CA1295169C - Adhesion promotion in photoresist lamination and processing - Google Patents
Adhesion promotion in photoresist lamination and processingInfo
- Publication number
- CA1295169C CA1295169C CA000531062A CA531062A CA1295169C CA 1295169 C CA1295169 C CA 1295169C CA 000531062 A CA000531062 A CA 000531062A CA 531062 A CA531062 A CA 531062A CA 1295169 C CA1295169 C CA 1295169C
- Authority
- CA
- Canada
- Prior art keywords
- substrate
- photosensitive layer
- formaldehyde
- layer
- areas
- 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 - Lifetime
Links
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces
- H05K3/0076—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces characterised by the composition of the mask
-
- 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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/12—Using specific substances
- H05K2203/122—Organic non-polymeric compounds, e.g. oil, wax, thiol
- H05K2203/124—Heterocyclic organic compounds, e.g. azole, furan
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
- H05K3/061—Etching masks
- H05K3/064—Photoresists
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/389—Improvement of the adhesion between the insulating substrate and the metal by the use of a coupling agent, e.g. silane
Abstract
TITLE
ADHESION PROMOTION IN
PHOTORESIST LAMINATION AND PROCESSING
ABSTRACTION OF THE INVENTION
Use of a photoresist is improved due to increased adhesive to a substrate through an additive in the resist of a condensation polymer of formaldehyde, toluene sulfonamide and either a triazine such as melamine or hydantoin.
ADHESION PROMOTION IN
PHOTORESIST LAMINATION AND PROCESSING
ABSTRACTION OF THE INVENTION
Use of a photoresist is improved due to increased adhesive to a substrate through an additive in the resist of a condensation polymer of formaldehyde, toluene sulfonamide and either a triazine such as melamine or hydantoin.
Description
L6~
TITLE
ADHESION PROMOTION IN
PHOTORESIST LAMINATION ~ND PRO OE SSING
This invention relates to p~oces6e~
particularly u~eSul for making prin~ed circuit boards employing a ~olid, photosen~itive layer employing an additive which function6 to promote adhe6ion of the layer to a 6ub~trate.
Photo6ensitive composition6 pa~ticula~ly useful as ehotoresi~ts in making p~inted circuit board6 a~e ~ell known in the ~rior art. Co~ventio~-ally thefie compo6ition& are ~tored in roll fo~m to minimize storage space. The photosensitive composition i6 adhered to a support fil~ to~orm a two ply material such as dis~losed in USP 4,293,635 or more conventlonally in a three ply mateLial such a6 USP 3.469,9a2 with the photosensitive ~omposition 6andwiched between a ~upport film and a co~P~ sheet.
The mateeial is un~ound from a Loll with the cover ~heet if present, removed from contact with ~he photosen6itive comæo~ition prior ~o u~e in laminatio~
to a substrate, e.g., a copper ~u~face. The laminated com~osition i6 imagewi6e exposed to actinic radiation with a supeort film 6tripped fro~ the ehotosensitive com~o6ition be~ore or a~ter the exposure step. The unexeosed areas of the ~tarting light-senfiitive layer are washed away to form a re6ist image oS polymeric mateeial. The area~ of ~he ~ubstrate surface which are not protected by the remaining areas o laminated material are pe~manently modi~ied by etching or by plating. ThereaSter the ehotorQ6ist is removed.
Various techniques have been disclosed to improve adhe6ion of the photosensitive layer to the ~ubstrate particulaely since areas o~ 6uch layer after expo6ure to actinic radiation mu~t adhere ~o the ~ub~trate during processing ~tep6 ~uch a~ atching of ehe substrate or by buildup of areas of the ~ubs~rate by depo~ition of a conductor.
A photopolymerizable Gompo~ition conventionally contains an adhe~ion promoter, i.e., an additive which aids in physically adhering ~he applied pho~opolymerizable layer in ~ubseguent proces~ing ~teps. U~eful adhe6i~e aid~ includ~
monome~ic or polymeric silanes and nitrogen containi~g heterocyclic com~ound6 such as di~clo~ed in USP 3,6450722 and ~SP 3~622~234n The p esent invention allows ~ inatio~ of conventional adhe~ion promoter~ in ehotose~itive ~ompo6ition~.
SUMMARY OF THE INVENTION
The pre6ent inven~ion is dire~ted to a process for ~orming a photoresist on a substrate compri~ing the ~tep~ of:
ta) laminating to tha substrate a supported solid photosensitive film layer which is ~hotopolymerizable or photocros61inkable, ~b) imagewi~e exposing the layer to actinic radiation, (c) removing unexposed areas of the layer to ~orm re6i5t area6.
(d) permanently modi~ying areas of the ~ubstrate which are unprotected by the resist areas by etching the substrate or by depositing a material onto the substrate, and te) removing the resist areas feom the s~bstrate, the photosensitive layer comprising:
~2~
(1~ polymerizable or cro~linkable ethylenically un~a~urated compound ~2) radia~ion sensitiYe, free radîcal generating photoinitiato~ or photoinitiator 6y8tem and (3~ op~ionally binder, wher~in the improvement ~omprises the photosen~itive l~yer containing an additi~e ~o in~rease adhesiou to a sub~tra~e ~hich i~ a conden~ation polymer Sormed from a tria~ine, fo~aldehyde and toluene $ulfonamide or hydantoin~ ~or~aldehyde and toluene sul~onamide. A ~referred tr~azine i8 melamine.
DETAILED DESCRIPTION OF THE INVENTION
The photosen~itive compo6ition useful ~ a photoresist contains conventional componen~ o~
polymerizable ethylenically unsaturated monomer, photoinitiator or photoinitiator system which initiate~ polymerization of the photosensiti~e compositio~ and binder.
The additive which impa~ts unique charac~eristic~ to the photo~ensitive compo6ition i6 a condensa~ion polymer of formaldehyde, toluene ~ulfonamide and either a tciazine or hydantoin. Each o~ these polymers e~f2c~ively function as an adhesion promoter. Mixture~ o~ these polymers can be employed. Either all or a portion o~ prior art adhe~ion promoter can be replaced by the named conden~ation polymer~. Examples of prior art adhesion promoters are described in Hurley et al., 35 U.S. Paten~ 3,6ZZ,334; Jones, U.S. Patent 3,645,772:
and Taguchi et al. U.S. Patent ~,320,1~9.
~ rhe laann~r o~ oYr~at~on o the ~or~densatio polyr~er of ~orDIaldehyde I eolu~n2 ~ul~onarahd~
eiSher triaæine or hydanto~n ca~ b~ in ~ccorflance wit~ sean~ard techn~que~ in for~ation o~ ~uch 5 polyme~ a~ for in~eance ~e~cr~bed in PqcI~to~hO U.5.
Pa~ant, 3,611~,650, Swi~zer et al. ~.S. Pa~ent 2,~53,109, ~ osh e~ al. U.S. Patent 3,412~03~:
TITLE
ADHESION PROMOTION IN
PHOTORESIST LAMINATION ~ND PRO OE SSING
This invention relates to p~oces6e~
particularly u~eSul for making prin~ed circuit boards employing a ~olid, photosen~itive layer employing an additive which function6 to promote adhe6ion of the layer to a 6ub~trate.
Photo6ensitive composition6 pa~ticula~ly useful as ehotoresi~ts in making p~inted circuit board6 a~e ~ell known in the ~rior art. Co~ventio~-ally thefie compo6ition& are ~tored in roll fo~m to minimize storage space. The photosensitive composition i6 adhered to a support fil~ to~orm a two ply material such as dis~losed in USP 4,293,635 or more conventlonally in a three ply mateLial such a6 USP 3.469,9a2 with the photosensitive ~omposition 6andwiched between a ~upport film and a co~P~ sheet.
The mateeial is un~ound from a Loll with the cover ~heet if present, removed from contact with ~he photosen6itive comæo~ition prior ~o u~e in laminatio~
to a substrate, e.g., a copper ~u~face. The laminated com~osition i6 imagewi6e exposed to actinic radiation with a supeort film 6tripped fro~ the ehotosensitive com~o6ition be~ore or a~ter the exposure step. The unexeosed areas of the ~tarting light-senfiitive layer are washed away to form a re6ist image oS polymeric mateeial. The area~ of ~he ~ubstrate surface which are not protected by the remaining areas o laminated material are pe~manently modi~ied by etching or by plating. ThereaSter the ehotorQ6ist is removed.
Various techniques have been disclosed to improve adhe6ion of the photosensitive layer to the ~ubstrate particulaely since areas o~ 6uch layer after expo6ure to actinic radiation mu~t adhere ~o the ~ub~trate during processing ~tep6 ~uch a~ atching of ehe substrate or by buildup of areas of the ~ubs~rate by depo~ition of a conductor.
A photopolymerizable Gompo~ition conventionally contains an adhe~ion promoter, i.e., an additive which aids in physically adhering ~he applied pho~opolymerizable layer in ~ubseguent proces~ing ~teps. U~eful adhe6i~e aid~ includ~
monome~ic or polymeric silanes and nitrogen containi~g heterocyclic com~ound6 such as di~clo~ed in USP 3,6450722 and ~SP 3~622~234n The p esent invention allows ~ inatio~ of conventional adhe~ion promoter~ in ehotose~itive ~ompo6ition~.
SUMMARY OF THE INVENTION
The pre6ent inven~ion is dire~ted to a process for ~orming a photoresist on a substrate compri~ing the ~tep~ of:
ta) laminating to tha substrate a supported solid photosensitive film layer which is ~hotopolymerizable or photocros61inkable, ~b) imagewi~e exposing the layer to actinic radiation, (c) removing unexposed areas of the layer to ~orm re6i5t area6.
(d) permanently modi~ying areas of the ~ubstrate which are unprotected by the resist areas by etching the substrate or by depositing a material onto the substrate, and te) removing the resist areas feom the s~bstrate, the photosensitive layer comprising:
~2~
(1~ polymerizable or cro~linkable ethylenically un~a~urated compound ~2) radia~ion sensitiYe, free radîcal generating photoinitiato~ or photoinitiator 6y8tem and (3~ op~ionally binder, wher~in the improvement ~omprises the photosen~itive l~yer containing an additi~e ~o in~rease adhesiou to a sub~tra~e ~hich i~ a conden~ation polymer Sormed from a tria~ine, fo~aldehyde and toluene $ulfonamide or hydantoin~ ~or~aldehyde and toluene sul~onamide. A ~referred tr~azine i8 melamine.
DETAILED DESCRIPTION OF THE INVENTION
The photosen~itive compo6ition useful ~ a photoresist contains conventional componen~ o~
polymerizable ethylenically unsaturated monomer, photoinitiator or photoinitiator system which initiate~ polymerization of the photosensiti~e compositio~ and binder.
The additive which impa~ts unique charac~eristic~ to the photo~ensitive compo6ition i6 a condensa~ion polymer of formaldehyde, toluene ~ulfonamide and either a tciazine or hydantoin. Each o~ these polymers e~f2c~ively function as an adhesion promoter. Mixture~ o~ these polymers can be employed. Either all or a portion o~ prior art adhe~ion promoter can be replaced by the named conden~ation polymer~. Examples of prior art adhesion promoters are described in Hurley et al., 35 U.S. Paten~ 3,6ZZ,334; Jones, U.S. Patent 3,645,772:
and Taguchi et al. U.S. Patent ~,320,1~9.
~ rhe laann~r o~ oYr~at~on o the ~or~densatio polyr~er of ~orDIaldehyde I eolu~n2 ~ul~onarahd~
eiSher triaæine or hydanto~n ca~ b~ in ~ccorflance wit~ sean~ard techn~que~ in for~ation o~ ~uch 5 polyme~ a~ for in~eance ~e~cr~bed in PqcI~to~hO U.5.
Pa~ant, 3,611~,650, Swi~zer et al. ~.S. Pa~ent 2,~53,109, ~ osh e~ al. U.S. Patent 3,412~03~:
3,~12,035, 3,412~036 a~d 3,4121,104: and lCa~e~a~ U~0 Patent 2, 8 O 9, 9 5 4 ar1d 2, 9 3 8, 8 7 3 . NOrma1 1Y the startlng material 10 will be p~esent in qua~ti~ies which ~re neag ~he s~o~h~omeeris ra~ios neces~ary ~o rorD~ She pslyaler.
HoweYe~ o~le or two o~ the component~ can be pr~e~t i~ ex~e~s ~n the polyme~izatio~ ~e~p and ~u~h e~
15 can be tolerate~ in the photo~ensit~e co~po~ltion.
The conde~6at~0~ poly~er ha~ bee~ employ~a a~ a ~omponent of a colora~t but ~u~h u~e i~ ~dhe~o~
promotion iB not known for replacemeAt o~ a~ adhes~o~
promoter~
The concentration of the ~onde~satio~
poly~er can vary within relatively wide li~its ba~ed on th* overall makeu~ o the monomer. photoi~itlator and binder. Generally the ~onden~atio~ polymer will be present in a con~entration o 0.5 to 25% by weight 2S of the photo~en~ e layer and mo~e typically 1 to 10~ by weight and even more typi~ally 2 to 6% by wei~h~.
Although improved adhesion result~ have been obtained with ~he conden~ation polymer o~
30 foe~aldehyde. toluene sulfoamide and either triazine or hydantoi~, an additional adhe~ion impco~ement has . been obtained when ~hs condensation poly~er i~
~ormulated in the presence of a dye or a combination o~ dye~. Improved re$ults have been ob~ained with 35 dyes compri~ing Brilliant Green (C.~.
~L25~5~
42040); Victoria Green (C.I. 42000) and Vietoria Blue (C.I. 42595). Brilliant Green Dye i8 pre~erred.
In practicing ~he lnvention, ehoto~ensi~ive ~ re6i~ element~ o~ various types may be uRQd~
I~ gene~al ehotohardenable, nega~ive-~orking element~
are photopoly~erizable element~ o~ the type di~closed in U.S. Patent 3,469,982~ U.5. 4,273,857 and U.S.
HoweYe~ o~le or two o~ the component~ can be pr~e~t i~ ex~e~s ~n the polyme~izatio~ ~e~p and ~u~h e~
15 can be tolerate~ in the photo~ensit~e co~po~ltion.
The conde~6at~0~ poly~er ha~ bee~ employ~a a~ a ~omponent of a colora~t but ~u~h u~e i~ ~dhe~o~
promotion iB not known for replacemeAt o~ a~ adhes~o~
promoter~
The concentration of the ~onde~satio~
poly~er can vary within relatively wide li~its ba~ed on th* overall makeu~ o the monomer. photoi~itlator and binder. Generally the ~onden~atio~ polymer will be present in a con~entration o 0.5 to 25% by weight 2S of the photo~en~ e layer and mo~e typically 1 to 10~ by weight and even more typi~ally 2 to 6% by wei~h~.
Although improved adhesion result~ have been obtained with ~he conden~ation polymer o~
30 foe~aldehyde. toluene sulfoamide and either triazine or hydantoi~, an additional adhe~ion impco~ement has . been obtained when ~hs condensation poly~er i~
~ormulated in the presence of a dye or a combination o~ dye~. Improved re$ults have been ob~ained with 35 dyes compri~ing Brilliant Green (C.~.
~L25~5~
42040); Victoria Green (C.I. 42000) and Vietoria Blue (C.I. 42595). Brilliant Green Dye i8 pre~erred.
In practicing ~he lnvention, ehoto~ensi~ive ~ re6i~ element~ o~ various types may be uRQd~
I~ gene~al ehotohardenable, nega~ive-~orking element~
are photopoly~erizable element~ o~ the type di~closed in U.S. Patent 3,469,982~ U.5. 4,273,857 and U.S.
4,293,635 a~d the photoeco~slin~able ele~ent~ o~ the ty~e di~elo6ed i~ U.S. Patent 3 9 526,S04. I~
proce$~i~g negative-wo~king photo~e~i6e eleme~s u~eYposed areas o~ the i~aged element are typi~ally ~emo~ed f~om the ~urface of a prineed eir~uit substrate by act~o~ of a developer liquid u~ually i~
a spray fo~m for a duration o~ several minu~es or le~s. Depending on the particular type of photoresi~t ¢ompositio~ the developer liquid may be a simple o~ganic sol~ent, a~ aqueous solution of an inorganic base, or, a~ in Alle6 U.S. 3,475,171, a eombinatio~ of o~gani~ solvent and aqueou~ base to form a ~emi-aqueou~ developer liquid.
Suitable monomers whieh ean be u3ed as ~he ~ole mo~omer or in eombination with other~ ~ueh as those in co~ventional ehotoresist include the follow-ing: t-butyl acrylate. l,5~pentanediol diaerylate, 25 N,N-diethylaminoethyl accylate, ethylene glycol diaerylate, 1,4-butanediol diacrylate, diethylene glycol diacrylate, hexamethylene glycol diacrylate, 1,3-pcopanediol diacrylate, decamethylene glycol diacrylate, decamethylene glycol dimethacrylate.
30 1,4-cyclohexanediol diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate, tripropylene glycol diacrylate, glycerol triacrylate, trimethyloleropane triacrylate, pentaerythcitol triacrylate, polyoxyethylated trimethylolp~opane triacrylate and 35 trimethacrylate and 6imilar comeounds as di~closed in U.S. Patent 3,380,831. 2,2-di(p-hydroxYphenyl)-propane diacrylate, pentaery~hritol te~raacrylate, 2,2-di-(p-hydLoxyphenyl)-proeane dimethacrylate, ~riethylene glycol diacrylate, polyoxyethyl-2,2-di-(p~
hydroxyphenyl)-propane dimethacrylate. di-(3-methac~yloxy-2-hydroxypropyl~ ether o~ bisphenol-A, di-~2-methacryloxyethyl) ether of bisphenol-Av di-(3-acryloxy-2-hydroxypropyl) ether of bi~phenol-~, di-~2-acryloxyethyl) ether o~ bisphenol-A, di-(3-methacryloxy-2-hyd~oxypropyl) ether of tetrachlo~o-bi~phenol-A, di-(2-methacryloxyethyl) ether of tetrachloro-bisphenol-A, di-(3-methacryloxy-2-hydroxypropyl) e~her o~ tetrabromo-bisphenol-A, di-(2-methacryloxyethyl~ ether o~ tetrabromo-bisphenol-~, di-(3-methacryloxy-2-hydroxypropyl) ether o~ 1,4-butanediol, di-(3-methacryloxy-2-hydroxy~opyl) ethe~ o~ d;phe~olic acid, triethylene glycol dimethacrylateO 2olyoxypropyltrimethylol propane triaclylate ~462), ethylene glycol dimethacrylate, butylene glycol dimethacrylate, 1,3-propaned;ol dimethacrylaee. 1,2,4-butanetriol trimethacrylate, 2,2,4-~imethyl-1,3-pentanediol dimethac~ylate, pentaerythritol trimethacrylate, l-phenyl ethylene-1,2-dimethacrylate, pentaerythritol tetramethacrylate, trimethylol propane trimethacrylat~, 1,5-pentanediol dimethacrylate, diallyl fuma~ate, styrene, l,~-benzenediol dimethacrylate, 1,4 diisopropenyl benzene. and 1,3,5-trii~opropenyl benzene.
In addition to the ethylenically unsaturated monomer~ mentioned above, the photoha~denable layer can a]so con~ain one or more fcee radical-initiated, chain-propagating, addition-polymerizable.
ethylenically unsaturated compounds generally having a molecular weight of at least about 300. P~efecred monomers of ~hi6 type are an alkylene or a polyalkylene glycol diacrylate prepared feom an alkylene glycol of 2 to 15 carbons or a polyalkylene ether glycol of 1 to 10 ether linkages, and ~ho6e di~closed in U.S. Patent 2,927,022, e.g., tho~e having a plueality o~ addition polymerizable e~hylenic linkage~ particularly when ~re~ent a6 terminal linkages. E~pecially preferred a~e ~ho~e wherein at lea~t one and pLefe~ably most o~ ~uch linkages are conjugated with a do~ble bonded carbon, including ~arbon double bonded to carbon and ~o ~uch hetesoa~om~ as nitrogen, oxygen and sul~ur.
Out~tandi~g are such ~aterial~ wherein the ethylenically un6atur~ted group6, e6peciall~ the vinylidene groups, are conju~ated with e6te~ o~ amide 6tructures .
Preferred f~ee radical-generating addition polymerization initiator6 activatable by actinic ligh~ and thermally inactive at and below 185C
include the substituted o~ unsub~tituted polynucle2r quinones which are eompounds ha~ing two in~racyclic carbon atomfi in a conjugated carbocyclic ring system, e.g., 9,10-anthraquinone, l-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 2-ethylan~hraquinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 1,2-benzanthraquinone, 2,3-benzanthcaquinone, 2-methyl-1,4-naphthoquinone, 2,3-dichloronaphthoquinone, 1,4-dimethylanthraquinone, 2,3-dimethylanthraquinone, 2-phenylanthraquinone, 2-3-diphenylanthraquinone, sodium salt of anthraquinone alpha-sulfonic acid, 3-chloro-2-methylanthraquinone, retenequinone, 7,8,9,10-tetrahydronaphthacenequinone, and 1,2,3,4-tetrahydcobenz(a)antheacene-7,12-dione.
35 Othee photoinitiator~ which are al60 useful, even ~29~
though some may be thermally active at temperatures a~ low as 85C, are de~cribed in U.S. Patent 2,760,863 and include vicinal ketaldonyl alcohol~, ~uch d8 benzoin, pivaloin, acyloin ethers, e.g., benzoin methyl and e~hyl etherfi; a-hydrocarbo~-sub~ti~uted aromatic acyloin~, including a-methylben~oin~
a-allylbenzoin and a-phenylbenzoin.
Photo~educible dye6 and reducing age~t~ di~clo~ed in U.S. Paten~: 2,850,445; 2D875~047 3,097,096:
10 3,074,974; 3,097,097: and 3,145,104 as well a~ dyes of the phenazine, oxazin~ and quinone classe~;
Michler'~ ketone, benzophenone, 2,4,5-triphenyl-imidazolyl dimers with hydrogen donor~, and mixtu thereof as described in U.S. Patent$: 3,427;161;
15 3,479,185; and 3,549,367 can be u~ed as initia~ors.
Similarly the cyclohexadienone compounds of U.S.
Patent No. 4.341,860 are useful as initiator~. Also useful with photoinitiators and photoinhibitor6 are 6en~itizec6 disclosed in U.S. Patent 4,162,162.
Suitable binder~ which are polymeric when employed with polymerizable monomers can be u~ed alone, or in combination with one another include the following: polyacrylate and alpha-alkyl polyacrylate e~ters~ e.g., polymethyl methacrylate and polyethyl methacrylate; polyvinyl esters, e.g., polyvinyl acetate, eolyvinyl acetate/acrylate, polyvinyl acetate/~ethacrylate and hydrolyzed polyvinyl acetate: ethylene/vinyl acetate copolymers:
polystyrene polymer~ and co~olymer6, e.g., with maleic anhydride and e6ter~; vinylidene chloride copolymers, e.g., vinylidene chloride/acrylonitrile:
vinylidene chloride/methacrylate and vinylidene chloride/vinyl acetate coeolymers: polyvinyl chloride and copolymers, e.g., polyvinyl chloride/acetate;
6aturated and unsaturated polyurethanes; ~ynthetic ~2"3~6~3 cubbers, e.g., butadiene~acrylonitrile, acrylonitrile/butadien2/6tyrene, methacrylate/ac~ylonitrile/butadiene/6tyrene copolymerFv, 2-chlorobutadiene-1,3 polymers, chlorinated rubber. and styrene/bu~adiene/styrene, styrene/isoprene/s~yrene block copolymer~: high molacular weight polyethylene oxides of polyglycols having average molecular weight~ from about ~,000 to 1,000,000; epoxideFv, e.g., epoxides containing acrylate or methacrylate groups: co~olyesters, e.g., thoRe prepared from the r0action product of a polymethylene glycol of the formula HO(CH2~nOH, where n i6 a whole numbel Z to 10 inclusive, and (1~ hexahydroterephthalic, ~ebacic and te~e~hthalic acids, (2) terephthalic, isophthalic and Fvebacic acids, (3) terephthalic and 6ebacic acids, (~) tecephthalic and isophthalic acids, and (5) mixtures of copolyesters prepared from said glycols and (i) terephthalic, isvophthalic and sebacic acids and (ii) tereph~halic, i60phthalic, sebacic and adipic acids: nylons or polyamide6, e.g., N-methoxymethyl ~olyhexamethylene adipamide:
cellulose e6ters, e.g., cellulose acetate, cellulose acetate succinate and cellulose acetate butyrate:
cellulo~e ethers, e.g., methyl cellulose, ethyl cellulose and benzyl cellulo~e: polycarbonates:
eolyvinyl acetal, e.g., polyvinyl butyral, polyvinyl formal polyformaldehydes. In place of or in addition to the polymeric binders listed above particulate thickeners with discrete, o~derly orientation can be used such as disclosed in Kuchta U.S. Patent 3,754,920, e.g., silicas, clays, alumina, bentonitesv kalonites, etc.
In the case where aqueous development of the photo~esist is desirable the binder should contain ~zg~
su~ficient acidic or o~her qroups ~o eender the composi~ion processible in aqueous developer. Useful agueous-proces~ible binders include those disclo6ed in U.S. Pa~ent 3,4s8,31i and in U.S. Patent 4,273,~57.
Ur;eful amphoteric polymers include interpolymers derived from an aminoalkyl acrylate o~ methacrylate.
acidic film-forming comonomer and an alkyl or hydloxyalkyl acrylate such as those disclosed in U.S. Patent 4,293,635. For aqueou~ develo~ment ehe photosensitive layer will be removed in ~ortions which are no~ exposed ~o radiation bue exeo~ed portions w;ll be substantially una~fected during development by a liquid 6uch as wholly aqueous ~olution~ containing 2~ 60dium carbonate by weight wiehin the ~ypical development ducation o~ several minute6, e.g., two minutes.
Thermal polymerization inhibitors that can be used in the photosensitive compositions are:
p-methoxy-phenol, hydroquinone, and alkyl and aryl-substituted hydroquinones and quinones, tert-butyl catechol, pyroqallol, copper resinate, naphthylamines, beta-naphthol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, phenothiazine, pyridine, nitrobenzene and dinitrobenzene, p-toluquinone and chloranil. Also useul oe theernal polymerization inhibitors are the nitroso compositions di6closed in U.S. 4,168,~82. Normally a thermal polymerization inhibitor will be present to increase stability in storaqe of the photo~en6itive composition6.
Various dyes and pigments may be added to increase the vi~ibility of the resist image. Any colorant used, however, should preferably be transparent to the actinic radiation used.
The following examples more fully illustrate the present invention. A11 parts and percentage6 are ~ 2~5~
by weigh~ and degrees are in centigrade unle~s othe~wi~e ;ndicated.
A "Ma~tec" coating ~olution wa6 prepared having the following composition:
In~redien~ Amoun~
Binde~ 1 351 Poly (methyl methacEylate/
meehacrylic acid) (90~10);
mixture of 7 parts o~ the ~olymer having a weight average .W. o~ 25000 and 1 pare of tha polymer having a weight average ~.W. of 50,000 15 Trimethylol propane triacrylate 226 Benzophenone 25 Michlel's ke~one 0.63 Tricresyl pho~phate 12.5 Z Triethylene glycol diacetate6.3 Methylene chloride 112B
Methanol 38 288 part~ by weight o~ the solution was coated to a wet thickness o~ 0.006 in. (0.152 ~m) on 0.001 in. (0.025 mm) polyethylene terephthalate film base and identified a~ coating ~. To five additional Z8~ parts by weight aliquots of the solution the 30 ~ollowing amounts o~ adhesion promoters listed in Table I we~e added and coated as abo~e:
~2~
TABLE-T
Component ~dded Amount Cgatinq None --5 Benzo~riazole 0.2 HFS~ 5.0 C
MFS** 5.0 D
MHP~* S.O E
10 Ben20guanamine 0.2 F
HFS i8 a conden~ation polymer of hydantoin, formaldehyde and mixed 0 ~ P toluene sulfo~amide fo~mulated with Brilliant Green (C.I. 42040) and C.l. Solvent Yellow 85.
~ ~FS is a condensation polymel o~ melamine, formaldehyde and mixed 0 ~ P toluene sulfonamide formulated with a red colorant.
*** M~IP is ~ toluene sulfonamide-formaldehyde plasticizing resin having a so~tening point of 62C and a ~peci~ic gravity of 1.35 at 25C and al60 sold as Santolite~MHP by the Monsanto Co.
Each coating after drying wa~ laminated to a copper clad circuit board substrate which was sceubbed with an abrasive brush, using a Riston~ hot roll laminator. The laminated boards were imagewi6e exeo~ed th~ough a 6 ~ Stouffec 41 steewedge u6ing a Rifiton~ PC 24 exposure device and develoeed using a semi-aqueoufi developer containing 11~ butyl Cellosolve~ and 1% boLax. The time of exposure was adju~ted to p~ovide a similar numbee, about 20, of developed image steps.
Sample~ of each developed board were tested using fitandard plating and etching techniques.
~z~
Plate and Etch Procedure:
Each board wa6 immer~ed foe 5 minutes in a 9.5~ aqueous ~olution o Metex~ s26B preæla~e cleaner at 130F (54.4C), rin~ed for 30 ~econds in S flowing water, immersed for 1 minute at room tempera~ure in 10% aqueou~ sul~uric acid, immer~ed in flowing water for 1 minute, immered in 18~ aqueous ammonium persulfate 801utio~, rin~ed in wa~e~ again, i~mer~ed in sulfuric acid once again ~or 1 ~inute and ~hen immer~ed in acidic CuS0~ plating ~slution and plated at 30 amps/sq. ft. ~0.333 amp6/~q. cm.) for 36 minu~es to produce 0.00 1 in. (0.025 mm) pla~ed copper .
The plated board wa~ ~in~ed in wat~r, i8 immer~ed for 1 minute in 20% aqueous fluoroboric acid ~olution, and then immersed in a commercial tin/~ead (60/40) fluoroborate olution (Hi-Thro~) and plated at 15 amps/sq. ~t. (0.166 amp6/sq. cm~ ~or 15 minutes to deposit 0.0004 in. tO.01 mmj solder on ~he coppe~
plated image.
The board was cin~ed with water and then the photopolymerized resist was stripped from the plated boacd using 9Z% methylene chloride/8% methanol solvent solution.
The 6trip~ed board wa8 6prayed at 30 psi with an aqueous ammoniacal copper chloride solution (pH 7.8--8.Z) (MacDermid Co. Ultra Etch~ Fine Line) for 1 minute a~ 130F (54.4C) to produce a solder plated copper circuit pattern.
30 Etchinc~ P~rocedure Each lmaged and developed board was sprayed at 30 p8i with an etchant solution at 130F (5~.4C) until all unprotected copper was removed. In the instance when an alkaline etchant was used, ~acDermid 35 Ultra Etch~ Fine Line was the etchant~ In the instance when acid etchant wa~ used, sufficient cupric chloride and hydrochloric acid was used to prnduce an aqueou~ 601ution with a pH about 2.3~ and containing ~g ounces of copper/gallon (177 g/l~ of e~chan~.
Evaluation of Plate and ~tch Board~
Each board wa~ examined with a 50 powe~
optical micloscope to determine i~ circuit line edges are "ragged" due ~o lifting of ~he edge~ of the resist with plating ~hereunder (known as ~underplating"), or connected to adjoining circuit lines ("short" c~rcuit) due to re8i8t "blistering".
U~derpla~ing and ~horts indicate resi6t adhesion failure during the plating proceduce re6ulting in re~ist delamination or blistering. The board~ are al~o exa~ined for the aepearance of a bright ring or "halo" around circuit lines. The presence of halo while not a defect ltself indicates the potential for underplating failure.
Evaluation of Etchant Board~
After board~ were etched the re6ist is stripped as previously described and examined with the optical microscope to determine if circuit line edge6 are "ragged", i.e., contain~ llnicks'l at the circuit line edges or if circuit line is "narrowed"
indicating adhesion failure of the resist during etching. Gro6s ~ailure leads ~o "breaks" or "opens"
in the ciccuit line.
~able II contains the evaluation of the 30 plated and etched board6 and the alkaline and acid etched boards. In the table "NF" indicates no failure o~ adhesion was ob~erved.
~2~
TABLE II
Proces6-ing Proced- Coated Board ure A a c D E F
Plate ~ "ragged" NF NF NF l'ragged'1 "ragged"
etch "shorts" "~hocts"
Alkaline "ragged" NF ~F NP "ragged" "ragged"
Etch Acid "ragged" NF NF "ragged" "ragged" "ragged"
Etch "breaks" "breaks" "break~" "brealcs"
Re6ult~ indicate that the polymeric compound~
added to the solvent coated film Punction a~ least a~
well as the conventio~al adhesion promoter ~or both the plate and etch procedure and the alkaline etch procedure. The hydantoin containing polymer algo functioned sati6factorily for the acid etching procedure .
EXAMPLE ?~
A solventless composition similar to coatings "B" and "D" of Example 1 were prepared having ~he following compo~ition and were melt coated u6ing the procedures described in Re~earch Disclo6ure No. 24919 published January, 1985.
_qredient Amount Bindec 1 56 Trimethylol propane triacrylate 36 Benzoehenone Michler's ketone 0.1 Tcicresyl phosphate 2 Triethylene glycol diacetate Ccy~tal Violet 0.04 Red Dye CI los 0.3 COATTNG_COMPOSITION
Component G_ H
~a6~er 2 9~.8 99. a Benzotriazole .2 .2 ~5 -- 5.0 Each coatinq wa~ processed and evaluated a~
in E~ample 1 and re6ults are presented in Table III.
TABLE III
Processing Procedure Coated~Board G H
Plate ~ Etch NF NF
Alkaline Etch "Ragged" NF
Acid Etch "Breaks" NF
"~assive Failure"
ZO
The above re~ult~ demon~trate the advantage o~ u6ing the adhesion e~omoeers of thi6 inven~ion when compa~ed to conventional adhesion p~omoters 6uch a~ benzotriazole.
- _ A master solution wa~ prepared as in Example 1 except the binder component was adjusted for the amount o~ adhesion promoter added as indicated in Table IV. In Table IV Formulation X is a control ~ince it contains no adhe~ion promotor.
~2~
Inqredient Amount Trimethylol propane triacrylate 226 Benzophenone 25 ~Sichler' 5 ketone 0.63 Tricresyl ~hospha~e 12.5 T~ie~hylene glycol diacetate 6.3 Methylene ~hloride 1128 Methanol 38 TABLE IV
Coatinq Composition Inaredient X I J K L M N
~aster 3 229 229 229 229 229 229 ~29 Binder 1 55.2 54.7 5~.2 52.2 51.2 50.2 49.2 HFS O .5 1.0 2.0 3.0 4.0 5.0 ~ ach solution was coated, proce6sed and evaluated a6 in Example 1. In addieion, the adhesion of pho~ore~i6t to copper prior to exposure was measured by removing the polyethylene terephthalate support and adhering 1 inch (2.54 cm) wide Scotch~
brand masking tape 2262MSR to the resist sucface.
One end of the tape was attached to an Instron~
30 Univec6al Testing Instrument model 1130 and peeled at a 180 direction at 5 inches/min (12.7 cm/min) ~rom the board substrate surface. The force needed to separate the resist from the coppec surface was identified as the "Copper ~dhesion" and represented as the numbee of grams per linear cm. In addition ~5~6~
the pla~e and etch and alkaline etching evaluations were quantified by identifying the number of defects for a test board having 125 lines 0.007 in. ~0.178 mm) with an eguivalent number and size space~
the~ebetween. Fo~ example in the in~tance where no HFS adhe~ion p~omotoe was u6ed (Coating X), ~he adhesion to copper p~ior to ex~osure wafi measured to be 13.~ g eee lineae cm. The te~t board after alkaline etching had 3 BLeaks and 8 Nick~ wieh eesi6 lifting and peeling and a similar board after platin~
had ~alos, Li~ting and Shorts. The results for the coatingfi at the inceea~ing concen~ration ar~
pre6e~ted ~Q Table V whe~e "NF" indieates no failure, "H" indicates eresence o~ halo~, "L" indicates Li~ting, ~S" indicate~ Shorts, "B" indica~es Break6.
"N" indicates Nick~ and coppee adhe6ion ;6 given in g/cm.
TABLE V
Inqredient X I_ J_ ~ L M N
Plate and H,L,S NF NF NF NF NF NF
Etch Alkaline 3B+ 1~ 9B~ ~B~ lB~ lB NF
Etch 8N 2N 2N LN
Coppar 13.4 18.9 18.9 13.9 26.6 27.6 52.6 25 Adhesion As little as 0.5% by weight of the polymeric adhesion promotee i~ sufficient to improve performance during plate and etch processing and overall eerormance is 0 improved with about 4% of the adhesion promoter.
EX~MPLE 4 Six additional coatings were prepared and eroces~ed and evaluated as in Example 3 exce~t that adhesion promoter MFS was used in place of HFS.
TABLE VI
Coatinq ComQo~îtion In~redient 0 P _Q_ R S T
Mafi~er 3 229 229 229 229 229 229 Binder 1 54~7 53.2 52.2 51.250.2 4~.2 MFS .5 1 2 3 ~ 5 The quan~ified r2~ult~ belo~ in Tabl~ VII
indicate that improvement of all ~unctions begins with around 3~ of this adhesion p~omoter and ri~es rapidly to optimum perfo~mance by about 5%.
TA~LE VII
Inqredien~ ~ O P _Q_ R S T
Plate and H,L~S H~L H~L H~ H*~ NF ~F
Etch Alkaline 3~+ lB 6B lOB 4B lN NF
Etch 8N
Copper 13.4 13.4 16.2 16.2 21.5 25.~ 26.
20 Adhesion * Rlight ~* veLy slight Re~ults o~ the te~t6 in Examples 3 and ~
indicate that addition of either HFS or MFS improve6 adhesion perfo~mance o~ the laminated Rolvent coated re~ist films either in the plate and etch mode or the alkaline etch mode o~ both.
EX~MPLE 5 Two ~olvent processable 0.002 inch thick photoresi~t ~ilm~ were prepared from the following coating ~olutions:
~ ~35~
~o Coating Coating U V
Poly(methylme~hacrylateJ 56 56 ethylmethacrylate) (75/25) inherent visco~ity 0.49 Trimethylol propane ethoxylat~d 30.9 30.9 triacryla~e, ~.W. 400 ~ 50 Ethyl Michle~'~ ketone 0.15 0.15 Benzophenone 4 4 4-Methyl-4-trichloromethyl 0.06 0.06 cy~lohexadiene-l-one p-Toluene ~ulfonic acid 0.05 0.05 Leuco Cry~tal Violet 0.25 0.25 Victoria Green Dye ~C.I. 42000) 0.04 0.04 Victoria Blue ~ye (C.I. 42595) 0.02 0.02 HFS-UP** ~ _ Santicizer~9 (mixed o and p 4.53 toluene ~ulfonamide) MHP~ - 8.53 Propylene glycol methyl ether 11 11 Methylene Chloride 175 17 * Trimethylolpropane ethoxylated triaceylate (TMPEOTA) has the following ethoxylate distribution which con6titutes a minimum of 92% o~ the distribution None 6~ Max Monoethoxy 10~20 Diethoxy-l 12~
Diethoxy~Z 14~Z1%
Triethoxy-l 21-29~
T.ciethoxy-2 6-10%
Tetraethoxy 12-20%
** HFS-UP i~ an unpigmented condensation polymer of hydantoin, fo~maldehyde and mixed o and p toluene sulfonamide formulated with phthalic anhydride.
ZO
~s~
~** M~IP is a toluene 6ulfonamide-formaldehyde pla~ticizing re~in having a softening point of 62C and a specific gravity of 1.35 at 25~C
and i~ purcha~ed a~ Santolite~MHP from the Mon6an~0 Co.
Each ~olution wa~ coated on a 0.001 inch thîck ~olye~hylene terephthalate ~uppor~ fil~ to give a dry coaeing thickne~s of 0.002 inch.
Each dried coated resis~ film wa~ laminated to three copper clad sub6trates which were scrubbQd with an abrasive bru~h ufiing a Ri~ton~ hot roll laminator. Each laminated board was imagewise exposed through a ~ Stouffer0 41 ~tepwedge using a Riseon~ PC 24 exposure de~ice and developed in a RistonO C Procesfio~ (at 60 to 70F with 20 psi s~ray ere~sure) containing stabilized 1,1~1 trichloroethaQe as the developer solvent.
Each of the develoeed boards were tested using the following rigorou~ plating and etching technique.
Each board was immersed ~or 5 minut~s in a 8.5% aqueous solution of Metex~ 9268 preplate cleaner at 130P (54.4C), rinsed for 1 min in f].owing wate~, immersed in 18% aqueous ammonium persulfate solution for 1 min or les~ to remove 10-15 inch coeper, rinsed in water again, immersed in sulfucic acid for 1 minute and ~hen immersed in alkaline coppec pycophosphate heating plating ~olution and plated at 20 amps/sq. t. for 59 minu~e~
to pcoduce 0.001 inch (O.OOZ5 cm) plated copper.
The plated board was rinsed in water, immer~ed fol 30 seconds in 20~ aqueous fluocaboric acid solution, and ~hen immersed in a commercial tin/lead (60/40) fluoroborate solution ~Hi-Thco~3 ~ ;~9~
and plated at 20 ampst6q. ft. (0.1667 amp~/6q. cm.) ~or 12 minu~e~ to deposit 0.0005 inch (0.01 mm) ~older on the copper plated image.
The board wa6 ~insed with wate~ and then the photopolymerized re~i6t wa~ stripped from the plated boaLd u~i~g methylene chlocide fiolvent.
The ~tripped board was s~rayed at 20 p8i wi~h an agueous ammoniacal coppe~ chloride solutio~
~pH 7.8-8.2~ (MacDermid Co., Ult~a Etch~ Fine Line) at 130CF ~5~.4C) to produce a solder plated ~oyper ~i~cuit pattern.
For each o~ the plated and etched board6 in which M~P was used in the resi~t formula~ion coppe~
staining occurred during the process which ls a defect indica~ing the potential for underplati~g. In co~tra~t no deects were observed for the ~lated and etched board~ which were prepared from the resi6t film containing HFS-UP.
The plated boa~d was rinsed in water, is immer6ed for 1 minute in Z0~ aqueous fluoroboric acid solution, and then immersed in a commercial tintlead (60/40) fluoroborate ~olution (Hi-Thro~) and plated at 15 amps/sq~ ft. (0.166 amps/sq. cm) for 15 minutes to deposit 0.0004 in. (0.01 mm) solder on the copeer elated image.
The board was rinsed with wate~ and ~hen ~he photopolymerized re6ist was stripped from the plated board ufiing 92~ methylene chlocide/8~ methanol ~olvent ~olution.
The 6tripped board was ~prayed at 30 psi with an aqueou6 ammoniacal copper chloride solution (pH 7.8-8.2) (MacDermid Co. Ultra Etch~ Fine Line) for 1 minute at 130F (54.~C) to produce a solder elated copper circuit pattern.
g EX~MPLE 6 Fouc ~olvent proceRsable 0.002 in thick photoresist films were prepared and ~ested for u6e under very cigorou~ plating and et~hing ~onditions.
A Ma6~er coating ~olution wa~ ~repared foe each coating having the following Composition:
Master 4 Com~osition ~mount Inq~edient in qram~
lo Poly(methylmethacrylate/ 728 ethylmethacrylate) (75J25) inherent vi~c08ity 0 . 49 Tcimethylol propane ethoxylated 401.7 triacrylate, M.W. 400 ~ 50 15 Ethyl Michler's ketone 1.95 Benzophenone 5Z.05 ~-Methyl-~-trichloromethyl 1.30 cyclohexadiene-l-one Tris-(4-diethylamino-2-tolyl) methane 1.95 Leuco Crystal Violet 3.25 Santicizer~9 tmixed o and p toluene 55.69 6ulfonamide) p-Toluene sulfucic acid 0.65 5-Chlocobenzotriazole 2.60 Pro~ylene glycol methyl ether142~58 Methylene chloride 2274.07 Coatinq Solution ''W'' contained the ingredients of Master solution 4 along with 0.52 y of Victoeia Gceen Dye: 0.39 g Victoria Blue Dye and 50.1 g of HFS-UP of Example 5.
Coatinq Solution "X" contained the 35 ingredients of Master solution 4 along with 51.01 g ~2g5~
o~ HFS-BG which is the condensaeion polymer of hydantoin, formaldehyde and mixed o and p ~oluene ~ulfonamide formulated wi~h 1~ Brilliant Green Dye ~C.I. 42040).
Coa~inq Solution "Y'' contain~ the ingredie~ts o~ Maste~ Solu~ion 4 along with 51.01 g of HFS-BGVB whieh is the condensation polymer o hydantoin, ocmaldehyd~ and mixed o and p ~oluene sulfonamide, formulated with 1% Brilliant Gcee~ D~e (C.I. ~2040) and 0.76~ Victo~ia Blue Dye (C.I. 425953.
Coatinq Solution "Z" contains tha ingredient6 of Master Solution 4 along with 51.01 g of HPS-VG~B whieh i8 the condensa~ion polymer o~
hydantoin, formaldehyde and mixed o and ~ t~luene sulfonamide, formulated with 1% Vi~toria Green Dye ~C.I. 42000) and 0.8% Victoria Blue Dye (C.I. 425953.
These coating solutions were coated, laminated exposed and develo~ed as i~ Example 5 and then te~ted using the copeer/tin-lead plating and etching procedure of Example 5 along ~ith a con~entional copper/nickel/gold plating procedure.
In this plating procedure the coeper i8 plated as in Example 5 the plated panel i6 rinfied in water for 1 minute and then nickel plated in an acidic nickel sulfamate solution using a current density of 30 amper6/square ~eet for 15 minutes to produce nickel plating 0.0003 inch thick. The nickel plated panel i5 then rinsed and immersed in a 10~ aqueous 6ulfuric acid both for 1 minute. rinsed again and then gold plted in a orosene~999 gold plating bath at ~3F
for 10 minutes at a cuccent den~ity of 10 amper6/square foot. In evaluating the result~ of these tests a ~eries of circuit board panel~ are processed for each coting and each panel is given a numerical value from 0 to 5 depending on whether the ~5~
panel has no defects, e.g., "0", non~unctional defect~, e.g.D 1, ~ and 3 (~uch as copper staininq) which ~ill produce accep~able circui~ board or func~ional defect~, e.g., 4 and 5~ ~ueh a~ ~
underplating and ~hort~ ~hich disquali~y the board foe use. The average value for each series of panels for each type of plating is given in Table VIII for each coating.
TABL~ VIII
Coatin~ Cllo~L~Cu/Ni~Au W(HFS-UP) 3.3 4.2 ~(HFS-BG) 2.0 2.25 Y(E~S-BGVB) 1.3 0.8 Z(HFS-VGVB) 3 3.1 While acceptable boards can be obtained from all of the coating6 u6ing Cu~Sn-Pb plating it i~
clear that best results are obtained using conden6ation polymecs ~ormulated in the presence of Brilliant Green Dye and some improvement is obtained with polymers formulated in the presence of Victoria ~lue and/or Vic~o~ia Green. This ~ame trend of impeovement is al60 present ~or panels prepared under the more severe condition6 of Cu/Ni/Au plating.
proce$~i~g negative-wo~king photo~e~i6e eleme~s u~eYposed areas o~ the i~aged element are typi~ally ~emo~ed f~om the ~urface of a prineed eir~uit substrate by act~o~ of a developer liquid u~ually i~
a spray fo~m for a duration o~ several minu~es or le~s. Depending on the particular type of photoresi~t ¢ompositio~ the developer liquid may be a simple o~ganic sol~ent, a~ aqueous solution of an inorganic base, or, a~ in Alle6 U.S. 3,475,171, a eombinatio~ of o~gani~ solvent and aqueou~ base to form a ~emi-aqueou~ developer liquid.
Suitable monomers whieh ean be u3ed as ~he ~ole mo~omer or in eombination with other~ ~ueh as those in co~ventional ehotoresist include the follow-ing: t-butyl acrylate. l,5~pentanediol diaerylate, 25 N,N-diethylaminoethyl accylate, ethylene glycol diaerylate, 1,4-butanediol diacrylate, diethylene glycol diacrylate, hexamethylene glycol diacrylate, 1,3-pcopanediol diacrylate, decamethylene glycol diacrylate, decamethylene glycol dimethacrylate.
30 1,4-cyclohexanediol diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate, tripropylene glycol diacrylate, glycerol triacrylate, trimethyloleropane triacrylate, pentaerythcitol triacrylate, polyoxyethylated trimethylolp~opane triacrylate and 35 trimethacrylate and 6imilar comeounds as di~closed in U.S. Patent 3,380,831. 2,2-di(p-hydroxYphenyl)-propane diacrylate, pentaery~hritol te~raacrylate, 2,2-di-(p-hydLoxyphenyl)-proeane dimethacrylate, ~riethylene glycol diacrylate, polyoxyethyl-2,2-di-(p~
hydroxyphenyl)-propane dimethacrylate. di-(3-methac~yloxy-2-hydroxypropyl~ ether o~ bisphenol-A, di-~2-methacryloxyethyl) ether of bisphenol-Av di-(3-acryloxy-2-hydroxypropyl) ether of bi~phenol-~, di-~2-acryloxyethyl) ether o~ bisphenol-A, di-(3-methacryloxy-2-hyd~oxypropyl) ether of tetrachlo~o-bi~phenol-A, di-(2-methacryloxyethyl) ether of tetrachloro-bisphenol-A, di-(3-methacryloxy-2-hydroxypropyl) e~her o~ tetrabromo-bisphenol-A, di-(2-methacryloxyethyl~ ether o~ tetrabromo-bisphenol-~, di-(3-methacryloxy-2-hydroxypropyl) ether o~ 1,4-butanediol, di-(3-methacryloxy-2-hydroxy~opyl) ethe~ o~ d;phe~olic acid, triethylene glycol dimethacrylateO 2olyoxypropyltrimethylol propane triaclylate ~462), ethylene glycol dimethacrylate, butylene glycol dimethacrylate, 1,3-propaned;ol dimethacrylaee. 1,2,4-butanetriol trimethacrylate, 2,2,4-~imethyl-1,3-pentanediol dimethac~ylate, pentaerythritol trimethacrylate, l-phenyl ethylene-1,2-dimethacrylate, pentaerythritol tetramethacrylate, trimethylol propane trimethacrylat~, 1,5-pentanediol dimethacrylate, diallyl fuma~ate, styrene, l,~-benzenediol dimethacrylate, 1,4 diisopropenyl benzene. and 1,3,5-trii~opropenyl benzene.
In addition to the ethylenically unsaturated monomer~ mentioned above, the photoha~denable layer can a]so con~ain one or more fcee radical-initiated, chain-propagating, addition-polymerizable.
ethylenically unsaturated compounds generally having a molecular weight of at least about 300. P~efecred monomers of ~hi6 type are an alkylene or a polyalkylene glycol diacrylate prepared feom an alkylene glycol of 2 to 15 carbons or a polyalkylene ether glycol of 1 to 10 ether linkages, and ~ho6e di~closed in U.S. Patent 2,927,022, e.g., tho~e having a plueality o~ addition polymerizable e~hylenic linkage~ particularly when ~re~ent a6 terminal linkages. E~pecially preferred a~e ~ho~e wherein at lea~t one and pLefe~ably most o~ ~uch linkages are conjugated with a do~ble bonded carbon, including ~arbon double bonded to carbon and ~o ~uch hetesoa~om~ as nitrogen, oxygen and sul~ur.
Out~tandi~g are such ~aterial~ wherein the ethylenically un6atur~ted group6, e6peciall~ the vinylidene groups, are conju~ated with e6te~ o~ amide 6tructures .
Preferred f~ee radical-generating addition polymerization initiator6 activatable by actinic ligh~ and thermally inactive at and below 185C
include the substituted o~ unsub~tituted polynucle2r quinones which are eompounds ha~ing two in~racyclic carbon atomfi in a conjugated carbocyclic ring system, e.g., 9,10-anthraquinone, l-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 2-ethylan~hraquinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 1,2-benzanthraquinone, 2,3-benzanthcaquinone, 2-methyl-1,4-naphthoquinone, 2,3-dichloronaphthoquinone, 1,4-dimethylanthraquinone, 2,3-dimethylanthraquinone, 2-phenylanthraquinone, 2-3-diphenylanthraquinone, sodium salt of anthraquinone alpha-sulfonic acid, 3-chloro-2-methylanthraquinone, retenequinone, 7,8,9,10-tetrahydronaphthacenequinone, and 1,2,3,4-tetrahydcobenz(a)antheacene-7,12-dione.
35 Othee photoinitiator~ which are al60 useful, even ~29~
though some may be thermally active at temperatures a~ low as 85C, are de~cribed in U.S. Patent 2,760,863 and include vicinal ketaldonyl alcohol~, ~uch d8 benzoin, pivaloin, acyloin ethers, e.g., benzoin methyl and e~hyl etherfi; a-hydrocarbo~-sub~ti~uted aromatic acyloin~, including a-methylben~oin~
a-allylbenzoin and a-phenylbenzoin.
Photo~educible dye6 and reducing age~t~ di~clo~ed in U.S. Paten~: 2,850,445; 2D875~047 3,097,096:
10 3,074,974; 3,097,097: and 3,145,104 as well a~ dyes of the phenazine, oxazin~ and quinone classe~;
Michler'~ ketone, benzophenone, 2,4,5-triphenyl-imidazolyl dimers with hydrogen donor~, and mixtu thereof as described in U.S. Patent$: 3,427;161;
15 3,479,185; and 3,549,367 can be u~ed as initia~ors.
Similarly the cyclohexadienone compounds of U.S.
Patent No. 4.341,860 are useful as initiator~. Also useful with photoinitiators and photoinhibitor6 are 6en~itizec6 disclosed in U.S. Patent 4,162,162.
Suitable binder~ which are polymeric when employed with polymerizable monomers can be u~ed alone, or in combination with one another include the following: polyacrylate and alpha-alkyl polyacrylate e~ters~ e.g., polymethyl methacrylate and polyethyl methacrylate; polyvinyl esters, e.g., polyvinyl acetate, eolyvinyl acetate/acrylate, polyvinyl acetate/~ethacrylate and hydrolyzed polyvinyl acetate: ethylene/vinyl acetate copolymers:
polystyrene polymer~ and co~olymer6, e.g., with maleic anhydride and e6ter~; vinylidene chloride copolymers, e.g., vinylidene chloride/acrylonitrile:
vinylidene chloride/methacrylate and vinylidene chloride/vinyl acetate coeolymers: polyvinyl chloride and copolymers, e.g., polyvinyl chloride/acetate;
6aturated and unsaturated polyurethanes; ~ynthetic ~2"3~6~3 cubbers, e.g., butadiene~acrylonitrile, acrylonitrile/butadien2/6tyrene, methacrylate/ac~ylonitrile/butadiene/6tyrene copolymerFv, 2-chlorobutadiene-1,3 polymers, chlorinated rubber. and styrene/bu~adiene/styrene, styrene/isoprene/s~yrene block copolymer~: high molacular weight polyethylene oxides of polyglycols having average molecular weight~ from about ~,000 to 1,000,000; epoxideFv, e.g., epoxides containing acrylate or methacrylate groups: co~olyesters, e.g., thoRe prepared from the r0action product of a polymethylene glycol of the formula HO(CH2~nOH, where n i6 a whole numbel Z to 10 inclusive, and (1~ hexahydroterephthalic, ~ebacic and te~e~hthalic acids, (2) terephthalic, isophthalic and Fvebacic acids, (3) terephthalic and 6ebacic acids, (~) tecephthalic and isophthalic acids, and (5) mixtures of copolyesters prepared from said glycols and (i) terephthalic, isvophthalic and sebacic acids and (ii) tereph~halic, i60phthalic, sebacic and adipic acids: nylons or polyamide6, e.g., N-methoxymethyl ~olyhexamethylene adipamide:
cellulose e6ters, e.g., cellulose acetate, cellulose acetate succinate and cellulose acetate butyrate:
cellulo~e ethers, e.g., methyl cellulose, ethyl cellulose and benzyl cellulo~e: polycarbonates:
eolyvinyl acetal, e.g., polyvinyl butyral, polyvinyl formal polyformaldehydes. In place of or in addition to the polymeric binders listed above particulate thickeners with discrete, o~derly orientation can be used such as disclosed in Kuchta U.S. Patent 3,754,920, e.g., silicas, clays, alumina, bentonitesv kalonites, etc.
In the case where aqueous development of the photo~esist is desirable the binder should contain ~zg~
su~ficient acidic or o~her qroups ~o eender the composi~ion processible in aqueous developer. Useful agueous-proces~ible binders include those disclo6ed in U.S. Pa~ent 3,4s8,31i and in U.S. Patent 4,273,~57.
Ur;eful amphoteric polymers include interpolymers derived from an aminoalkyl acrylate o~ methacrylate.
acidic film-forming comonomer and an alkyl or hydloxyalkyl acrylate such as those disclosed in U.S. Patent 4,293,635. For aqueou~ develo~ment ehe photosensitive layer will be removed in ~ortions which are no~ exposed ~o radiation bue exeo~ed portions w;ll be substantially una~fected during development by a liquid 6uch as wholly aqueous ~olution~ containing 2~ 60dium carbonate by weight wiehin the ~ypical development ducation o~ several minute6, e.g., two minutes.
Thermal polymerization inhibitors that can be used in the photosensitive compositions are:
p-methoxy-phenol, hydroquinone, and alkyl and aryl-substituted hydroquinones and quinones, tert-butyl catechol, pyroqallol, copper resinate, naphthylamines, beta-naphthol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, phenothiazine, pyridine, nitrobenzene and dinitrobenzene, p-toluquinone and chloranil. Also useul oe theernal polymerization inhibitors are the nitroso compositions di6closed in U.S. 4,168,~82. Normally a thermal polymerization inhibitor will be present to increase stability in storaqe of the photo~en6itive composition6.
Various dyes and pigments may be added to increase the vi~ibility of the resist image. Any colorant used, however, should preferably be transparent to the actinic radiation used.
The following examples more fully illustrate the present invention. A11 parts and percentage6 are ~ 2~5~
by weigh~ and degrees are in centigrade unle~s othe~wi~e ;ndicated.
A "Ma~tec" coating ~olution wa6 prepared having the following composition:
In~redien~ Amoun~
Binde~ 1 351 Poly (methyl methacEylate/
meehacrylic acid) (90~10);
mixture of 7 parts o~ the ~olymer having a weight average .W. o~ 25000 and 1 pare of tha polymer having a weight average ~.W. of 50,000 15 Trimethylol propane triacrylate 226 Benzophenone 25 Michlel's ke~one 0.63 Tricresyl pho~phate 12.5 Z Triethylene glycol diacetate6.3 Methylene chloride 112B
Methanol 38 288 part~ by weight o~ the solution was coated to a wet thickness o~ 0.006 in. (0.152 ~m) on 0.001 in. (0.025 mm) polyethylene terephthalate film base and identified a~ coating ~. To five additional Z8~ parts by weight aliquots of the solution the 30 ~ollowing amounts o~ adhesion promoters listed in Table I we~e added and coated as abo~e:
~2~
TABLE-T
Component ~dded Amount Cgatinq None --5 Benzo~riazole 0.2 HFS~ 5.0 C
MFS** 5.0 D
MHP~* S.O E
10 Ben20guanamine 0.2 F
HFS i8 a conden~ation polymer of hydantoin, formaldehyde and mixed 0 ~ P toluene sulfo~amide fo~mulated with Brilliant Green (C.I. 42040) and C.l. Solvent Yellow 85.
~ ~FS is a condensation polymel o~ melamine, formaldehyde and mixed 0 ~ P toluene sulfonamide formulated with a red colorant.
*** M~IP is ~ toluene sulfonamide-formaldehyde plasticizing resin having a so~tening point of 62C and a ~peci~ic gravity of 1.35 at 25C and al60 sold as Santolite~MHP by the Monsanto Co.
Each coating after drying wa~ laminated to a copper clad circuit board substrate which was sceubbed with an abrasive brush, using a Riston~ hot roll laminator. The laminated boards were imagewi6e exeo~ed th~ough a 6 ~ Stouffec 41 steewedge u6ing a Rifiton~ PC 24 exposure device and develoeed using a semi-aqueoufi developer containing 11~ butyl Cellosolve~ and 1% boLax. The time of exposure was adju~ted to p~ovide a similar numbee, about 20, of developed image steps.
Sample~ of each developed board were tested using fitandard plating and etching techniques.
~z~
Plate and Etch Procedure:
Each board wa6 immer~ed foe 5 minutes in a 9.5~ aqueous ~olution o Metex~ s26B preæla~e cleaner at 130F (54.4C), rin~ed for 30 ~econds in S flowing water, immersed for 1 minute at room tempera~ure in 10% aqueou~ sul~uric acid, immer~ed in flowing water for 1 minute, immered in 18~ aqueous ammonium persulfate 801utio~, rin~ed in wa~e~ again, i~mer~ed in sulfuric acid once again ~or 1 ~inute and ~hen immer~ed in acidic CuS0~ plating ~slution and plated at 30 amps/sq. ft. ~0.333 amp6/~q. cm.) for 36 minu~es to produce 0.00 1 in. (0.025 mm) pla~ed copper .
The plated board wa~ ~in~ed in wat~r, i8 immer~ed for 1 minute in 20% aqueous fluoroboric acid ~olution, and then immersed in a commercial tin/~ead (60/40) fluoroborate olution (Hi-Thro~) and plated at 15 amps/sq. ~t. (0.166 amp6/sq. cm~ ~or 15 minutes to deposit 0.0004 in. tO.01 mmj solder on ~he coppe~
plated image.
The board was cin~ed with water and then the photopolymerized resist was stripped from the plated boacd using 9Z% methylene chloride/8% methanol solvent solution.
The 6trip~ed board wa8 6prayed at 30 psi with an aqueous ammoniacal copper chloride solution (pH 7.8--8.Z) (MacDermid Co. Ultra Etch~ Fine Line) for 1 minute a~ 130F (54.4C) to produce a solder plated copper circuit pattern.
30 Etchinc~ P~rocedure Each lmaged and developed board was sprayed at 30 p8i with an etchant solution at 130F (5~.4C) until all unprotected copper was removed. In the instance when an alkaline etchant was used, ~acDermid 35 Ultra Etch~ Fine Line was the etchant~ In the instance when acid etchant wa~ used, sufficient cupric chloride and hydrochloric acid was used to prnduce an aqueou~ 601ution with a pH about 2.3~ and containing ~g ounces of copper/gallon (177 g/l~ of e~chan~.
Evaluation of Plate and ~tch Board~
Each board wa~ examined with a 50 powe~
optical micloscope to determine i~ circuit line edges are "ragged" due ~o lifting of ~he edge~ of the resist with plating ~hereunder (known as ~underplating"), or connected to adjoining circuit lines ("short" c~rcuit) due to re8i8t "blistering".
U~derpla~ing and ~horts indicate resi6t adhesion failure during the plating proceduce re6ulting in re~ist delamination or blistering. The board~ are al~o exa~ined for the aepearance of a bright ring or "halo" around circuit lines. The presence of halo while not a defect ltself indicates the potential for underplating failure.
Evaluation of Etchant Board~
After board~ were etched the re6ist is stripped as previously described and examined with the optical microscope to determine if circuit line edge6 are "ragged", i.e., contain~ llnicks'l at the circuit line edges or if circuit line is "narrowed"
indicating adhesion failure of the resist during etching. Gro6s ~ailure leads ~o "breaks" or "opens"
in the ciccuit line.
~able II contains the evaluation of the 30 plated and etched board6 and the alkaline and acid etched boards. In the table "NF" indicates no failure o~ adhesion was ob~erved.
~2~
TABLE II
Proces6-ing Proced- Coated Board ure A a c D E F
Plate ~ "ragged" NF NF NF l'ragged'1 "ragged"
etch "shorts" "~hocts"
Alkaline "ragged" NF ~F NP "ragged" "ragged"
Etch Acid "ragged" NF NF "ragged" "ragged" "ragged"
Etch "breaks" "breaks" "break~" "brealcs"
Re6ult~ indicate that the polymeric compound~
added to the solvent coated film Punction a~ least a~
well as the conventio~al adhesion promoter ~or both the plate and etch procedure and the alkaline etch procedure. The hydantoin containing polymer algo functioned sati6factorily for the acid etching procedure .
EXAMPLE ?~
A solventless composition similar to coatings "B" and "D" of Example 1 were prepared having ~he following compo~ition and were melt coated u6ing the procedures described in Re~earch Disclo6ure No. 24919 published January, 1985.
_qredient Amount Bindec 1 56 Trimethylol propane triacrylate 36 Benzoehenone Michler's ketone 0.1 Tcicresyl phosphate 2 Triethylene glycol diacetate Ccy~tal Violet 0.04 Red Dye CI los 0.3 COATTNG_COMPOSITION
Component G_ H
~a6~er 2 9~.8 99. a Benzotriazole .2 .2 ~5 -- 5.0 Each coatinq wa~ processed and evaluated a~
in E~ample 1 and re6ults are presented in Table III.
TABLE III
Processing Procedure Coated~Board G H
Plate ~ Etch NF NF
Alkaline Etch "Ragged" NF
Acid Etch "Breaks" NF
"~assive Failure"
ZO
The above re~ult~ demon~trate the advantage o~ u6ing the adhesion e~omoeers of thi6 inven~ion when compa~ed to conventional adhesion p~omoters 6uch a~ benzotriazole.
- _ A master solution wa~ prepared as in Example 1 except the binder component was adjusted for the amount o~ adhesion promoter added as indicated in Table IV. In Table IV Formulation X is a control ~ince it contains no adhe~ion promotor.
~2~
Inqredient Amount Trimethylol propane triacrylate 226 Benzophenone 25 ~Sichler' 5 ketone 0.63 Tricresyl ~hospha~e 12.5 T~ie~hylene glycol diacetate 6.3 Methylene ~hloride 1128 Methanol 38 TABLE IV
Coatinq Composition Inaredient X I J K L M N
~aster 3 229 229 229 229 229 229 ~29 Binder 1 55.2 54.7 5~.2 52.2 51.2 50.2 49.2 HFS O .5 1.0 2.0 3.0 4.0 5.0 ~ ach solution was coated, proce6sed and evaluated a6 in Example 1. In addieion, the adhesion of pho~ore~i6t to copper prior to exposure was measured by removing the polyethylene terephthalate support and adhering 1 inch (2.54 cm) wide Scotch~
brand masking tape 2262MSR to the resist sucface.
One end of the tape was attached to an Instron~
30 Univec6al Testing Instrument model 1130 and peeled at a 180 direction at 5 inches/min (12.7 cm/min) ~rom the board substrate surface. The force needed to separate the resist from the coppec surface was identified as the "Copper ~dhesion" and represented as the numbee of grams per linear cm. In addition ~5~6~
the pla~e and etch and alkaline etching evaluations were quantified by identifying the number of defects for a test board having 125 lines 0.007 in. ~0.178 mm) with an eguivalent number and size space~
the~ebetween. Fo~ example in the in~tance where no HFS adhe~ion p~omotoe was u6ed (Coating X), ~he adhesion to copper p~ior to ex~osure wafi measured to be 13.~ g eee lineae cm. The te~t board after alkaline etching had 3 BLeaks and 8 Nick~ wieh eesi6 lifting and peeling and a similar board after platin~
had ~alos, Li~ting and Shorts. The results for the coatingfi at the inceea~ing concen~ration ar~
pre6e~ted ~Q Table V whe~e "NF" indieates no failure, "H" indicates eresence o~ halo~, "L" indicates Li~ting, ~S" indicate~ Shorts, "B" indica~es Break6.
"N" indicates Nick~ and coppee adhe6ion ;6 given in g/cm.
TABLE V
Inqredient X I_ J_ ~ L M N
Plate and H,L,S NF NF NF NF NF NF
Etch Alkaline 3B+ 1~ 9B~ ~B~ lB~ lB NF
Etch 8N 2N 2N LN
Coppar 13.4 18.9 18.9 13.9 26.6 27.6 52.6 25 Adhesion As little as 0.5% by weight of the polymeric adhesion promotee i~ sufficient to improve performance during plate and etch processing and overall eerormance is 0 improved with about 4% of the adhesion promoter.
EX~MPLE 4 Six additional coatings were prepared and eroces~ed and evaluated as in Example 3 exce~t that adhesion promoter MFS was used in place of HFS.
TABLE VI
Coatinq ComQo~îtion In~redient 0 P _Q_ R S T
Mafi~er 3 229 229 229 229 229 229 Binder 1 54~7 53.2 52.2 51.250.2 4~.2 MFS .5 1 2 3 ~ 5 The quan~ified r2~ult~ belo~ in Tabl~ VII
indicate that improvement of all ~unctions begins with around 3~ of this adhesion p~omoter and ri~es rapidly to optimum perfo~mance by about 5%.
TA~LE VII
Inqredien~ ~ O P _Q_ R S T
Plate and H,L~S H~L H~L H~ H*~ NF ~F
Etch Alkaline 3~+ lB 6B lOB 4B lN NF
Etch 8N
Copper 13.4 13.4 16.2 16.2 21.5 25.~ 26.
20 Adhesion * Rlight ~* veLy slight Re~ults o~ the te~t6 in Examples 3 and ~
indicate that addition of either HFS or MFS improve6 adhesion perfo~mance o~ the laminated Rolvent coated re~ist films either in the plate and etch mode or the alkaline etch mode o~ both.
EX~MPLE 5 Two ~olvent processable 0.002 inch thick photoresi~t ~ilm~ were prepared from the following coating ~olutions:
~ ~35~
~o Coating Coating U V
Poly(methylme~hacrylateJ 56 56 ethylmethacrylate) (75/25) inherent visco~ity 0.49 Trimethylol propane ethoxylat~d 30.9 30.9 triacryla~e, ~.W. 400 ~ 50 Ethyl Michle~'~ ketone 0.15 0.15 Benzophenone 4 4 4-Methyl-4-trichloromethyl 0.06 0.06 cy~lohexadiene-l-one p-Toluene ~ulfonic acid 0.05 0.05 Leuco Cry~tal Violet 0.25 0.25 Victoria Green Dye ~C.I. 42000) 0.04 0.04 Victoria Blue ~ye (C.I. 42595) 0.02 0.02 HFS-UP** ~ _ Santicizer~9 (mixed o and p 4.53 toluene ~ulfonamide) MHP~ - 8.53 Propylene glycol methyl ether 11 11 Methylene Chloride 175 17 * Trimethylolpropane ethoxylated triaceylate (TMPEOTA) has the following ethoxylate distribution which con6titutes a minimum of 92% o~ the distribution None 6~ Max Monoethoxy 10~20 Diethoxy-l 12~
Diethoxy~Z 14~Z1%
Triethoxy-l 21-29~
T.ciethoxy-2 6-10%
Tetraethoxy 12-20%
** HFS-UP i~ an unpigmented condensation polymer of hydantoin, fo~maldehyde and mixed o and p toluene sulfonamide formulated with phthalic anhydride.
ZO
~s~
~** M~IP is a toluene 6ulfonamide-formaldehyde pla~ticizing re~in having a softening point of 62C and a specific gravity of 1.35 at 25~C
and i~ purcha~ed a~ Santolite~MHP from the Mon6an~0 Co.
Each ~olution wa~ coated on a 0.001 inch thîck ~olye~hylene terephthalate ~uppor~ fil~ to give a dry coaeing thickne~s of 0.002 inch.
Each dried coated resis~ film wa~ laminated to three copper clad sub6trates which were scrubbQd with an abrasive bru~h ufiing a Ri~ton~ hot roll laminator. Each laminated board was imagewise exposed through a ~ Stouffer0 41 ~tepwedge using a Riseon~ PC 24 exposure de~ice and developed in a RistonO C Procesfio~ (at 60 to 70F with 20 psi s~ray ere~sure) containing stabilized 1,1~1 trichloroethaQe as the developer solvent.
Each of the develoeed boards were tested using the following rigorou~ plating and etching technique.
Each board was immersed ~or 5 minut~s in a 8.5% aqueous solution of Metex~ 9268 preplate cleaner at 130P (54.4C), rinsed for 1 min in f].owing wate~, immersed in 18% aqueous ammonium persulfate solution for 1 min or les~ to remove 10-15 inch coeper, rinsed in water again, immersed in sulfucic acid for 1 minute and ~hen immersed in alkaline coppec pycophosphate heating plating ~olution and plated at 20 amps/sq. t. for 59 minu~e~
to pcoduce 0.001 inch (O.OOZ5 cm) plated copper.
The plated board was rinsed in water, immer~ed fol 30 seconds in 20~ aqueous fluocaboric acid solution, and ~hen immersed in a commercial tin/lead (60/40) fluoroborate solution ~Hi-Thco~3 ~ ;~9~
and plated at 20 ampst6q. ft. (0.1667 amp~/6q. cm.) ~or 12 minu~e~ to deposit 0.0005 inch (0.01 mm) ~older on the copper plated image.
The board wa6 ~insed with wate~ and then the photopolymerized re~i6t wa~ stripped from the plated boaLd u~i~g methylene chlocide fiolvent.
The ~tripped board was s~rayed at 20 p8i wi~h an agueous ammoniacal coppe~ chloride solutio~
~pH 7.8-8.2~ (MacDermid Co., Ult~a Etch~ Fine Line) at 130CF ~5~.4C) to produce a solder plated ~oyper ~i~cuit pattern.
For each o~ the plated and etched board6 in which M~P was used in the resi~t formula~ion coppe~
staining occurred during the process which ls a defect indica~ing the potential for underplati~g. In co~tra~t no deects were observed for the ~lated and etched board~ which were prepared from the resi6t film containing HFS-UP.
The plated boa~d was rinsed in water, is immer6ed for 1 minute in Z0~ aqueous fluoroboric acid solution, and then immersed in a commercial tintlead (60/40) fluoroborate ~olution (Hi-Thro~) and plated at 15 amps/sq~ ft. (0.166 amps/sq. cm) for 15 minutes to deposit 0.0004 in. (0.01 mm) solder on the copeer elated image.
The board was rinsed with wate~ and ~hen ~he photopolymerized re6ist was stripped from the plated board ufiing 92~ methylene chlocide/8~ methanol ~olvent ~olution.
The 6tripped board was ~prayed at 30 psi with an aqueou6 ammoniacal copper chloride solution (pH 7.8-8.2) (MacDermid Co. Ultra Etch~ Fine Line) for 1 minute at 130F (54.~C) to produce a solder elated copper circuit pattern.
g EX~MPLE 6 Fouc ~olvent proceRsable 0.002 in thick photoresist films were prepared and ~ested for u6e under very cigorou~ plating and et~hing ~onditions.
A Ma6~er coating ~olution wa~ ~repared foe each coating having the following Composition:
Master 4 Com~osition ~mount Inq~edient in qram~
lo Poly(methylmethacrylate/ 728 ethylmethacrylate) (75J25) inherent vi~c08ity 0 . 49 Tcimethylol propane ethoxylated 401.7 triacrylate, M.W. 400 ~ 50 15 Ethyl Michler's ketone 1.95 Benzophenone 5Z.05 ~-Methyl-~-trichloromethyl 1.30 cyclohexadiene-l-one Tris-(4-diethylamino-2-tolyl) methane 1.95 Leuco Crystal Violet 3.25 Santicizer~9 tmixed o and p toluene 55.69 6ulfonamide) p-Toluene sulfucic acid 0.65 5-Chlocobenzotriazole 2.60 Pro~ylene glycol methyl ether142~58 Methylene chloride 2274.07 Coatinq Solution ''W'' contained the ingredients of Master solution 4 along with 0.52 y of Victoeia Gceen Dye: 0.39 g Victoria Blue Dye and 50.1 g of HFS-UP of Example 5.
Coatinq Solution "X" contained the 35 ingredients of Master solution 4 along with 51.01 g ~2g5~
o~ HFS-BG which is the condensaeion polymer of hydantoin, formaldehyde and mixed o and p ~oluene ~ulfonamide formulated wi~h 1~ Brilliant Green Dye ~C.I. 42040).
Coa~inq Solution "Y'' contain~ the ingredie~ts o~ Maste~ Solu~ion 4 along with 51.01 g of HFS-BGVB whieh is the condensation polymer o hydantoin, ocmaldehyd~ and mixed o and p ~oluene sulfonamide, formulated with 1% Brilliant Gcee~ D~e (C.I. ~2040) and 0.76~ Victo~ia Blue Dye (C.I. 425953.
Coatinq Solution "Z" contains tha ingredient6 of Master Solution 4 along with 51.01 g of HPS-VG~B whieh i8 the condensa~ion polymer o~
hydantoin, formaldehyde and mixed o and ~ t~luene sulfonamide, formulated with 1% Vi~toria Green Dye ~C.I. 42000) and 0.8% Victoria Blue Dye (C.I. 425953.
These coating solutions were coated, laminated exposed and develo~ed as i~ Example 5 and then te~ted using the copeer/tin-lead plating and etching procedure of Example 5 along ~ith a con~entional copper/nickel/gold plating procedure.
In this plating procedure the coeper i8 plated as in Example 5 the plated panel i6 rinfied in water for 1 minute and then nickel plated in an acidic nickel sulfamate solution using a current density of 30 amper6/square ~eet for 15 minutes to produce nickel plating 0.0003 inch thick. The nickel plated panel i5 then rinsed and immersed in a 10~ aqueous 6ulfuric acid both for 1 minute. rinsed again and then gold plted in a orosene~999 gold plating bath at ~3F
for 10 minutes at a cuccent den~ity of 10 amper6/square foot. In evaluating the result~ of these tests a ~eries of circuit board panel~ are processed for each coting and each panel is given a numerical value from 0 to 5 depending on whether the ~5~
panel has no defects, e.g., "0", non~unctional defect~, e.g.D 1, ~ and 3 (~uch as copper staininq) which ~ill produce accep~able circui~ board or func~ional defect~, e.g., 4 and 5~ ~ueh a~ ~
underplating and ~hort~ ~hich disquali~y the board foe use. The average value for each series of panels for each type of plating is given in Table VIII for each coating.
TABL~ VIII
Coatin~ Cllo~L~Cu/Ni~Au W(HFS-UP) 3.3 4.2 ~(HFS-BG) 2.0 2.25 Y(E~S-BGVB) 1.3 0.8 Z(HFS-VGVB) 3 3.1 While acceptable boards can be obtained from all of the coating6 u6ing Cu~Sn-Pb plating it i~
clear that best results are obtained using conden6ation polymecs ~ormulated in the presence of Brilliant Green Dye and some improvement is obtained with polymers formulated in the presence of Victoria ~lue and/or Vic~o~ia Green. This ~ame trend of impeovement is al60 present ~or panels prepared under the more severe condition6 of Cu/Ni/Au plating.
Claims (11)
1. In a process for forming a photoresist on a substrate comprising the steps of:
(a) laminating to the substrate a supported solid photosensitive film layer which is photopolymerizable or photocrosslinkable, (b) imagewise exposing the layer to actinic radiation, (c) removing unexposed areas of the layer to form resist areas, (d) permanently modifying areas of the substrate which are unprotected by the resist areas by etching the substrate or by depositing a material onto the substrate, and (e) removing the resist areas from the substrate, the photosensitive layer comprising:
(1) polymerizable or crosslinkable ethylenically unsaturated compound, and (2) radiation sensitive, free radical generating photoinitiator or photoinitiator system, wherein the improvement comprises the photosensitive layer containing an additive to increase adhesion to a substrate which is a condensation polymer formed from a triazine, formaldehyde and toluene sulfonamide or hydantoin, formaldehyde and toluene sulfonamide.
(a) laminating to the substrate a supported solid photosensitive film layer which is photopolymerizable or photocrosslinkable, (b) imagewise exposing the layer to actinic radiation, (c) removing unexposed areas of the layer to form resist areas, (d) permanently modifying areas of the substrate which are unprotected by the resist areas by etching the substrate or by depositing a material onto the substrate, and (e) removing the resist areas from the substrate, the photosensitive layer comprising:
(1) polymerizable or crosslinkable ethylenically unsaturated compound, and (2) radiation sensitive, free radical generating photoinitiator or photoinitiator system, wherein the improvement comprises the photosensitive layer containing an additive to increase adhesion to a substrate which is a condensation polymer formed from a triazine, formaldehyde and toluene sulfonamide or hydantoin, formaldehyde and toluene sulfonamide.
2. The process of claim 1 wherein the condensation polymer is formed from a triazine, formaldehyde and toluene sulfonamide.
3. The process of claim 1 wherein the triazine is melamine.
4. The process of claim 1 wherein the condensation polymer is formed from hydantoin.
formaldehyde and toluene sulfonamide.
formaldehyde and toluene sulfonamide.
5. The process of claim 1 wherein the condensation polymer is present in a concentration in a range from 0.5 to 25% by weight of the photosensitive layer.
6. The process of claim 1 wherein the concentration is in a range from 1 to 10% by weight of the photosensitive layer.
7. The process of claim 1 wherein the concentration is in a range from 2 to 6% by weight of the photosensitive layer.
8. The process of claim 1 wherein binder is present in the photosensitive layer.
9. The process of claim 1 wherein binder is absent in the photosensitive layer.
10. The process of claim 1 wherein the condensation polymr is formulated in the presence of a dye comprising Brilliant Green (C.I. 42040), Victoria Green (C.I. 42000) and Victoria Blue.
11. The process of claim 10 wherein the dye is Brilliant Green (C.I. 42020).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/837,389 US4693959A (en) | 1986-03-07 | 1986-03-07 | Adhesion promotion in photoresist lamination and processing |
| US837,389 | 1992-02-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1295169C true CA1295169C (en) | 1992-02-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000531062A Expired - Lifetime CA1295169C (en) | 1986-03-07 | 1987-03-03 | Adhesion promotion in photoresist lamination and processing |
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| Country | Link |
|---|---|
| US (1) | US4693959A (en) |
| EP (1) | EP0236950B1 (en) |
| JP (1) | JPS62240950A (en) |
| KR (1) | KR900006040B1 (en) |
| BR (1) | BR8700993A (en) |
| CA (1) | CA1295169C (en) |
| DE (1) | DE3779450T2 (en) |
| HK (1) | HK73592A (en) |
| SG (1) | SG77192G (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| JPH02202570A (en) * | 1989-01-30 | 1990-08-10 | Nitto Denko Corp | Double-sided adhesive tape for fixing photosensitive material |
| US5047313A (en) * | 1989-08-21 | 1991-09-10 | E. I. Du Pont De Nemours And Company | Photosensitive semi-aqueous developable copper conductor composition |
| JP2733143B2 (en) * | 1991-03-14 | 1998-03-30 | 冨士薬品工業株式会社 | Photosensitive composition for forming phosphor screen |
| US5268260A (en) * | 1991-10-22 | 1993-12-07 | International Business Machines Corporation | Photoresist develop and strip solvent compositions and method for their use |
| US5989689A (en) * | 1991-12-11 | 1999-11-23 | The Chromaline Corporation | Sandblast mask laminate with blastable pressure sensitive adhesive |
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| US6093335A (en) * | 1996-08-28 | 2000-07-25 | International Business Machines Corporation | Method of surface finishes for eliminating surface irregularities and defects |
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| US6268457B1 (en) | 1999-06-10 | 2001-07-31 | Allied Signal, Inc. | Spin-on glass anti-reflective coatings for photolithography |
| US6824879B2 (en) | 1999-06-10 | 2004-11-30 | Honeywell International Inc. | Spin-on-glass anti-reflective coatings for photolithography |
| US6297294B1 (en) * | 1999-10-07 | 2001-10-02 | E. I. Du Pont De Nemours And Company | Method for improving the adhesion of a photopolymerizable composition to copper |
| KR20040075866A (en) | 2001-11-15 | 2004-08-30 | 허니웰 인터내셔날 인코포레이티드 | Spin-on anti-reflective coating for photolithography |
| US8053159B2 (en) | 2003-11-18 | 2011-11-08 | Honeywell International Inc. | Antireflective coatings for via fill and photolithography applications and methods of preparation thereof |
| TWI257189B (en) * | 2004-12-08 | 2006-06-21 | Nan Ya Printed Circuit Board C | Electrode plate of a flat panel direct methanol fuel cell and manufacturing method thereof |
| JP2006330193A (en) * | 2005-05-24 | 2006-12-07 | Hitachi Chem Co Ltd | Photosensitive resin composition, photosensitive element and method for producing printed wiring board using therefor |
| US20080156346A1 (en) * | 2006-12-28 | 2008-07-03 | Taiwan Semiconductor Manufacturing Company, Ltd. | Method and apparatus for cleaning a substrate |
| US8557877B2 (en) | 2009-06-10 | 2013-10-15 | Honeywell International Inc. | Anti-reflective coatings for optically transparent substrates |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3469982A (en) * | 1968-09-11 | 1969-09-30 | Jack Richard Celeste | Process for making photoresists |
| US3645722A (en) * | 1969-09-04 | 1972-02-29 | Carpenter Technology Corp | Free machining stainless steel alloy |
| US3622234A (en) * | 1969-12-29 | 1971-11-23 | Gen Electric | Hot corrosion resistant superalloys |
| US4056453A (en) * | 1973-11-27 | 1977-11-01 | Basf Aktiengesellschaft | Uv-curing printing inks |
| US4312934A (en) * | 1976-10-21 | 1982-01-26 | Bard Laboratories, Inc. | Photosensitive compositions |
| US4293635A (en) * | 1980-05-27 | 1981-10-06 | E. I. Du Pont De Nemours And Company | Photopolymerizable composition with polymeric binder |
| DE3045516A1 (en) * | 1980-12-03 | 1982-07-08 | Basf Ag, 6700 Ludwigshafen | LIGHT SENSITIVE MULTILAYER MATERIAL AND METHOD FOR PRODUCING ADHESIVE LAYERS THEREFOR |
| US4442198A (en) * | 1981-01-16 | 1984-04-10 | W. R. Grace & Co. | Polymer composition having terminal alkene and terminal carboxyl groups |
| US4528261A (en) * | 1983-03-28 | 1985-07-09 | E. I. Du Pont De Nemours And Company | Prelamination, imagewise exposure of photohardenable layer in process for sensitizing, registering and exposing circuit boards |
-
1986
- 1986-03-07 US US06/837,389 patent/US4693959A/en not_active Expired - Fee Related
-
1987
- 1987-02-27 BR BR8700993A patent/BR8700993A/en unknown
- 1987-03-03 CA CA000531062A patent/CA1295169C/en not_active Expired - Lifetime
- 1987-03-05 EP EP87103129A patent/EP0236950B1/en not_active Expired - Lifetime
- 1987-03-05 DE DE8787103129T patent/DE3779450T2/en not_active Expired - Fee Related
- 1987-03-06 JP JP62050420A patent/JPS62240950A/en active Granted
- 1987-03-07 KR KR878702061A patent/KR900006040B1/en not_active IP Right Cessation
-
1992
- 1992-07-28 SG SG771/92A patent/SG77192G/en unknown
- 1992-09-24 HK HK735/92A patent/HK73592A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| SG77192G (en) | 1992-10-02 |
| KR870009617A (en) | 1987-10-27 |
| KR900006040B1 (en) | 1990-08-20 |
| DE3779450T2 (en) | 1993-01-28 |
| DE3779450D1 (en) | 1992-07-09 |
| HK73592A (en) | 1992-10-02 |
| EP0236950B1 (en) | 1992-06-03 |
| EP0236950A2 (en) | 1987-09-16 |
| US4693959A (en) | 1987-09-15 |
| JPH0415464B2 (en) | 1992-03-18 |
| BR8700993A (en) | 1987-12-22 |
| JPS62240950A (en) | 1987-10-21 |
| EP0236950A3 (en) | 1989-03-22 |
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