperature for 1 minute . in the same developing solution containing sodium silicate as used in Example 4 to obtain a printing plate which was somewhat .
inferior in its oleophilic property but comparable in the other ' properties to the printing plate prepared from the smooth-".,' , ,; surfaced aluminum sheet in Example 2.
, ~ , ;, EXAMPLE 6: . . , . A conical flask was charged'with 60 g of monomethacrylate ,",'15~ ' of a poly(oxypropylene) glycol of an average molecular weight ,,:,'~' of 250, 40 g of methyl methacrylate, 1 g of benzoin ethyl ". . :'ether as a photopolymerization initiator and 200 g of dioxane ' as a solvent and exposed for 4 days to outdoor sunlight to ~;~ ,, prepare a poly(oxypropylene)glycol monomethacrylate - methyl .~ 20'~, methacrylate copolymer solution with a non-volatile matter content of 30.5~. -To the same'silicate-treated smooth-surfaced aluminum ;' ' sheet as used in Example 1 there was applied the following 'y,,l ~ photosensitive solution. The application and drying of the ,;.,, ~ , , ~photosensitive'solution were carried out under the same manner as;in Example 1.' 2 g ;; ~. : . . .
.~ , .. . .
., ~ , ~: . ~ : ' ' 1~4~3~6 30.5% Dioxane solution of poly(oxypropylene)3.00 g glycol monomethacrylate copolymer Diazo resin of Example 1 0.40 g 2-Methoxyethanol 20.00 g ; , . ~ .
S Methanol ~ 5~00 g - Ethylene dichloride 5.00 g . . .
. , .
,,l .
The dry coating weight was 1.06 g/m2. The photo-sensitive planographic plate was exposed imagewise for 60 seconds to a carbon arc lamp of 30 Amp. loca~ed 70 cm apart ., therefrom, then soaked at room temperature for 1 minute in the same acidic developing solution as in Example 2 and lightly rubbed by absorbent cotton for removal of the unexposed area to obtain a planographic plate. The printing plate, on a press, exhibited good oleophilic properties in the image area and , ~., 15~ ` gave fine prints with a high reproducibility.
,, . ~ . ,~ , .: , 1. ~ I . , , ~
~ 30 -, , ,, . ,~; ~ , : ' :, :
. . :
; The viscosity of this solution was 1,500 cps.
; A 2S aluminum sheet was immersed for 3 minutes in a 10% aqueous solution of tertiary sodium phosphate maintained `at 80C. to degrease it, washed with water, and then desmutted ~ by means of a 70% aqueous nitric acid, washed with water, immersed for 1 minute in a 3~ aqueous solution of sodium silicate maintained at 70C. washed with water and dried. A photosen-sitive solution of the following composition was applied to the ; smooth-surfaced aluminum sheet thus pretrea~ed by means of a ~ ~ wire and dried at 100C. for 2 minutes.
~, ~
h, .,. ~ . .
~L0~13~f~
32% Solution in 2-methoxyethanol of poly ~beta-hydroxyethyl methacrylate). 2.40 g An acrylic urethane compound prepared by reacting "CORONATE L" (trade mark for an adduct of 3 moles of 2,4-toluene diisocyanate to one mole of tri-methylol-propane, supplied by Nippon Polyurethane Xogyo Kabushiki Kaisha, with beta-hydroxyethyl acrylate in the equal proportions with respect to functional groups, i.e., NCO:OH = 1:1. 0.20 g 10 2-Methoxy-4-hydroxy-5-benzoylbenzene-sulfonate of a condensate of p-diazodi-` phenylamine with para formaldehyde. 0.20 g Oil Blue #603 (Orient Kagaku Kogyo Kabushiki Kaisha~. 0.03 g 2-Methoxyethanol 20.00 g Methanol 5-00 g -. The weight of dried coating was 0.98 g/m2. The p.hoto-sensitive planographic plate was exposed for 30 seconds to a carbon arc lamp of 30 Amp. located 70 cm apart from the plate, . 20 immersed at room temperature for 1 minute in a developing .
solution of the following composition and the unexposea area removed by lightly rubbing it with an absorbent cotton to .:
obtain a planographic plate.
Benzyl alcohol 20.00 g ~.
40% aqueous solution of sodium silicate 10.00 g Monogen Y - 100 30.00 g :
~ Water 940 00 g : . .
''' ' ':
"',:
. ' :'`' ~, ~
~. . .
.
: ~ - 22 -: . ..: . , : . -., : ., . .: , . , -~)413~
. ~r.;len printing was carried out using the plate mounted on a press, the plate ex~ibited good olephilic properties - ~` in the image area and gave printed matter`with a very good ~:
reproducibility. . . ~~
;
, . ..
T~: 5. EXAMPLE 2:
.. . ._ - A conical flask was charged with 70 g of beta-hydroxyethyl methacrylate, 30 g of methyl methacrylate, 0.5 - ~ g of benzoin ethyl ether and 200 g of dioxane and exposed for .:4 hours to outdoor sunlight to synthesize a beta-hydroxy- ., ethyl methacrylate/methyl methacrylate copolymer. The copol~mier solution thus obtained had a non-volatile matter content of 31~ and the average molecular weight of the copolymer determined by gel permeation chromatography was 55,000.
To the same silicate-treated smooth-surfaced aluminum ,~, 15~ sheet as used in Example 1 and to an aluminum sheet which had been subjected to silicate treatment under the same condition as in Example l.and to an aluminum sheet which had been subjected to silicate treatment under the same condition as in Example 1, after sandblasting there was applied a ,;,~20 .photosensitive solution of the following composition.
` 31% Dioxane solution of beta-hydroxyethyl methacrylate ~ methyl methacrylate =70/
30 copolymer ~ 3.00 g .,`.1'"~'~ '~,.. ! '~:'~ ',' '~ " The same diaæo resin as used in Example 1 :0.20 g ,.~5 ~ Oil Blue.#6.03 0.03 g ; 2-Methoxyethanol ~ . 20.00 g Methanol 5 00 g Ethylene dichloride 5.00 g 134~
The weight of dried coating after coating at 100C
for 2 minutes of the photosensitive layer thus fo~med was 1.02 g/m in case of the smooth-surfaced aluminum sheet support and 1.20 g/m2 in case of the sand matted aluminum sheet support.
The photosensitive planographic plates were exposed for 40 seconds to a carbon arc lamp of 30 Amp. located 70 cm apart from the plate and developed at room temperature for 1 minute by immersing them in a developing solution of the following ~
composit on: ~ ;
Benzyl alcohol 5.00 g ~ ~
. . . j Magnesium sulfate heptahydrate 15.00 g Citric acid 5.00 g `~
Monogen Y - 10030.00 g Water 945.00 g After development, the plates were lightly rubbed with absorbent cotton to remove unexposed areas. The printing plate just developed and washed with water was mounted on a "ROTA" ~Trademark~ press (Nippon Jimuki Kabushiki Kaishal and printing was carried out. On this occasion, there were obtained .. ~ .
fine prints except for the initial S or 6 sheets. In the case of the smooth-surfaced support the printing durability was 18,000 and in the case of the sand matted support it was 47,000 sheets. It was found that the printing durability could be enhanced by about 50% by drying the developed and washed plate ;~
: .i at 100C for 5 minutes.
.
,,',''"' ' ' ~
. .
., .
;, ' ~
. j .
':
39L~;
In another test, developing was carried out using, in place of'the aforesaid acidic developing solution, an alkaline - ~ developing solution of the following composition.
.
.. . ..
40% Aqueous sodium silicate ~ lO.OOig ` 5 - Monogen Y - 100 20.00 y ! Water ' g .
~ ' The printing durability of the printing plate thus obtained .. . .
'' and having a smooth-surfaced aluminum sheet support was 15,000 , ;~ ' ' sheets and thus was lower than that of a printing plate developed by the aoresaid acidic developing solution.
I ..j ' ~ However, a blanket on the non-image area was less soiled by the plate developed by the alkaline developing solution ' containing sodium-silicate than by the plate developed by the alkaline developing solution.
... . . .
~15 ~ EXAMPLE 3-~" ' A beta-hydroxyethyl methacrylate ' methyl methacrylate=S0/so , ' " ~ copolymer was synthesized in a similar manner to that in ~' Example 2. The non-volatile'matter content of the copolymer ~-~ solution was 31% and the average molecular wei'ght as determined ~;~ ? ~ by a gel permeation chromatography of the copolymer was 30,000.
' To the same'silicate-treated smooth-surfaced aluminum sheet as in Example 2 there was applied a photosensitive :¢,~
solution of the following composition.
t ' - 2 5 -. . ~ . ~ . ..
~ '' ~' '; ' ~;":
,,~; ~.
., . ~ .
~i ~!~
31% Dioxane solution of beta-hydroxyethyl methac.ylate/methyl 3.00 g methacrylate=50/50 copolymer ; Diazo resin as used in Example l 0.40 g -~ 2-Methoxyethanol 2.00 g -. 5 Methanol -5.00,g Ethylene dichloride ' ' ' ~;OO g , The coated aluminum sheet was dried at 100C. for 2 minutes to obtain a photosensitive planographic plate having a photosensitive layer having a weight o~ dried coating of 0~79 g/m2.
: The photosensiti~e plate was exposed through a transparency ~or 100 seconds to a aarbon arc lamp of 30 Amp.
. .
located 70 cm apart from the plate and immersed at room tempera-. ~ . ture for 1 minute in the following developing solution to obtain 15 ~ a printing plate.
Benzyl alcohol 30.00 g n-Propyl alcohol 20.00 g ,,, . .:,. ~
; - 85% Phosphoric acid . 10.00 g i ;, .
Magnesium sulfate heptahydrate . . . 10.00 g .~ 20 . ~. Monogen Y-100 20.00 g Water ~ ~910.00 g The printing plate exhibited improved oleophilic properties in the image area compared to the printing plate of ~ Example 2, through the sensitivity of the photosensitive plate /~^',~ 25 ~ of this example was one half or less that of the photosensitive plate of Example 2.
: ~ . .
. . .
." .
EXAMPLE 4: 10~1346 To the same silicate-treated smooth-surfaced aluminum sheet as in Example 2 there was applied the following photo-sensitive solution: ~;
31% Dioxane solution of beta-hydroxyethyl 2.00 g methacrylate/methyl methacrylate = 70/30 Copolymer of Example 2 "ULTRAMIDE"(Trademark) IC àlcoholic solu~ 0.20 g ble polyamide, supplied by Badishe Aniline und Soda Fabrik., A.G., West Germany Diazo resin as used in Example 10.20 g 2-methoxyethanol 10.00 g ; Methanol 10.00 g Ethylene dichloride 10.00 g Oil Blue #603 0.04 g The coated sheet was dried at 100C or 2 minutes to obtain a photosensitive planographic plate having a photosen-sitive layer with a dried coating weight of 0.82 g/m2 The photosensitive plate was exposed to a carbon arc lamp of 30 Amp. located 70 cm apart from the plate for 40 seconds and developed by immersing at room temperature for 1 minute 1 in the following developing solution: ;
Benzyl alcohol 5.00 g 40~ Aqueous sodium silicate 10.00 g , .
Monogen Y - 100 30.00 g Water 995.00 g :
: .
~' .
i :, ~ .
;. . .
~ . .
`` ~ 27 -.. . .
: ~)4~46 :
... .
The printing plate thus obtained was superior in toughness o~ the resist in the image area and in the olephilic properties to the printing plate from the smooth-surfaced aluminum sheet in Example 2 and exhibited a printing durability on a R ot a press vf 18,000 sheets or more.
.~ .
; EXAMPLE 5:_ ;. . In this example, there was eMployed, in place of the diazo resin of Example 2, a diazo compound of the following . structural formula:
Complex salt of:
' .: ~: , . .
;.: , ~ .
~ SOH4C2H - C C - N~ ~ N2C1 '`~ I \C~ IC330-~-CO~~
. I . OC2H5 OH
¦ ;
. ~ : H5C2 ~ N2Cl ~ L
, ! : ' 1` ~ ' : ~ ' :
''' ,, ~,' ,~' ' ' ' : i ` , ~ . : ' ' '' " ' .~' i ' ~ i :
. ~,, ' ~, .~ ' .'' ~ . ' 1 i ~
. . ~ : _, . ..
" ~ ~
1. ', ~ .
'.,~' ' ' :
".. '.'~' ' ' ' . - 28 - ~
-~4~6 ' The same procedure as in Example 2 was followed :::
: except for the diazo compound employed to obtain a printing ~; material having a photosensitive layer with a dry coating weight of 0.96 g/m2.
S The printing material was exposed for' 40 secoh'ds''to : a carbon arc lamp of 30 Amp. located 70 cm apart therefrom - and developed by immersing it at room temperature for 1 minute . in the same developing solution containing sodium silicate as used in Example 4 to obtain a printing plate which was somewhat .
inferior in its oleophilic property but comparable in the other ' properties to the printing plate prepared from the smooth-".,' , ,; surfaced aluminum sheet in Example 2.
, ~ , ;, EXAMPLE 6: . . , . A conical flask was charged'with 60 g of monomethacrylate ,",'15~ ' of a poly(oxypropylene) glycol of an average molecular weight ,,:,'~' of 250, 40 g of methyl methacrylate, 1 g of benzoin ethyl ". . :'ether as a photopolymerization initiator and 200 g of dioxane ' as a solvent and exposed for 4 days to outdoor sunlight to ~;~ ,, prepare a poly(oxypropylene)glycol monomethacrylate - methyl .~ 20'~, methacrylate copolymer solution with a non-volatile matter content of 30.5~. -To the same'silicate-treated smooth-surfaced aluminum ;' ' sheet as used in Example 1 there was applied the following 'y,,l ~ photosensitive solution. The application and drying of the ,;.,, ~ , , ~photosensitive'solution were carried out under the same manner as;in Example 1.' 2 g ;; ~. : . . .
.~ , .. . .
., ~ , ~: . ~ : ' ' 1~4~3~6 30.5% Dioxane solution of poly(oxypropylene)3.00 g glycol monomethacrylate copolymer Diazo resin of Example 1 0.40 g 2-Methoxyethanol 20.00 g ; , . ~ .
S Methanol ~ 5~00 g - Ethylene dichloride 5.00 g . . .
. , .
,,l .
The dry coating weight was 1.06 g/m2. The photo-sensitive planographic plate was exposed imagewise for 60 seconds to a carbon arc lamp of 30 Amp. loca~ed 70 cm apart ., therefrom, then soaked at room temperature for 1 minute in the same acidic developing solution as in Example 2 and lightly rubbed by absorbent cotton for removal of the unexposed area to obtain a planographic plate. The printing plate, on a press, exhibited good oleophilic properties in the image area and , ~., 15~ ` gave fine prints with a high reproducibility.
,, . ~ . ,~ , .: , 1. ~ I . , , ~
~ 30 -, , ,, . ,~; ~ , : ' :, :
. . :
Claims (16)
1. A photosensitive composition, comprising (a) a diazo-aromatic compound which has been reacted with at least one coupling agent to form a reaction product which is at least partially soluble in organic solvents, has a light sensitivity not substantially less than the initial diazo-aromatic compound and is, at the most, slightly water soluble, and (b) a polymer containing 50 to 100% by weight of the recurring unit represented by the following general formula (I):
(I) wherein R1 represents a hydrogen atom or methyl group, R2 re-presents a hydrogen atom or a methyl, ethyl or chloromethyl group and n is an integer of from 1 to 10, the balance of the units of said polymer consisting essentially of units of a monoethylenically unsaturated compound which is selected from the group consisting of organic acrylates or methacrylates, acrylamide or methacrylamide, mono or di-N-alkyl-, cycloalkyl- or aryl-acrylamide or methacrylamide, hydroxy-alkyl or hydroxyaryl acrylamide or methacrylamide, allyl esters and ethers, vinyl ethers, vinyl esters, styrene, alkylstyrenes, halostyrenes, halomethyl styrenes, alkoxyalkyl styrenes, alkyl crotonates, dialkyl itaconates, dialkyl maleates, dialkyl fumarates, acrylonitrile and methacrylonitrile, said diazo-aromatic compound being present in an amount of about 5 to about 50% by weight based on the total weight of diazo-aromatic compound and polymer.
(I) wherein R1 represents a hydrogen atom or methyl group, R2 re-presents a hydrogen atom or a methyl, ethyl or chloromethyl group and n is an integer of from 1 to 10, the balance of the units of said polymer consisting essentially of units of a monoethylenically unsaturated compound which is selected from the group consisting of organic acrylates or methacrylates, acrylamide or methacrylamide, mono or di-N-alkyl-, cycloalkyl- or aryl-acrylamide or methacrylamide, hydroxy-alkyl or hydroxyaryl acrylamide or methacrylamide, allyl esters and ethers, vinyl ethers, vinyl esters, styrene, alkylstyrenes, halostyrenes, halomethyl styrenes, alkoxyalkyl styrenes, alkyl crotonates, dialkyl itaconates, dialkyl maleates, dialkyl fumarates, acrylonitrile and methacrylonitrile, said diazo-aromatic compound being present in an amount of about 5 to about 50% by weight based on the total weight of diazo-aromatic compound and polymer.
2. A photosensitive composition according to Claim 1, wherein said diazo-aromatic compound is contained in an amount of about 10 to 30% by weight based on the total weight of said polymerizate and said diazo-aromatic compound.
3. A photosensitive composition according to Claim 1, wherein said polymer is a copolymer containing 65 to 80% by weight of units of a compound represented by the following general formula (II):
(II) wherein R1 represents a hydrogen atom or a methyl group, R2 represents a hydrogen atom or a methyl, ethyl or chloromethyl group and n is an integer of 1 to 10.
(II) wherein R1 represents a hydrogen atom or a methyl group, R2 represents a hydrogen atom or a methyl, ethyl or chloromethyl group and n is an integer of 1 to 10.
4. A photosensitive composition according to Claim 1, wherein said polymer has a molecular weight within the range of from about 10,000 to 100,000.
5. A photosensitive composition according to Claim 1, wherein the polymer is a copolymer of a compound providing the units of formula I and an alkyl acrylate or methacrylate.
6. A photosensitive composition according to Claim 5, wherein the polymer is a copolymer of the compound providing the units of formula I and methyl methacrylate.
7. A photosensitive composition acccording to Claim 6, wherein the polymer is a copolymer of hydroxyethyl methacrylate and methyl methacrylate.
8. A photosensitive composition according to Claim 1, wherein the polymer is essentially hydroxyethyl methacrylate homopolymer.
9. A presensitized printing plate having a photosensitive layer including the composition of Claim 1.
10. A photoresist material containing the photosensitive composition according to Claim 1.
11. A photomask containing the photosensitive composition according to Claim 1.
12. A presensitized planographic printing plate which comprises a support having a layer comprising the photosensitive composition of Claim 1.
13. A presensitized printing plate according to Claim 12, wherein said layer is provided with the composition in amount of 0.5 to 5 g/m2.
14. A presensitized printing plate according to Claim 12, wherein the support is a sheet or foil selected from the group consisting of paper, plastic, metal and glass.
15. A presensitized printing plate according to Claim 14, wherein said support is aluminum.
16. A presensitized printing plate according to Claim 15, wherein the surface of said aluminum is a passivatably treated surface.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP48082850A JPS527364B2 (en) | 1973-07-23 | 1973-07-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1041346A true CA1041346A (en) | 1978-10-31 |
Family
ID=13785839
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA205,472A Expired CA1041346A (en) | 1973-07-23 | 1974-07-23 | Photosensitive composition |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4275138A (en) |
| JP (1) | JPS527364B2 (en) |
| CA (1) | CA1041346A (en) |
| DE (1) | DE2434912C2 (en) |
| FR (1) | FR2238952B1 (en) |
| GB (1) | GB1460978A (en) |
Families Citing this family (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS533216A (en) * | 1976-06-28 | 1978-01-12 | Fuji Photo Film Co Ltd | Diazo photosensitive composition |
| JPS5498613A (en) * | 1978-01-09 | 1979-08-03 | Konishiroku Photo Ind Co Ltd | Photosensitive composition |
| DE2933827A1 (en) * | 1979-08-21 | 1981-03-12 | Siemens AG, 1000 Berlin und 8000 München | METHOD FOR PRODUCING HIGH-TEMPERATURE-RESISTANT RELIEF STRUCTURES AND THE USE THEREOF. |
| EP0051080A1 (en) * | 1980-11-03 | 1982-05-12 | Howard A. Fromson | Aluminum lithographic plate with visible image and process |
| JPS5964396A (en) * | 1982-10-05 | 1984-04-12 | Fuji Photo Film Co Ltd | Plate surface protecting agent for planographic printing plate |
| US4511640A (en) * | 1983-08-25 | 1985-04-16 | American Hoechst Corporation | Aqueous developable diazo lithographic printing plates with admixture of polyvinyl acetate and styrene maleic acid ester copolymer |
| JPS60186837A (en) * | 1984-03-07 | 1985-09-24 | Somar Corp | Photosensitive composition |
| US4539285A (en) * | 1984-03-14 | 1985-09-03 | American Hoechst Corporation | Photosensitive negative diazo composition with two acrylic polymers for photolithography |
| DE3504658A1 (en) * | 1985-02-12 | 1986-08-14 | Hoechst Ag, 6230 Frankfurt | LIGHT-SENSITIVE MIXTURE AND RECORDING MATERIAL MADE THEREFOR |
| JPS63170646A (en) * | 1987-01-08 | 1988-07-14 | Konica Corp | Preparation of printing plate from photosensitive lithographic printing plate which is improved in developability and the like |
| JPH07117747B2 (en) * | 1987-04-21 | 1995-12-18 | 富士写真フイルム株式会社 | Photosensitive composition |
| US4914000A (en) * | 1988-02-03 | 1990-04-03 | Hoechst Celanese Corporation | Three dimensional reproduction material diazonium condensates and use in light sensitive |
| JP2668540B2 (en) * | 1988-03-03 | 1997-10-27 | 富士写真フイルム株式会社 | Photosensitive composition |
| JPH01307745A (en) * | 1988-06-07 | 1989-12-12 | Fuji Photo Film Co Ltd | Photosensitive recording material |
| DE4002397A1 (en) * | 1990-01-27 | 1991-08-01 | Hoechst Ag | Positive photosensitive mixt. contg. hydroxy-aralkyl acrylate polymer - and sensitiser, useful in printing plate mfr. and as photoresist |
| US5086143A (en) * | 1990-07-25 | 1992-02-04 | Eastman Kodak Company | Copolymers containing polyoxyalkylene side chains |
| DE69230237T2 (en) * | 1991-07-04 | 2000-02-17 | Mitsubishi Chem Corp | Light sensitive composition |
| US5698361A (en) * | 1991-10-07 | 1997-12-16 | Fuji Photo Film Co., Ltd. | Photosensitive composition |
| EP0583962B1 (en) * | 1992-08-17 | 1997-07-16 | Konica Corporation | Light-sensitive composition |
| DE4430680A1 (en) * | 1994-08-29 | 1996-03-07 | Hoechst Ag | Photosensitive mixture |
| US5731127A (en) * | 1995-04-11 | 1998-03-24 | Dainippon Ink And Chemicals, Inc. | Photosensitive composition and photosensitive planographic printing plate having a resin with urea bonds in the side chain |
| US6653427B2 (en) * | 2000-03-31 | 2003-11-25 | Avery Dennison Corporation | Hydrophilic polymers, pressure sensitive adhesives and coatings |
| US6706836B1 (en) | 2000-03-31 | 2004-03-16 | Avery Dennison Corporation | Hydrophilic polymers, pressure sensitive adhesives and coatings |
| US6743880B2 (en) | 2000-03-31 | 2004-06-01 | Avery Denison Corporation | Hydrophilic polymers and methods of preparation |
| US20090081592A1 (en) | 2007-09-26 | 2009-03-26 | Fujifilm Corporation | Fountain solution composition for lithographic printing and heat-set offset rotary printing process |
| US20090078140A1 (en) | 2007-09-26 | 2009-03-26 | Fujifilm Corporation | Fountain solution composition for lithographic printing and heat-set offset rotary printing process |
| JP2009083106A (en) | 2007-09-27 | 2009-04-23 | Fujifilm Corp | Lithographic printing plate surface protective agent and plate making method for lithographic printing plate |
| JP2009234247A (en) | 2008-03-07 | 2009-10-15 | Fujifilm Corp | Dampening water composition for lithographic printing and heat-set rotary offset printing process |
| JP5288268B2 (en) | 2009-03-25 | 2013-09-11 | 富士フイルム株式会社 | Dampening solution composition for lithographic printing and heat set-off ring printing method |
| JP5281130B2 (en) | 2011-07-05 | 2013-09-04 | 富士フイルム株式会社 | Dampening solution composition for lithographic printing |
Family Cites Families (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA614181A (en) * | 1961-02-07 | J. Mcgraw William | Photopolymerizable compositions, elements and processes | |
| NL35423C (en) * | 1931-12-09 | |||
| US2937085A (en) * | 1954-01-11 | 1960-05-17 | Ditto Inc | Composite photosensitive plate, and method of making printing plate therefrom |
| US2980534A (en) | 1956-12-17 | 1961-04-18 | Monsanto Chemicals | Photographic compositions and photographic elements |
| NL254617A (en) * | 1959-08-05 | |||
| US3418295A (en) * | 1965-04-27 | 1968-12-24 | Du Pont | Polymers and their preparation |
| JPS4910841B1 (en) * | 1965-12-18 | 1974-03-13 | ||
| US3549373A (en) * | 1966-03-19 | 1970-12-22 | Ricoh Kk | Negative-to-positive reversible copy sheet |
| GB1277029A (en) * | 1968-11-26 | 1972-06-07 | Agfa Gevaert | Photopolymerisation of ethylenically unsaturated organic compounds |
| JPS4818563B1 (en) * | 1969-03-07 | 1973-06-07 | ||
| US3679419A (en) * | 1969-05-20 | 1972-07-25 | Azoplate Corp | Light-sensitive diazo condensate containing reproduction material |
| US3837860A (en) * | 1969-06-16 | 1974-09-24 | L Roos | PHOTOSENSITIVE MATERIALS COMPRISING POLYMERS HAVING RECURRING PENDENT o-QUINONE DIAZIDE GROUPS |
| US3660097A (en) * | 1969-11-28 | 1972-05-02 | Polychrome Corp | Diazo-polyurethane light-sensitive compositions |
| JPS492286B1 (en) * | 1970-02-19 | 1974-01-19 | ||
| DE2053363C3 (en) * | 1970-10-30 | 1980-09-18 | Hoechst Ag, 6000 Frankfurt | Photosensitive mixture |
| US3778270A (en) * | 1970-11-12 | 1973-12-11 | Du Pont | Photosensitive bis-diazonium salt compositions and elements |
| US3715211A (en) * | 1971-02-01 | 1973-02-06 | Horizons Inc | Process and product of cold sealing an anodized aluminum article by a photo-polymerization process |
| IT948621B (en) * | 1971-02-19 | 1973-06-11 | Howson Algraphy Ltd | PROCEDURE FOR PRODUCING LITHOGRAPHIC PRINTING PLATES AND PLATES THIS OBTAINED |
| US3841874A (en) * | 1971-03-15 | 1974-10-15 | Xidex Corp | Method for improving the photographic characteristics of vesicular photographic materials |
| US3751257A (en) * | 1971-04-16 | 1973-08-07 | Minnesota Mining & Mfg | Polyamide-diazo resin composition |
| US3790382A (en) * | 1971-04-16 | 1974-02-05 | Minnesota Mining & Mfg | Fluorinated polyamide-diazo resin coating composition |
| US3859099A (en) * | 1972-12-22 | 1975-01-07 | Eastman Kodak Co | Positive plate incorporating diazoquinone |
| US4123276A (en) * | 1974-02-28 | 1978-10-31 | Fuji Photo Film Co., Ltd. | Photosensitive composition |
-
1973
- 1973-07-23 JP JP48082850A patent/JPS527364B2/ja not_active Expired
-
1974
- 1974-07-11 GB GB3083574A patent/GB1460978A/en not_active Expired
- 1974-07-19 DE DE2434912A patent/DE2434912C2/en not_active Expired
- 1974-07-23 CA CA205,472A patent/CA1041346A/en not_active Expired
- 1974-07-23 FR FR7425584A patent/FR2238952B1/fr not_active Expired
-
1976
- 1976-09-14 US US05/723,061 patent/US4275138A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| FR2238952A1 (en) | 1975-02-21 |
| FR2238952B1 (en) | 1978-11-24 |
| US4275138A (en) | 1981-06-23 |
| JPS527364B2 (en) | 1977-03-02 |
| DE2434912A1 (en) | 1975-02-06 |
| GB1460978A (en) | 1977-01-06 |
| JPS5030604A (en) | 1975-03-26 |
| DE2434912C2 (en) | 1983-08-11 |
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