HK1056920A1 - Photoresist composition - Google Patents
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- HK1056920A1 HK1056920A1 HK03109274A HK03109274A HK1056920A1 HK 1056920 A1 HK1056920 A1 HK 1056920A1 HK 03109274 A HK03109274 A HK 03109274A HK 03109274 A HK03109274 A HK 03109274A HK 1056920 A1 HK1056920 A1 HK 1056920A1
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Description
Technical Field
The present invention relates to the field of photoresists. In particular, the present invention relates to photoresists having improved removal characteristics, particularly for use in the manufacture of printed wiring boards.
Background
The photoresist is used to transfer an image to a photosensitive film of a substrate. A photoresist coating is formed on a substrate and the photoresist layer is then exposed to an activating radiation source through a mask. The mask has some areas that are opaque to activating radiation and other areas that are transparent to activating radiation. Exposure to activating radiation provides a photo-induced chemical transformation in the photoresist coating that transfers the image of the reticle to the photoresist coated substrate. After exposure, the photoresist is developed to provide a relief image that allows the substrate to be selectively processed.
The photoresist may be positive or negative acting. In the case of negative-phase photoresists, the areas of the coating exposed to activating radiation undergo a polymerization or crosslinking reaction between the polymerizing agent and the photoactive compound of the photoresist composition. Thus, the exposed areas of the coating are less soluble in a developer solution than the unexposed areas. For a positive-working photoresist, the exposed regions are relatively soluble in a developer solution, and the unexposed regions remain relatively insoluble in the developer. Generally, photoresist compositions comprise at least a resinous binder component and a photoactive agent.
A variety of different polymeric or resinous binders may be used for the photoresist. Such polymeric binders may include one or more acid functional monomers, such as acrylic acid or methacrylic acid, as a polymeric ingredient. For example, U.S. patent No. 5,952,153 (Lundy et al) discloses optical imaging compositions that contain sufficient acid functionality as a polymeric binder to render the optical imaging composition developable in aqueous alkaline solutions.
The photoresist may be liquid or dry film. The liquid photoresist is first dispensed onto the substrate and then cured. The photoresist dry film can be laminated to a substrate. The photoresist dry film is particularly suitable for the manufacture of printed wiring boards. A problem with conventional photoresist dry film compositions is that they are difficult to remove from electrolytically plated circuit boards using known alkaline aqueous removal solutions (e.g., 3% sodium hydroxide solution). This problem is caused by the reduced size of the printed circuit board for the manufacturer of the printed circuit board to increase its functionality. Therefore, circuit lines and space of the circuit board are continuously reduced as more circuit circuits need to be accommodated in a smaller space. Meanwhile, the height of the plated metal must be higher than the thickness of the photoresist. The metal protrudes from the photoresist, and the narrow space containing the photoresist is substantially enclosed in the plated metal. The photoresist is limited by the plating overhang, making it difficult to access and remove by conventional methods. If the photoresist is not completely removed, it can cause undesirable rough copper circuit lines after etching, resulting in board shorts.
Some circuit board manufacturers attempt to increase the thickness of the photoresist while increasing the plating height to accommodate, however, this approach is expensive and limits the resolution of the circuit lines. Specifically, the use of organic-based (amine or organic solvent containing) alkaline scavenging solutions produces tiny scavenging particles that aid in scavenging. Thus, it is preferred to remove the photoresist by such organic-based purges, but they are more expensive relative to inorganic-based purges (e.g., sodium or potassium hydroxide) and have more associated waste disposal and environmental concerns. Photoresists that can clear solvent are also undesirable due to factory regulatory restrictions or to reduce solvent emissions.
Accordingly, it is still desirable to provide a photoresist composition that can be easily removed using an alkali-soluble removing solution based on inorganic materials.
Various trihalomethyl-substituted compounds are known as photoactive components. For example, U.S. Pat. No. 4,935,330 (Hofmann et al) discloses trihalomethyl-substituted triazazines as photoactive components in the manufacture of lithographic printing plates.
Thermo-responsive recording materials comprising a support having substantially adjacent electron donating dye precursors and alpha-trichloromethyl benzyl acetate thereon are disclosed in U.S. patent No. 5,668,080 (Cove et al). No photoresist composition is disclosed and proposed in this patent.
Disclosure of Invention
It has surprisingly been found that the addition of one or more non-polymeric photoresist removal enhancers provides a photoimaging composition having improved removal or removal. The photoresist removal enhancer is a compound having one or more trihalomethyl substituents in the alpha position relative to the substituent capable of stabilizing a negative charge. It has also been surprisingly found that such non-polymeric photoresist removal enhancers do not adversely affect other characteristics of the photoresist adhesive (e.g., chemical resistance). Thus, the compositions of the invention exhibit improved removal without substantially diminishing chemical resistance as compared to an otherwise identical composition lacking the non-polymeric photoresist removal enhancer.
In one aspect, the present invention provides a photoresist composition comprising a polymeric binder, a photoactive component, a photoresist removal enhancer, and optionally a crosslinker, wherein the photoresist removal enhancer having the structure of the formula is not polymerized with the polymeric binder, the optional crosslinker, or both,
wherein each X is independently chlorine, bromine, fluorine or iodine; z-cyano, aryl, substituted aryl, C (Y) -R1、C≡C-R2And C (R)3)＝CR4R5(ii) a Y ═ oxygen or sulfur; r ═ Z, hydrogen, (C)1-C4) Alkyl, (C)1-C4) Alkoxy, substituted (C)1-C4) Alkyl, substituted (C)1-C4) An alkoxy group; r1＝(C1-C8) Alkyl, (C)1-C8) Alkoxy, substituted (C)1-C8) Alkyl, substituted (C)1-C8) Alkoxy, aryl or substituted aryl; r2Hydrogen, (C)1-C8) Alkyl, substituted (C)1-C8) Alkyl, aryl or substituted aryl; r3、R4And R5Independently selected from hydrogen, halogen or R1。
In another aspect, the invention provides a method for enhancing removal of a photoresist composition from a substrate comprising the step of combining a photoresist composition with a photoresist removal enhancer, the photoresist composition comprising a polymeric binder, a photoactive component, and optionally a crosslinker, wherein the photoresist removal enhancer having the structure of the formula is not polymerized with the polymeric binder, the optional crosslinker, or both,
wherein each X is independently chlorine, bromine, fluorine or iodine; z-cyano, aryl, substituted aryl, C (Y) -R1、C≡C-R2And C (R)3)＝CR4R5(ii) a Y ═ oxygen or sulfur; r ═ Z, hydrogen, (C)1-C4) Alkyl, (C)1-C4) Alkoxy, substituted (C)1-C4) Alkyl, substituted (C)1-C4) An alkoxy group; r1＝(C1-C8) Alkyl, (C)1-C8) Alkoxy, substituted (C)1-C8) Alkyl, substituted (C)1-C8) Alkoxy, aryl or substituted aryl; r2Hydrogen, (C)1-C8) Alkyl, substituted (C)1-C8) Alkyl, aryl or substituted aryl; r3、R4And R5Independently selected from hydrogen, halogen or R1。
In yet another aspect, the present invention provides a method of manufacturing a printed wiring board, comprising the steps of: a) dispersing a photoresist composition on a substrate of a printed wiring board, the photoresist composition comprising a polymeric binder, a photoactive component, a photoresist removal enhancer, and optionally a crosslinker, wherein an organic acid having the structure of the formula is not polymerized with the polymeric binder and the optional crosslinker,
wherein each X is independently chlorine, bromine, fluorine or iodine; z-cyano, aryl, substituted aryl, C (Y) -R1、C≡C-R2And C (R)3)＝CR4R5(ii) a Y ═ oxygen or sulfur; r ═ Z, hydrogen, (C)1-C4) Alkyl, (C)1-C4) Alkoxy, substituted (C)1-C4) Alkyl, substituted (C)1-C4) An alkoxy group; r1＝(C1-C8) Alkyl, (C)1-C8) Alkoxy, substituted (C)1-C8) Alkyl, substituted (C)1-C8) Alkoxy, aryl or substituted aryl; r2Hydrogen, (C)1-C8) Alkyl, substituted (C)1-C8) Alkyl, aryl or substituted aryl; r3、R4And R5Independently selected from hydrogen, halogen or R1(ii) a b) Imaging the photoresist; and c) developing the photoresist.
In another aspect, the invention provides a method of enhancing removal of a photoresist composition from a substrate comprising the step of combining a curing agent having a net acrylate functionality of about 2 or more with a photoresist composition comprising a polymeric binder and a photoactive compound.
In this specification, unless otherwise indicated, the following abbreviations shall have the following meanings: DEG C is centigrade; g is gram; mg ═ mg; tg ═ glass transition temperature; f ═ Fahrenheit; wt% -% by weight; and mil 0.001 inch.
"resin" and "polymer" are used interchangeably in this specification. The term "alkyl" refers to straight-chain, branched, and cyclic alkyl groups. "halogen" and "halo" include fluorine, chlorine, bromine and iodine. Thus, "halogenated" refers to fluorinated, chlorinated, brominated, and iodinated. "Polymer" refers to homopolymers and copolymers and includes dimers, trimers, oligomers, and the like. "(meth) acrylate" means acrylate and methacrylate. Similarly, "(meth) acrylic" refers to both acrylic and methacrylic. "monomer" means any polymerizable ethylenically or acetylenically unsaturated compound. "crosslinker" and "crosslinker" are used interchangeably in this specification. "printed wiring board" and "printed circuit board" are used interchangeably in this specification.
All amounts are weight% and all proportions are weight ratios unless otherwise indicated. All numerical ranges are inclusive and combinable.
The photoresist composition of the invention comprises a polymeric binder, a photoactive component, a photoresist removal enhancer, and optionally a crosslinker, wherein the photoresist removal enhancer having the structure of the formula is not polymerized with the polymeric binder, the optional crosslinker, or both,
wherein each X is independently chlorine, bromine, fluorine or iodine; z-cyano, aryl, substituted aryl, C (Y) -R1、C≡C-R2And C (R)3)＝CR4R5(ii) a Y ═ oxygen or sulfur; r ═ Z, hydrogen, (C)1-C4) Alkyl, (C)1-C4) Alkoxy, substituted (C)1-C4) Alkyl, substituted (C)1-C4) An alkoxy group; r1＝(C1-C8) Alkyl, (C)1-C8) Alkoxy, substituted (C)1-C8) Alkyl, substituted (C)1-C8) Alkoxy, aryl or substituted aryl; r2Hydrogen, (C)1-C8) Alkyl, substituted (C)1-C8) Alkyl, aryl or substituted aryl; r3、R4And R5Independently selected from hydrogen, halogen or R1。
A variety of polymeric binders are suitable for use in the present invention. Suitable polymeric binders contain one or more ethylenically or acetylenically unsaturated monomers as polymerized units. Suitable monomers include, but are not limited to, (meth) acrylic acid, (meth) acrylamide, alkyl (meth) acrylates, alkenyl (meth) acrylates, aromatic (meth) acrylates, vinyl aromatic monomers, nitrogen containing compounds and their sulfur analogs, substituted ethylene monomers, cyclic olefins, substituted cyclic olefins, and the like. Preferred monomers comprise: (meth) acrylic acid, alkyl (meth) acrylates, and vinyl aromatic monomers. These polymeric binders may be homopolymers or copolymers, preferably copolymers. It is further understood that mixtures of binder polymers may also be used in the present invention. Thus, the light imaging compositions of the present invention may comprise one or more polymeric binders.
Specifically, the alkyl (meth) acrylate usable in the present invention is (C)1-C24) Alkyl (meth) acrylates. Suitable alkyl (meth) acrylates include, but are not limited to, "low cut" alkyl (meth) acrylates, "medium cut" alkyl (meth) acrylates, and "high cut" alkyl (meth) acrylates.
"Low cut" alkyl (meth) acrylates generally means that the alkyl group contains from 1 to 6 carbon atoms. Suitable low cut alkyl (meth) acrylates include, but are not limited to, methyl methacrylate ("MMA"), methyl acrylate, ethyl acrylate, propyl methacrylate, butyl methacrylate ("BMA"), butyl acrylate ("BA"), isobutyl methacrylate ("IBMA"), hexyl methacrylate, cyclohexyl acrylate, and mixtures thereof.
"cut-in" alkyl (meth) acrylates generally means that the alkyl group contains from 7 to 15 carbon atoms. Suitable middle cut alkyl (meth) acrylates include, but are not limited to, 2-ethylhexyl acrylate ("EHA"), 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, isodecyl methacrylate ("IDMA", branched (C)10) Mixtures predominantly of alkyl isomers), undecyl methacrylate, dodecyl methacrylate (i.e., lauryl methacrylate), tridecyl methacrylate, tetradecyl methacrylate (i.e., myristyl methacrylate), pentadecyl methacrylate, and mixtures thereof. Particularly useful mixtures comprise dodeca-pentadecyl methacrylate ("DPMA"); mixtures of linear and branched chain isomers of dodecyl, tridecyl, tetradecyl, and pentadecyl methacrylates; and lauryl-myristyl methacrylate ("LMA").
"high cut" alkyl (meth) acrylates generally means that the alkyl group contains from 16 to 24 carbon atoms. Suitable high cut alkyl (meth) acrylates include, but are not limited to, cetyl methacrylate, heptadecyl methacrylate, octadecyl methacrylate, nonadecyl methacrylate, eicosyl methacrylate, and mixtures thereof. Particularly useful high cut alkyl (meth) acrylate blends include, but are not limited to, cetyl-eicosyl methacrylate ("CEMA"), which is a mixture of cetyl, stearyl, arachidyl and eicosyl methacrylates; and cetearyl methacrylate ("SMA"), which is a mixture of cetyl and stearyl methacrylates.
The medium and high alkyl (meth) acrylate monomers described above are typically prepared by standard esterification reactions using technical grade long chain aliphatic alcohols, and these commercially available alcohols are mixtures of alcohols of varying chain lengths between 10 and 15 carbon atoms or between 16 and 20 carbon atoms in the alkyl group. Examples of such alcohols are: various Ziegler-catalyzed ALFOL alcohols from Vista chemical company, ALFOL 1618 and ALFOL 1620; various Ziegler-catalyzed NEODOL alcohols from Shell chemical company, NEODOL 25L, and natural alcohols such as TA-1618 and CO-1270 from Proctor & Gamble. Thus, for the purposes of the present invention, alkyl (meth) acrylates tend to comprise not only the individual alkyl (meth) acrylate products mentioned, but also mixtures of alkyl (meth) acrylates with the particular predominant alkyl (meth) acrylates mentioned.
The alkyl (meth) acrylate monomer used in the present invention may be a single monomer or a mixture having a different number of carbon atoms in the alkyl moiety. In addition, the (meth) acrylamide and alkyl (meth) acrylate monomers used in the present invention may be optionally substituted. Suitable optionally substituted (meth) acrylamide and alkyl (meth) acrylate monomers include, but are not limited to, hydroxy (C)2-C6) Alkyl (meth) acrylate, dialkylamino (C)2-C6) Alkyl (meth) acrylate, dialkylamino (C)2-C6) Alkyl (meth) acrylamides.
Particularly useful substituted alkyl (meth) acrylate monomers are those having one or more hydroxyl groups in the alkyl group, particularly those having a hydroxyl group in the beta-position (2-position) of the alkyl group. The substituted alkyl substituent in the hydroxyalkyl (meth) acrylate monomer is preferably branched or unbranched (C)2-C6) An alkyl group. Suitable hydroxyalkyl (meth) acrylate monomers include, but are not limited to, 2-hydroxyethyl methacrylate ("HEMA"), 2-hydroxyethyl acrylate ("HEA"), 2-hydroxypropyl methacrylate, 1-methyl-2-hydroxyethyl methacrylate, 2-hydroxy-propyl acrylate, 1-methyl-2-hydroxyethyl acrylate, 2-hydroxybutyl methacrylateAcrylates and mixtures thereof. Preferred hydroxyalkyl (meth) acrylate monomers are HEMA, 1-methyl-2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and mixtures thereof. The mixture of the last two monomers is commonly referred to as "hydroxypropyl methacrylate" or HPMA.
Other substituted (meth) acrylate and (meth) acrylamide monomers useful in the present invention are those having a dialkylamino group or dialkylaminoalkyl group in the alkyl group. Examples of such substituted (meth) acrylates and (meth) acrylamides include, but are not limited to: dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, N-dimethylaminoethyl methacrylamide, N-dimethyl-aminopropyl methacrylamide, N-dimethylaminobutyl methacrylamide, N-diethylaminoethyl methacrylamide, N-diethylaminopropyl methacrylamide, N-diethylaminobutyl methacrylamide, N- (1, 1-dimethyl-3-oxobutyl) acrylamide, N- (1, 3-diphenyl-1-ethyl-3-oxobutyl) acrylamide, N- (1-methyl-1-phenyl-3-oxobutyl) methacrylamide and 2-hydroxyethyl acrylamide, N-methacrylamide of aminoethyl ethylene urea, N-methacryloxyethyl morpholine, N-cis-butadienimide of dimethylaminopropylamine and mixtures thereof.
Other substituted (meth) acrylate monomers useful in the present invention are silicon-containing monomers, such as gamma-propyltri (C)1-C6) Alkoxysilyl (meth) acrylate, gamma-propyltri (C)1-C6) Alkylsilyl (meth) acrylate, gamma-propyldi (C)1-C6) Alkoxy (C)1-C6) Alkylsilyl (meth) acrylate, gamma-propyldi (C)1-C6) Alkyl radical (C)1-C6) Alkoxysilyl (meth) acrylate, vinyl tris (C)1-C6) Alkoxysilyl (meth) acrylate, vinyl di (C)1-C6) Alkoxy (C)1-C6) Alkylsilyl (meth) acrylate, vinyl (C)1-C6) Alkoxy di (C)1-C6) Alkylsilyl (meth) propenesAcid ester, vinyl tris (C)1-C6) Alkylsilyl (meth) acrylates, 2-propylsiloxane half (meth) acrylates and mixtures thereof.
Vinyl aromatic monomers useful as unsaturated monomers in the present invention include, but are not limited to, styrene ("STY"), hydroxystyrene, alpha-methylstyrene, vinyltoluene, p-methylstyrene, ethylvinylbenzene, vinylnaphthalene, vinylxylene, and mixtures thereof. Vinyl aromatic monomers also include their corresponding substituted counterparts, e.g., halogenated derivatives, i.e., containing one or more halogen groups, such as fluorine, chlorine or bromine; and nitro, cyano, (C)1-C10) Alkoxy, halo (C)1-C10) Alkyl, carbonyl (C)1-G10) Alkoxy, carboxyl, amino, (C)1-C10) Alkylamine derivatives, and the like.
Nitrogen-containing compounds and sulfur-analogs thereof useful as unsaturated monomers in the present invention include, but are not limited to, vinylpyridines, such as 2-vinylpyridine or 4-vinylpyridine; lower alkyl (C)1-C8) Substituted N-vinylpyridines, such as 2-methyl-5-vinylpyridine, 2-ethyl-5-vinylpyridine, 3-methyl-5-vinylpyridine, 2, 3-dimethyl-5-vinylpyridine and 2-methyl-3-ethyl-5-vinylpyridine; methyl-substituted quinolines and isoquinolines; n-vinyl caprolactam; n-vinyl butyrolactam; n-vinyl pyrrolidone; vinylimidazole; n-vinylcarbazole; n-vinyl-succinimide; (meth) acrylonitrile; ortho-, meta-, or para-aminostyrene; maleimide; n-vinyl-oxazolidinone; n, N-dimethylaminoethyl-vinyl-ether; ethyl-2-cyanoacrylate; vinyl acetonitrile; n-vinyl phthalimide; n-vinyl-pyrrolidones, e.g. N-vinyl-thio-pyrrolidone, 3-methyl-1-vinyl-pyrrolidone, 4-methyl-1-vinyl-pyrrolidone, 5-methyl-1-vinyl-pyrrolidone, 3-ethyl-1-vinyl-pyrrolidone, 3-butyl-1-vinyl-pyrrolidone, 3-dimethyl-1-vinyl-pyrrolidone, 4, 5-dimethyl-1-vinyl-pyrrolidone, 5-dimethyl-1-vinyl-pyrrolidone,3, 3, 5-trimethyl-1-vinyl-pyrrolidone, 4-ethyl-1-vinyl-pyrrolidone, 5-methyl-5-ethyl-1-vinyl-pyrrolidone and 3, 4, 5-trimethyl-1-vinyl-pyrrolidone; vinyl pyrrole; vinylaniline and vinylpiperidine.
Substituted ethylene monomers useful as unsaturated monomers in the present invention include, but are not limited to: vinyl acetate, vinyl formamide, vinyl chloride, vinyl fluoride, vinyl bromide, vinylidene chloride, vinylidene fluoride, vinylidene bromide, tetrafluoroethylene, trifluoroethylene, trifluoromethyl vinyl acetate, vinyl ether, and itaconic anhydride.
Suitable cycloolefin monomers in the present invention are (C)5-C10) Cyclic olefins such as cyclopentene, cyclopentadiene, dicyclopentene, cyclohexene, cyclohexadiene, cycloheptene, cycloheptadiene, cyclooctene, cyclooctadiene, norbornene, maleic anhydride, and the like. Such cyclic olefins also include spirocyclic olefin monomers such as spironorbornyl monomers, spirocyclic cyclohexene monomers, spirocyclic cycloheptene monomers, and mixtures thereof. Suitable substituted cyclic olefin monomers include, but are not limited to, cyclic olefins having one or more substituents selected from the group consisting of: hydroxy, aryloxy, halo, (C)1-C12) Alkyl, (C)1-C12) Haloalkyl, (C)1-C12) Hydroxyalkyl radical, (C)1-C12) Halo-hydroxyalkyl radicals, e.g. (CH)2)n·C(CF3)2OH, n' is 0 to 4, (C)1-C12) Alkoxy, thio, amino, (C)1-C6) Alkylamine, (C)1-C6) Dialkylamine, (C)1-C12) Alkyl sulfur, carbonyl (C)1-C20) Alkoxy, carbonyl (C)1-C20) Haloalkoxy, (C)1-C12) Acyl, (C)1-C6) Alkylcarbonyl (C)1-C6) Alkyl groups, and the like. Particularly suitable substituted cycloalkenes include maleic anhydride and compounds containing one or more hydroxy, aryloxy, (C)1-C12) Alkyl, (C)1-C12) Haloalkyl, (C)1-C12) Hydroxyalkyl radical, (C)1-C12) Halohydroxyalkyl, carbonyl (C)1-C20) Alkoxy and carbonyl (C)1-C20) Haloalkoxy cycloalkenes. It will be appreciated by those skilled in the art that alkyl and alkoxy substituents may optionally be substituted, for example with halogen, hydroxy, cyano, (C)1-C6) Alkoxy, mercapto, (C)1-C6) Alkylthio, amino, acid labile leaving groups, and the like. Suitable carbons (C)1-C20) Alkoxy substituents include, but are not limited to, those of the formula C (O) O-LG, wherein LG is a leaving group, including, but not limited to, alkyl groups having 4 or more carbon atoms with at least one quaternary carbon atom directly bonded to the oxo group, such as tert-butyl, 2, 3-dimethylbutyl, 2-methylpentyl, 2, 3, 4-trimethylpentyl, cycloaliphatic, vinyl ether, or acetal or ketal formed from an enol, such as-O- (CH) O-LG3)OC2H5) or-O- (CH)2OC2H5) Tetrahydropyrans ("THPs"). Alicyclic esters suitable as leaving groups include adamantyl, methyladamantyl, ethyladamantyl, methylnorbornyl, ethylnorbornyl, ethyltrimethylnorbornyl, ethylfenchyl alcohol and the like.
In addition, the preferred polymeric binders contain sufficient acid functionality to render the binding polymer soluble and removable after development. "acid functional group" refers to any functional group that forms a salt upon contact with an alkaline developer; alkaline developers, for example dilute aqueous sodium or potassium hydroxide solutions, such as 1 to 3% by weight solutions. Suitable acid functional groups include, but are not limited to, carboxylic acids, sulfonic acids, phosphonic acids, and phenols. Generally, the binding polymer can have an acid number of up to about 250, preferably up to about 200. Typical acid numbers range from 15 to 250, preferably 50 to 250. The acid number is based on the amount (milligrams) of potassium hydroxide ("KOH") required to neutralize 1 gram (dry weight) of the binding polymer.
Suitable polymeric binders are commercially available from a variety of different sources, such as Rohm and Haas company (Philadelphia, Pennsylvania) or are prepared in various ways known in the literature. Specifically, the polymeric binder is present in the photoimageable composition in an amount up to 90% by weight, preferably 20 to 90% by weight, more preferably 25 to 85% by weight, and most preferably 30 to 80% by weight, based on the total weight of the composition.
A variety of different photoresist removal enhancers can be used in the present invention which do not polymerize with the polymeric binder, the optional crosslinker, or both, without incorporating an adhesive polymer or crosslinker. Thus, the photoresist removal enhancer used in the present invention is substantially absent, preferably absent, of an adhesion polymerizer or crosslinker after curing. The photoresist removal enhancer is a compound having one or more trihalomethyl substituents in the alpha position relative to the substituent capable of stabilizing a negative charge. Without wishing to be bound by theory, it is believed that such trihalomethyl substituted compounds form carboxylate anions during the alkaline photoresist stripping step. Thus, any trihalomethyl-substituted compound that can form such carboxylate anions is suitable for use in the present invention.
Suitable photoresist removal enhancers have the formula:
wherein each X is independently chlorine, bromine, fluorine or iodine; z ═ cyano, aryl, substituted aryl, -C (Y) -R1、-O-C(Y)-R1、-C≡C-R2and-C (R)3)＝CR4R5(ii) a Y ═ oxygen or sulfur; r ═ Z, hydrogen, (C)1-C4) Alkyl, (C)1-C4) Alkoxy, substituted (C)1-C4) Alkyl, substituted (C)1-C4) An alkoxy group; r1＝(C1-C8) Alkyl, (C)1-C8) Alkoxy, substituted (C)1-C8) Alkyl, substituted (C)1-C8) Alkoxy, aryl or substituted aryl; r2Hydrogen, (C)1-C8) Alkyl, substituted (C)1-C8) Alkyl, aryl or substituted aryl(ii) a And R3、R4And R5Is independently selected from hydrogen, halogen or R1. "substituted alkyl" or "substituted alkoxy" refers to one or more hydrogen atoms of an alkyl or alkoxy group substituted with one or more other substituents, such as hydrogen, hydroxy, (C)1-C6) Alkoxy, phenyl, phenoxy, substituted phenyl, cyano, and the like. Similarly, "substituted aryl" or "substituted phenyl" refers to one or more hydrogen atoms of an aryl or phenyl group, substituted with one or more other substituents, such as hydrogen, (C)1-C6) Alkyl, (C)1-C6) Alkoxy, phenyl, phenoxy, substituted phenyl, cyano, and the like.
Preferably, in the photoresist removal enhancer, at least one of Z and R is an aryl or alkenyl group, preferably a phenyl or alkenyl group. Preferably, R is phenyl or alkenyl and Z is aryl, -C (Y) -R1or-O-C (Y) -R1. Photoresist removal enhancers include, but are not limited to, alpha-trichloromethyl benzyl acetate, alpha-tribromomethyl benzyl acetate, alpha-triiodomethyl benzyl acetate, trichloromethyl allyl acetate, tribromomethyl allyl acetate, alpha-trichloromethyl benzyl propionate, alpha-tribromomethyl benzyl propionate, alpha-triiodomethyl benzyl propionate, trichloromethyl allyl propionate, tribromomethyl allyl propionate, alpha-trichloromethyl benzyl benzoate, alpha-tribromomethyl benzyl benzoate, alpha-triiodomethyl benzyl benzoate, trichloromethyl allyl benzoate, tribromomethyl allyl benzoate, and alpha-bromodichloromethyl benzyl acetate.
It will be appreciated by those skilled in the art that more than one photoresist removal enhancer may be advantageously used in the compositions of the present invention. Thus, the photoimaging compositions of the present invention may comprise one or more photoresist removal enhancers. It will also be appreciated by those skilled in the art that increasing the level of such non-polymeric photoresist removal enhancers in the compositions of the present invention allows for the use of polymeric binders having fewer acid functional groups without substantially diminishing the removal effectiveness. Thus, polymeric binders having other enhanced properties (e.g., enhanced chemical resistance), but lacking desirable cleaning properties, can be used in combination with the photoresist cleaning enhancer of the invention to provide readily removable photoimaging compositions.
The photoresist removal enhancer is generally commercially available from a variety of different sources, such as Aldrich Chemical Co. (Milwaukee, Wisconsin), and is used without further purification. Generally, the compositions of the present invention comprise one or more photoresist removal enhancers in an amount of up to about 10 wt.%, preferably up to about 8 wt.%, more preferably up to about 5 wt.%, based on the total dry weight of the adhesive polymer. Specifically, one or more photoresist removal enhancers are present in an amount of 0.125 wt% or more. The photoresist removal enhancer is present in an amount of 0.5 to 5 parts per 40 parts of polymeric binder on a dry weight/weight basis.
Suitable crosslinking agents for use in the present invention include di-, tri-, tetra-or higher functional ethylenically unsaturated monomers. Examples of crosslinking agents useful in the present invention include, but are not limited to, trivinylbenzene, divinyltoluene, divinylpyridine, divinylnaphthalene, and divinylxylene, such as ethylene glycol diacrylate, trimethylolpropane triacrylate ("TMPTA"), diethylene glycol divinyl ether, trivinylcyclohexane, allyl methacrylate ("ALMA"), ethylene glycol dimethacrylate ("EGDMA"), diethylene glycol dimethacrylate ("DEGDMA"), propylene glycol dimethacrylate, propylene glycol diacrylate, trimethylolpropane trimethacrylate ("TMPTMA"), divinylbenzene ("DVB"), glycidyl methacrylate, 2-dimethylpropane 1, 3-diacrylate, 1, 3-butanediol dimethacrylate, di-vinyl acetate, 1, 4-butanediol diacrylate, diethylene glycol dimethacrylate, 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, tripropylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, polyethylene glycol 200 diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, ethoxylated bisphenol A diacrylate, oxidized bisphenol A dimethacrylate, polyethylene glycol 600 dimethacrylate, poly (butylene glycol) diacrylate, pentaerythritol triacrylate, trimethylolpropane triethoxy triacrylate, glyceryl propoxy triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, diisopentaerythritol monohydroxypentaacrylate, pentaerythritol monohydroxypentaacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, Ethoxylated diacrylates, ethoxylated triacrylates (e.g., ethoxylated TMPTA and ethoxylated TMPTMA), ethoxylated tetraacrylates, divinylsilane, trivinylsilane, dimethyldivinylsilane, divinylmethylsilane, methyltrivinylsilane, diphenyldivinylsilane, divinylphenylsilane, trivinylphenylsilane, divinylmethylphenylsilane, tetravinylsilane, dimethylvinyldisiloxane, poly (methylvinylsiloxane), poly (vinylhydrosiloxane), poly (phenylvinylsiloxane), glycosylureas (including di-, tri-and tetra-glycosylureas), epoxies, and mixtures thereof. These crosslinking agents are generally commercially available.
One skilled in the art will recognize that the desired properties of the photoimageable composition may be imparted by combining two or more crosslinking agents. Therefore, a mixture of crosslinking agents is preferably used in the present invention. The photoresist composition of the present invention preferably comprises one or more crosslinkers. Specifically, the content of such a crosslinking agent in the optical imaging composition is from 5 to 75% by weight, preferably from 15 to 70% by weight, and more preferably from 20 to 65% by weight.
In another embodiment, one or more monomers are desirably combined with one or more crosslinkers to provide a curing agent system. In the curing agent system, one or more monomers are selected to provide certain desired characteristics in the cured photoresist. For example, the (meth) acrylate functional crosslinker may be combined with one or more monomers, preferably one or more (meth) acrylate monomers. "(meth) acrylate functional crosslinker" means a crosslinker having one or more (meth) acrylate groups, preferably two or more (meth) acrylate groups, i.e., of formula H2C ═ C (H or CH)3) The group of C (O) -O-. Specifically, theIn other words, the amount of crosslinker and monomer in the curative system is selected to provide the desired net (meth) acrylate functionality. "neat (meth) acrylate functionality" refers to the average (meth) acrylate functionality in the curative component. The net (meth) acrylate functionality is determined by averaging the amounts of the multi- (meth) acrylate-functional compound (i.e., crosslinker) and the mono- (meth) acrylate-functional compound (i.e., (meth) acrylate monomer) on a weight basis. For example, a triacrylate crosslinker (e.g., TMPTA) used in a 1: 1 weight mixture with acrylate monomers (i.e., compounds having one acrylate group) has a net (meth) acrylate functionality of about 2. In the optical imaging composition of the present invention, a curing agent system is preferably used as a crosslinking agent.
By selecting the neat (meth) acrylate functionality, the chemical resistance of the photoresist to photovoltaics is balanced for ease of removal or removal. Generally, increasing the branching of the cured photoresist (i.e., increasing the amount of crosslinking) increases the chemical resistance. Reducing the branching of the cured photoresist (i.e., reducing the amount of crosslinking) increases the cleaning efficacy of the cured photoresist, while reducing the chemical resistance of the cured photoresist. It has surprisingly been found that when the neat (meth) acrylic acid finger functionality is about 2, excellent chemical resistance is provided, while providing enhanced cleaning efficacy of the cured photoresist. When the neat (meth) acrylate functionality is greater than 2, the chemical resistance of the cured photoresist increases, but removal of such cured photoresist is not facilitated. When the neat (meth) acrylate functionality is less than 2, the removal efficacy of the cured photoresist is increased, but is detrimental to the chemical resistance of the cured photoresist.
Accordingly, the present invention provides a method for enhancing removal of a photoresist composition from a substrate comprising the step of combining a curing agent having a net (meth) acrylate functionality of about 2 or greater with a photoresist composition comprising a polymeric binder and a photoactive component. When the curing agent comprises acrylate functionality, the net acrylate functionality is preferably about 2 or greater, more preferably about 2. When the curing agent comprises methacrylate functionality, the neat methacrylate functionality is preferably 2 or less. The curing agent preferably comprises one or more acrylate crosslinkers and one or more non-crosslinking acrylate monomers. The curing agent preferably contains a triacrylate crosslinking agent and a non-crosslinkable acrylate monomer. The preferred curing agent is one that contains ethoxylated TMPTA as the crosslinking agent and the reaction product of epsilon caprolactone and HEA as the monomer. More preferably, the weight ratio of triacrylate crosslinker to non-crosslinkable acrylate monomer is about 1: 1. The curing agent preferably does not contain methacrylate functionality. When such a curing agent system does not contain methacrylate, it may have a net acrylate functionality.
The present invention also provides a photoimageable composition comprising one or more polymeric binders, one or more photoactive components, and a curing agent system comprising one or more crosslinkers and one or more monomers, wherein the curing agent system has a neat (meth) acrylate functionality of about 2.
The inventive photoimageable compositions contain one or more photoactive components. The photoactive component used in the present invention may be a photoacid generator, a photobase generator, or a radical generator. The light imaging compositions of the present invention may be positive acting or negative acting, with negative acting being preferred. It will be appreciated by those skilled in the art that mixtures of photoactive components can be used to render the composition photoactive for a particular application.
Suitable photoacid generators include halogenated triazines, onium salts, sulfonated esters, halogenated sulfonyloxy dicarboximides, diazodisulfones, alpha-cyanoamine sulfonates, imide sulfonates, ketone diazosulfones, sulfonyl diazoesters, 1, 2- (arylsulfonyl) hydrazines, and the like. Particularly useful halogenated triazazines include halomethyl-s-triazazine.
Suitable free radical generators include, but are not limited to, N-phenylglycine, aromatic ketones such as diphenyl ketone, N ' -tetramethyl-4, 4 ' -diaminediphenyl ketone "Michler's ketone", N ' -tetraethyl-4, 4 ' -diaminediphenyl ketone, 4-methoxy-4 ' -dimethylamine diphenyl ketone, 3 ' -dimethyl-4-methoxy diphenyl ketone, p ' -bis (dimethylamine) diphenyl ketone, p ' -bis (diethylamine) diphenyl ketone, anthraquinone, 2-ethylanthraquinone, naphthoquinone, and phenanthrenequinone; benzophenones, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin; benzyl derivatives such as benzhydryl, benzhydryldithio and benzhydryldimethyl ketal; acridine derivatives, such as 9-phenylacridine and 1, 7-bis (9-acridinyl) heptane; 9-oxodibenzothiopyrans such as 2-chloro-9-oxodibenzothiopyran, 2-methyl-9-oxodibenzothiopyran, 2, 4-diethyl-9-oxodibenzothiopyran, 2, 4-dimethyl-9-oxodibenzothiopyran and 2-isopropyl-9-oxodibenzothiopyran; acetophenones, such as 1, 1-dichloroacetophenone, p-tert-butyldichloro-acetophenone, 2-diethoxyacetophenone, 2-dimethoxy-2-phenylacetophenone and 2, 2-dichloro-4-phenoxyacetophenone; 2, 4, 5-triarylimidazole dimers such as 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4, 5-bis (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4, 5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer, 2, 4-bis (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2, 4-dimethoxyphenyl) -4, 5-diphenylimidazole dimer and 2- (p-methylthiophenyl) -4, 5-diphenylimidazole dimer, and the like. However, the free radical generator (triphenylphosphine) is not included in the photoactive chemical system as a catalyst. The free radical generator is suitable for use in negative acting photo imaging composition, preferably in the negative acting photo imaging dry film composition of the present invention.
In particular, the amount of the photoactive composition is from 0.05 to 10 wt%, preferably from 0.1 to 5 wt%, more preferably from 0.1 to 2 wt%, based on the total weight of the composition.
The optical imaging composition of the present invention may optionally contain a solvent. Suitable solvents include, but are not limited to, ketone solvents such as ethanone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; polyhydric alcohols and derivatives thereof, such as ethylene glycol, ethylene glycol monoethyl ester, diethylene glycol monoethyl ester, propylene glycol monoethyl ester, dipropylene glycol and dipropylene glycol monoethyl ester, and monomethyl, monoethyl, monopropyl, monobutyl and monophenyl ethers thereof; cyclic ether solvents such as dioxane; ester solvents such as methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxy propionate, and ethyl ethoxy propionate; amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone; 3-ethoxyethyl propionate; 2-heptanone; gamma-butyrolactone and mixtures thereof.
Additives that may be used in the optional photo-imageable compositions of the present invention include, but are not limited to, anti-striation agents, plasticizers, speed enhancers, fillers, dyes, film formers, non-polymeric acids, and the like. Suitable plasticizers include esters, such as benzoate esters. The luminescent imaging compositions of the present invention are preferably formulated with one or more non-polymeric organic acids. Suitable organic acids are substantially non-polymerizable with the polymeric binder, the optional crosslinker, or both. A variety of different organic acids are suitable for addition to the light emitting resist compositions of the present invention. Suitable organic acids include, but are not limited to, alkane carboxylic acids and arene carboxylic acids, sulfonic acids, such as alkane sulfonic acids and arene sulfonic acids, phosphonic acids, such as alkyl phosphonic acids and aryl phosphonic acids, and the like. Examples of carboxylic acids include, but are not limited to, (C)1-C12) Alkyl carboxylic acids; (C)1-C12) Alkyl dicarboxylic acids; (C)1-C12) Alkyl tricarboxylic acids; substituted (C)1-C12) Alkyl carboxylic acids; substituted (C)1-C12) Alkyl dicarboxylic acids; substituted (C)1-C12) Alkyl tricarboxylic acids; amine carboxylic acids such as ethylenediaminetetraacetic acid; aromatic carboxylic acids such as aromatic monocarboxylic acids, aromatic dicarboxylic acids and aromatic tricarboxylic acids; and substituted aryl carboxylic acids. Preferred organic acids include: formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, glycolic acid, lactic acid, tartaric acid, citric acid or malic acid, ethylenediaminetetraacetic acid, phthalic acid, succinic acid, adipic acid, lactic acid, tartaric acid, citric acid, malic acid, ethylenediaminetetraacetic acid, phthalic acid, maleic,Benzene tricarboxylic acid, silicic acid, cyclohexane carboxylic acid, 1, 4-cyclohexane dicarboxylic acid, and sebacic acid.
These optional additives may be present in the photoresist composition in a variety of concentrations. For example, fillers and dyes may be used in relatively large concentrations, for example in amounts of about 5 to 30% by weight, based on the total weight of the dry ingredients of the composition. Such organic acids are generally present in amounts of up to about 10 wt.%, preferably in amounts of up to about 8 wt.%, more preferably up to about 5 wt.%, based on total dry weight of the adhesive polymer.
The light emitting resist compositions of the present invention are generally prepared by combining, in any order, a polymeric binder, a photoactive component, a resist removal enhancer, an optional crosslinking agent, an optional solvent, and optional additives.
The preparation of the photoimaging or photoresist composition of the present invention can be any known method. In the conventional method, a photoresist layer applied to a substrate may be formed from a liquid composition or converted from a dry film to a photoresist layer. When the liquid photoresist composition is used, it may be applied to the substrate by any known method, such as spin coating, dip coating, roll coating, etc.
The photoresist composition of the present invention can be used for various substrates for the manufacture of electronic components such as printed wiring boards and integrated circuits. Suitable substrates include copper surfaces of copper plating plates, inner and outer layers of printed wiring boards, wafers used in the manufacture of integrated circuits, and the like.
After the photoresist is applied to the substrate, it is exposed to activating radiation in an image or through an appropriate pattern. In the case of negative-acting photoresists, exposure to activating radiation polymerizes the crosslinking agent in the exposed areas, producing a crosslinked structure that is resistant to developer. Subsequently, the composition was developed using a diluted aqueous alkaline solution. Suitable developers comprise 1 to 3% by weight aqueous sodium hydroxide or potassium hydroxide. An organic-based developer (e.g., tetraalkylammonium hydroxide-based developer) can be used, but this is not preferred. During development, the acidic groups of the binding polymer form salts that render the binding polymer soluble or removable.
In the case where a negative-acting photoresist is applied to the copper surface of a copper plating plate, the copper may be removed from the areas where the photoresist has been removed using an etchant after development to form a printed circuit. The remaining photoresist is then removed with a scavenger.
Accordingly, the present invention provides a method of manufacturing a printed wiring board, comprising the steps of: a) dispersing a photoresist composition on a substrate of a printed wiring board, the composition comprising a polymeric binder, a photoactive component, a photoresist removal enhancer, and optionally a crosslinker, wherein an organic acid having the structure of the formula is not polymerized with the polymeric binder and the optional crosslinker;
wherein each X is independently chlorine, bromine, fluorine or iodine; z-cyano, aryl, substituted aryl, C (Y) -R1、C≡C-R2And C (R)3)＝CR4R5(ii) a Y ═ oxygen or sulfur; r ═ Z, hydrogen, (C)1-C4) Alkyl, (C)1-C4) Alkoxy, substituted (C)1-C4) Alkyl, substituted (C)1-C4) An alkoxy group; r1＝(C1-C8) Alkyl, (C)1-C8) Alkoxy, substituted (C)1-C8) Alkyl, substituted (C)1-C8) Alkoxy, aryl or substituted aryl; r2Hydrogen, (C)1-C8) Alkyl, substituted (C)1-C8) Alkyl, aryl or substituted aryl; r3、R4And R5Independently selected from hydrogen, halogen or R1(ii) a b) Imaging the photoresist; and c) developing the photoresist.
The light emitting resist compositions of the present invention exhibit improved removal compared to conventional non-polymeric organic acid free light emitting resists. Accordingly, the present invention also provides a method for enhancing removal of a photoresist composition from a substrate comprising the step of combining a photoresist composition with a photoresist removal enhancer, the photoresist composition comprising a polymeric binder, a photoactive component, and optionally a crosslinker, wherein the photoresist removal enhancer having the structure of the formula is not polymerized with the polymeric binder, the optional crosslinker, or both,
wherein each X is independently chlorine, bromine, fluorine or iodine; z-cyano, aryl, substituted aryl, C (Y) -R1、C≡C-R2And C (R)3)＝CR4R5(ii) a Y ═ oxygen or sulfur; r ═ Z, hydrogen, (C)1-C4) Alkyl, (C)1-C4) Alkoxy, substituted (C)1-C4) Alkyl, substituted (C)1-C4) An alkoxy group; r1＝(C1-C8) Alkyl, (C)1-C8) Alkoxy, substituted (C)1-C8) Alkyl, substituted (C)1-C8) Alkoxy, aryl or substituted aryl; r2Hydrogen, (C)1-C8) Alkyl, substituted (C)1-C8) Alkyl, aryl or substituted aryl; r3、R4And R5Independently selected from hydrogen, halogen or R1。
It has also been surprisingly found that such non-polymeric photoresist removal enhancers do not adversely affect other characteristics of the photoresist adhesive, such as chemical resistance. Thus, the photoresist compositions of the invention exhibit improved removal without a substantial loss in chemical resistance as compared to the same composition without the non-polymeric photoresist removal enhancing compound.
Detailed Description
The following examples are intended to illustrate various aspects of the present invention in further detail, and are not intended to limit the scope of the present invention in any way.
Examples
Example 1
Four negative acting photoresist composition dry film samples A-D were prepared combining the amounts of the ingredients listed in Table 1. The polymeric binder is an acid functional group. A mixture of ethoxylated TMPTA was used as the curative and the reaction product of epsilon-caprolactone and HEA was used as the hydroxy-functional mono-acrylate monomer and mixed in a 1: 1 weight ratio to give a net acrylate functionality of about 2. A mixture of three free-radical generators was used as a light-starting system. A mixture of two adhesion promoters was used in each sample. Each sample contained trichloromethyl benzyl acetate ("TCMBA") as a photoresist removal enhancer containing a hydrophobic trihalomethyl group. To sample D, 1, 4-cyclohexanedicarboxylic acid (a non-polymeric organic acid) was added. The dye package used is a photochromic tautomer dye mixture. Samples A through D were prepared as dry films of photoresist according to conventional processing techniques.
TABLE 1
| Sample (I) | A | B | C | D |
| (meth) acrylate adhesive Polymer 1 (g) | 0 | 0 | 0 | 40 |
| (meth) acrylate adhesive Polymer 2 (g) | 36 | 36 | 36 | 0 |
| (meth) acrylate adhesive Polymer 4 (g) | 4 | 4 | 4 | 0 |
| Curing agent (gram) | 28 | 28 | 28 | 28 |
| Light starting system (gram) | 2.5 | 2.5 | 2.5 | 6 |
| 1, 4-Cyclohexanedicarboxylic acid (g) | 0 | 0 | 0 | 2 |
| TCMBA (gram) | 1 | 3 | 5 | 1 |
| Adhesion promoter (Ke) | 0.1 | 0.1 | 0.1 | 0.1 |
| Dye bag (gram) | 0.6 | 0.6 | 0.6 | 0.6 |
| Other Compounds (g) | 0.1 | 0.1 | 0.1 | 0.3 |
Example 2
Samples a to D of example 1 were applied to a separation panel. Comparative samples C-1 and C-2 were applied to separate panels. Each panel was treated in the same manner, i.e., using the same pre-plating procedure, cleaning procedure, etc. Comparative sample C1 is a commercially available negative-acting electroplated photoresist dry film (available from Shipley, MA) containing an acid functional (meth) acrylate binder, a curing agent comprising a crosslinker and a mono (meth) acrylate, a free-radical generating photoinitiator system, and a dye package. Comparative sample C1 did not contain a curing agent system having a net acrylate functionality of about 2, a non-polymeric organic acid, nor any hydrophobic trihalomethyl-containing photoresist removal enhancer. Comparative sample C2 is a commercially available electroplated photoresist Dry film (RISTON)TM9020) (available from Dupont Printed Circuits (Wilmingto, DE)) and is free of non-polymeric organic acids and any hydrophobic trihalomethyl-containing photoresist removal enhancers contained in C1.
The panels containing the photoresist of samples A through D and comparative samples C-1 and C-2 were evaluated for development limit, relative exposure rate (photospeed), post exposure contrast, post developed photoresist sidewall appearance, copper/tin plating performance, and photoresist clean-up time. The evaluation results are shown in Table 2. The exposure rate was determined using a Stouffer21 stepped optical wedge (copper 9) at 50% (i.e., the unexposed resist was washed off halfway through the development chamber). Post exposure contrast is best when the color difference between exposed and unexposed areas of the panel is visually inspected, with a rating of "1".
The appearance of the photoresist sidewalls after development was determined by scanning electron microscopy. Scanning electron micrographs of the panel after development were evaluated to determine the side erosion and/or pedestal grade of the photoresist sidewalls. A sidewall rating of "1" indicates substantially no side attack or pedestal, and a rating of "2" or "3" indicates a partial side attack or pedestal on the photoresist sidewall.
Copper/tin ("Cu/Sn") plating efficacy is a measure of the platability of a photoresist. According to this performance test, the vertical electroplated copper traces were examined to determine whether the photoresist had washed away. The photoresist wash-off can be measured by bottom copper electroplating. Each panel was punched to one square centimeter and the amount of bottom plating was visually inspected by light microscopy. A rating of "1" indicates substantially no bottom plating, and a rating of "2" or "3" indicates varying degrees of bottom plating.
The photoresist removal time is the number of seconds required to completely remove or remove the photoresist at 130 ° F using 3% caustic soda.
TABLE 2
| Sample (I) | A | B | C | D | C-1* | C-2* |
| Development Limit (seconds) | 25.6 | 24.6 | 24.0 | 25.9 | 24.8 | 25.1 |
| Exposure Rate (Cu, 50%) (mJ/cm)2) | 168 | 168 | 168 | 60 | 84 | 84 |
| Contrast after exposure | 1 | 1 | 1 | 1 | 3 | 2 |
| Developed photoresist sidewall appearance | 1 | 1 | 1 | 1 | 3 | 1 |
| Copper/tin plating performance | 1 | 1 | 1 | 1 | 1 | 2 |
| Photoresist clean-up time (seconds) | 37.8 | 36.9 | 38.2 | 35.7 | 50.3 | 52.2 |
The above data clearly show that the photoresist composition of the present invention has improved properties compared to known photoresist dry films and can be removed significantly more rapidly than known photoresists.
Claims (9)
1. A photoresist composition comprising a polymeric binder, a photoactive component, a photoresist removal enhancer, and optionally a crosslinker, wherein the photoresist removal enhancer having the formula does not polymerize with the polymeric binder, the optional crosslinker, or both,
wherein each X is independently chlorine, bromine, fluorine or iodine; z-cyano, aryl, substituted aryl, C (Y) -R1、C≡C-R2And C (R)3)＝CR4R5(ii) a Y ═ oxygen or sulfur; r ═ Z, hydrogen, (C)1-C4) Alkyl, (C)1-C4) Alkoxy, substituted (C)1-C4) Alkyl, substituted (C)1-C4) An alkoxy group; r1＝(C1-C8) Alkyl, (C)1-C8) Alkoxy, substituted (C)1-C8) Alkyl, substituted (C)1-C8) Alkoxy, aryl or substituted aryl; r2Hydrogen, (C)1-C8) Alkyl, substituted (C)1-C8) Alkyl, aryl or substituted aryl; r3、R4And R5Independently selected from hydrogen, halogen or R1Wherein the photoresist removal enhancer is selected from the group consisting of α -trichloromethyl benzyl acetate, α -tribromomethyl benzyl acetate, α -triiodomethyl benzyl acetate, trichloromethyl allyl acetate, tribromomethyl allyl acetate, α -trichloromethyl benzyl propionate, α -tribromomethyl benzyl propionate, α -triiodomethyl benzyl propionate, trichloromethyl allyl propionate, tribromomethyl allyl propionate, α -trichloromethyl benzyl benzoate, α -tribromomethyl benzyl benzoate, α -triiodomethyl benzyl benzoate, trichloromethyl allyl benzoate, tribromomethyl allyl benzoate, and α -bromodichloromethyl benzyl acetate.
2. The composition of claim 1 wherein at least one of Z and R is aryl or alkenyl.
3. The composition of claim 1 wherein the photoresist stripper enhancer is present in an amount up to 10% by weight.
4. A method for enhancing removal of a photoresist composition from a substrate comprising the step of combining a photoresist composition with a photoresist removal enhancer, the photoresist composition comprising a polymeric binder, a photoactive component, and optionally a crosslinker, wherein the photoresist removal enhancer having the structure of the formula does not polymerize with the polymeric binder, the optional crosslinker, or both,
wherein each X is independently chlorine, bromine, fluorine or iodine; z-cyano, aryl, substituted aryl, C (Y) -R1、C≡C-R2And C (R)3)＝CR4R5(ii) a Y ═ oxygen or sulfur; r ═ Z, hydrogen, (C)1-C4) Alkyl, (C)1-C4) Alkoxy, substituted (C)1-C4) Alkyl, substituted (C)1-C4) An alkoxy group; r1＝(C1-C8) Alkyl, (C)1-C8) Alkoxy, substituted (C)1-C8) Alkyl, substituted (C)1-C8) Alkoxy, aryl or substituted aryl; r2Hydrogen, (C)1-C8) Alkyl, substituted (C)1-C8) Alkyl, aryl or substituted aryl; r3、R4And R5Independently selected from hydrogen, halogen or R1Wherein the photoresist removal enhancer is selected from the group consisting of α -trichloromethyl benzyl acetate, α -tribromomethyl benzyl acetate, α -triiodomethyl benzyl acetate, trichloromethyl allyl acetate, tribromomethyl allyl acetate, α -trichloromethyl benzyl propionate, α -tribromomethyl benzyl propionate, α -triiodomethyl benzyl propionate, trichloromethyl allyl propionate, tribromomethyl allyl propionate, α -trichloromethyl benzyl benzoate, α -tribromomethyl benzyl benzoate, α -triiodomethyl benzyl benzoate, trichloromethyl allyl benzoate, tribromomethyl allyl benzoate, and α -bromodichloromethyl benzyl acetate.
5. A method of manufacturing a printed wiring board, comprising the steps of: a) disposing a photoresist composition on a substrate of a printed wiring board, the photoresist composition comprising a polymeric binder, a photoactive component, a photoresist removal enhancer, and optionally a crosslinker, wherein an organic acid having the structure of the formula is not polymerized with the polymeric binder and the optional crosslinker,
wherein each X is independently chlorine, bromine, fluorine or iodine; z-cyano, aryl, substituted aryl, C (Y) -R1、C≡C-R2And C (R)3)＝CR4R5(ii) a Y ═ oxygen or sulfur; r ═ Z, hydrogen, (C)1-C4) Alkyl, (C)1-C4) Alkoxy, substituted (C)1-C4) Alkyl, substituted (C)1-C4) An alkoxy group; r1＝(C1-C8) Alkyl, (C)1-C8) Alkoxy, substituted (C)1-C8) Alkyl, substituted (C)1-C8) Alkoxy, aryl or substituted aryl; r2Hydrogen, (C)1-C8) Alkyl, substituted (C)1-C8) Alkyl, aryl or substituted aryl; r3、R4And R5Independently selected from hydrogen, halogen or R1(ii) a b) Imaging the photoresist; and c) developing the photoresist, wherein the photoresist removal enhancer is selected from the group consisting of alpha-trichloromethyl benzyl acetate, alpha-tribromomethyl benzyl acetate, alpha-triiodomethyl benzyl acetate, trichloromethyl allyl acetate, tribromomethyl allyl acetate, alpha-trichloromethyl benzyl propionate, alpha-tribromomethyl benzyl propionate, alpha-triiodomethyl benzyl propionate, trichloromethyl allyl propionate, tribromomethyl allyl propionate, alpha-trichloromethyl benzyl benzoate, alpha-tribromomethyl benzyl benzoate, alpha-triiodomethyl benzyl benzoate, trichloromethyl allyl benzoate, tribromomethyl allyl benzoate, and alpha-bromodichloromethyl benzyl acetate.
6. The method of claim 4 or 5, wherein at least one of Z and R is aryl or alkenyl.
7. The method of claim 4 or 5, wherein R is phenyl or alkenyl and Z is aryl,-C(Y)-R1or-O-C (Y) -R1。
8. A process according to claim 4 or 5 wherein the cross-linking agent is a curing agent having a net acrylate functionality of 2 or more.
9. The method of claim 8, wherein the curing agent comprises one or more acrylate cross-linking agents and one or more non-cross-linkable acrylate monomers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HK03109274.5A HK1056920B (en) | 2003-12-20 | Photoresist composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HK03109274.5A HK1056920B (en) | 2003-12-20 | Photoresist composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| HK1056920A1 true HK1056920A1 (en) | 2004-03-05 |
| HK1056920B HK1056920B (en) | 2006-04-21 |
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Effective date: 20211223 |