text:
|Publication number
|Publication type
|Application number
|Publication date
|Jul 9, 1991
|Filing date
|Aug 10, 1989
|Priority date
|Aug 11, 1988
|Fee status
|Also published as
|Publication number
|Sadao Fujikura, Masayuki Iwasaki, Minoru Maeda, Minoru Wada
|Original Assignee
|Fuji Photo Film Co., Ltd.
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (13), Referenced by (30), Classifications (30), Legal Events (5)
|External Links: USPTO, USPTO Assignment, Espacenet
A3 r--SO2 CZ3 IIIc
The present invention relates to a photo-polymerizable composition containing photo-polymerization initiator systems in a novel combination. More particularly, it relates to a photo-polymerizable composition which is adapted for the use in lithographic printing plates, resinous letter press printing plates, and as photoresists or photomasks for making print bases having a high sensitivity, a high resolving power and an excellent efficiency of printing out, and which provides excellent film properties.
Recently in the electronics industry there has been a demand for an increase in integration thus requiring a photo resist having a higher resolving power. In addition, a higher sensitivity is demanded so as to shorten the time required for production steps.
Studies for enhancing sensitivity of a photo-polymerizable composition have conventionally been conducted and, as a result, many photo-polymerization initiators (systems) have been proposed. For example, U.S. Pat. No. 2,448,828 describes benzoin ethers, U.S. Pat. No. 3,046,127 describes anthraquinones, JP-B-49-11936 (the term "JP-B" as used herein means an "examined Japanese patent publication") (corresponding to U.S. Pat. No. 3,661,588) describes aminophenylketone and an active methylene or amino compound, U.S. Pat. No. 3,682,641 describes Michler's ketones and benzophenone, JP-B-48-38403 describes benzophenone and 4-N,N-diethylaminobenzophenone, JP-B-45-37377 and JP-B-48-38403 describe Michler's ketones and lophine dimers, JP-A-56-35134 (the term "JP-A" as used herein means an "unexamined published Japanese patent application") describes lophine dimers and photo-polymerizable unsaturated monomers, JP-A-59-78339 describes a ternary system of 4-N,N-dialkylaminobenzophenones, benzophenone and an organic halogen compound, and the like.
It is true that the use of these photo-polymerization initiator systems serves to improve sensitivity and resolving power to some extent, but the degree of improvement is still insufficient for satisfying the recent requirements. In addition, when used as dry film resists to be used upon preparation of printed circuit boards, they provide a tenting film with only an insufficient strength upon formation of through-holes according to the tenting process, and hence a film-breaking trouble has been liable to take place during a development or etching step. It is well known that breakage of a film during the development or etching step can cause a serious problem of conduction failure as a result of dissolution with an etching solution of the copper-plated portion inside the through-hole conducting the surface side and the back side to each other.
It is therefore and object of the present invention to provide a photo-polymerizable composition which has a high sensitivity and a high resolving power, and which can provide excellent film properties.
This and other objects of the present invention will become apparent from the following description thereof.
As a result of various investigations, the inventors have found a photo-polymerizable composition containing a novel combination of photo-polymerization initiator systems capable of attaining the above-described and other objects of the present invention.
That is, the above-described and other objects of the present invention are attained by using a photo-polymerizable composition comprising:
(1) a thermoplastic polymeric binder;
(2) a non-gaseous ethylenically unsaturated compound;
(3) a photo-polymerization initiator system composed of 4,4'-bis(dialkylamino)benzophenone, an aromatic ketone, and a lophine dimer;
(4) an organic halogen compound; and
(5) a leuco dye.
The reason why the composition obtains superior effects is not understood, but may be attributed to that the combination serves to markedly enhance the efficiency of photo-polymerization reaction of the non-gaseous ethylenically unsaturated compound.
As the thermoplastic polymeric binder to be used in the photo-polymerizable composition of the present invention, those which satisfy the following requirements are selected from among a wide variety of synthetic, semi-synthetic and natural polymeric substances. That is, compatibility of the binder with the non-gaseous ethylenically unsaturated compound, the photo-polymerization initiator system, the organic halogen compound, and the leuco dye must be good enough not to cause destruction (Separating out) of the mixed state in the production steps of from preparation of a coating solution to a coating and drying step and during storage of coated products, the binder must have properties adapted for the intended use of the present invention (for example, in the case of using as photo resist for tenting, it must possess strength, stretchability, abrasion resistance, chemical resistance, etc.), and molecular weight, intermolecular force, hardness, softening temperature, crystallinity, elongation at breakage, etc. of the binder should be satisfactory for the in tended use.
Specific examples of the binders include homopolymers or copolymers such as chlorinated polyolefins (for example, chlorinated polyethylene and chlorinated polypropylene), polyalkyl (meth)acrylates (examples of the alkyl group include a methyl group, an ethyl group and a butyl group, and examples of the polyalkyl (meth)acrylates include polymethyl (meth)acrylate), copolymers between (meth)acrylic acid and alkyl (meth)acrylate, poly(meth)acrylic acid, copolymers between alkyl (meth)acrylate (examples of the alkyl group are the same as mentioned above) and at least one monomer such as acrylonitrile, vinyl chloride, vinylidene chloride, styrene, butadiene, etc., polyvinyl chloride, a copolymer between vinyl chloride and acrylonitrile, polyvinylidene chloride, a copolymer between vinylidene chloride and acrylonitrile, a copolymer between vinyl acetate and vinyl chloride, polyacrylonitrile, a copolymer between acrylonitrile and styrene, a copolymer between acrylonitrile, butadiene and styrene, a copolymer between styrene and an unsaturated dibasic acid anhydride such as maleic anhydride, polyvinyl butyral, styrene-butadiene rubber, chlorinated rubber, cyclized rubber, acetyl cellulose, and the like.
With copolymers, content ratios of the component monomers may be selected from a wide range but, in general, each comonomer is contained in an amount of preferably 5 mol % or more. Other polymers than are described above may also be used as binders in the present invention as long as they satisfy the foregoing requirements.
Of the above-described polymers, those which are preferably used as the binder of the present invention are chlorinated polyethylene, chlorinated polypropylene, polymethyl methacrylate, methyl methacrylate-acrylonitrile copolymer (molar content of methyl methacrylate: 20 to 80%), vinyl chloride-acrylonitrile copolymer (molar content of vinyl chloride: 20 to 80%), vinylidene chloride-acrylonitrile copolymer (molar content of vinylidene chloride: 20 to 80%), styrene-maleic anhydride copolymer, and binders described in JP-A-60-258539 (binder being methyl methacrylate/methacrylic acid/2-ethylhexyl methacrylate/benzyl methacrylate quaternary copolymer), JP-B-54-34327 (corresponding to U.S. Pat. No. 3,804,631) (binders being, for example, a methyl methacrylate/2-ethylhexyl methacrylate/methacrylic acid ternary copolymer), JP-B-55-38961 (binder being a styrene/mono-n-butyl maleate copolymer), JP-B-54-25957 (binders being, for example, a styrene/methyl methacrylate/ethyl acrylate/methacrylic acid quaternary copolymer), JP-A-52-99810 (corresponding to U.S. Pat. No. 4,139,391) (binders being, for example, a benzyl methacrylate/methacrylic acid copolymer), JP-B-58-12577 (binders being, for example, an acrylonitrile/2-ethylhexyl methacrylate/methacrylic acid terpolymer) and JP-B-55-6210 (binders being, for example, a methyl methacrylate/ethyl acrylate/acrylic acid terpolymer and a styrene/maleic acid anhydride copolymer partially esterified with isopropanol). Of these, methyl methacrylate/methacrylic acid/2-ethylhexyl methacrylate/benzyl methacrylate quaternary copolymer is a particularly preferable binder.
These binders may be used independently, or two or more polymers having enough compatibility with each other not to cause separation out of the mixed state in the steps of preparation of a coating solution to coating and drying and during storage of the coated products may be mixed in a proper ratio for use as a binder.
The molecular weight of the high molecular substance to be used as a binder may vary over a wide range depending upon the kind of polymer and intended use but, in general, polymers with a molecular weight of 5,000 to 2,000,000, more preferably 50,000 to 1,000,000 are preferably used in the present invention.
The amount of the binder is 5 to 95 wt %, preferably 40 to 80 wt %, based on the solid components of the photo-polymerizable composition.
Preferable ethylenically unsaturated compounds to be used in the present invention are those compounds which have at least two terminal unsaturated groups and which can be photo-polymerized by irradiation with actinic radiation (e.g., ultraviolet light, etc.). Hereinafter, they are abbreviated as polyfunctional monomers.
Specific examples thereof are the following compounds described in, for example, JP-B-35-5093, JP-B-35-14719 and JP-B-44-28727.
First, as acrylic esters and methacrylic esters, there are illustrated polyacrylates and polymethacrylates (the term "poly" as used herein means "di or more") of polyhydric alcohols. Examples of the polyhydric alcohols include polyethylene glycol, polypropylene glycol, polybutylene glycol, polycyclohexene oxide, polystyrene oxide, polycyclobutane, polytetrahydrofuran, cyclohexanediol, xylylenediol, di-(β-hydroxyethoxy)benzene, glycerin, diglycerin, neopentyl glycol, trimethylolpropane, trimethylolethane, pentaerythritol, dipentaerythritol, sorbitan, sorbitol, butanediol, butanetriol, 2-butene-1,4-diol, 2-n butyl-2-ethylpropanediol, 2-butyne-1,4-diol, 3-chloro-1,2-propanediol, 1,4-cyclohexanedimethanol, 3-cyclohexene-1,1-dimethanol, decalindiol, 2,3-dibromo-2-butene-1,4-diol, 2,2-diethyl-1,3-propanediol, 1,5-dihydroxy-1,2,3,4-tetrahydronaphthalene, 2,5-dimethyl-2,5-hexanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diphenyl-1,3-propanediol, dodecanediol, meso-erythritol, 2 ethyl-1,3-hexanediol, 2-ethyl-2-(hydroxymethyl)-1,3-propanediol, 2-ethyl-2-methyl-1,3-propanediol, heptanediol, hexanediol, 3-hexene-2,5-diol, hydroxybenzyl alcohol, hydroxyethylresorcinol, 2-methyl-1,4-butanediol, 2-methyl-2,4-pentanediol, nonanediol, octanediol, pentanediol, 1-phenyl-1,2-ethanediol, propanediol, 2,2,4,4-tetra-memthyl-1,3-cyclobutanediol, 2,3,5,6-tetramethyl-p-xylene-α,α'-diol, 1,1,4,4-tetraphenyl-1,4-butanediol, 1,1,4,4-tetraphenyl-2-butyne-1,4-diol, 1,2,6-trihydroxyhexane, 1,1'-bi-2-naphthol, dihydroxynaphthalene, 1,1'-methylene-di-2-naphthol, 1,2,4-benzenetriol, biphenol, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(hydroxyphenyl)methane, catechol, 4-chlororesorcinol, 3,4-dihydroxyhydrocinnamic acid, hydroquinone, hydroxybenzyl alcohol, methyl hydroquinone, methyl-2,4,6-trihydroxybenzoate, phloroglucinol, pyrogallol, resorcinol, glucose, α-(1-aminoethyl)p-hydroxybenzyl alcohol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propanediol, N-(3-aminopropyl)-diethanolamine, N,N-bis(2-hydroxyethyl)piperazine, 2,2-bis(hydroxymethyl)2,2',2''-nitrilotriethanol, 2,2-bis(hydroxymethyl)propionic acid, 1,3-bis(hydroxymethyl)urea, 1,2-bis(4-pyridyl)-1,2-ethanediol, N-n-butyldiethanolamine, diethanolamine, N-ethylenediethanolamine, 3-mercapto-1,2-propanediol, 3-piperidino-1,2-propanediol, 2-(2-pyridyl)-1,3-propanediol, triethanolamine, α-(1-aminoethyl)p-hydroxybenzyl alcohol, 3-amino-4-hydroxyphenylsulfone, etc. Of these acrylic esters and methacrylic esters, the most preferable ones in view of availability include ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, tetrapropylene glycol diacrylate, dodecapropylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, dipentaerythritol pentaacrylate, glycerin triacrylate, diglycerin dimethacrylane, 1,3-propanediol diacrylate, 1,2,4-bytanetriol trimethacrylate, 1,4-cyclohexanediol diacrylate, 1,5-pentanediol diacrylate, neopentyl glycol diacrylate, ethylene oxide-added trimethylolpropane triacrylate, etc.
On the other hand, as acrylamides and methacrylamides, there are illustrated polyacrylamides and polymethacrylamides of ethylenediamine, diaminopropane, diaminobutane, pentamethylenediamine, hexamethylene-bis(2-aminopropyl)amine, diethylenetriaminediamine, heptamethylenediamine, octamethylenediamine, polyamine interrupted by a hetero atom or atoms, and ring-containing polyamine (e.g., phenylenediamine, xylylenediamine, β-(4-aminophenyl)ethylamine, diaminobenzoic acid, diaminotoluene, diaminoanthraquinone, or diaminofluorene) as well as methylenebisacrylamide and methylenebismethacrylamide.
As allyl compounds, there are illustrated, for example, diallyl esters of dicarboxylic acids (e.g., phthalic acid, terephthalic acid, sebacic acid, adipic acid, glutaric acid, malonic acid and oxalic acid) and diallyl esters or diallylamides of disulfonic acids (e.g., anthraquinonedisulfonic acid, benzenedisulfonic acid, 2,5-dihydroxy-p-benzenedisulfonic acid, dihydroxynaphthalene-disulfonic acid and naphthalenedisulfonic acid).
As vinyl ether compounds, there are illustrated polyvinyl ethers of the aforementioned polyhydric alcohols such as ethylene glycol divinyl ether, 1,3,5-tri-β-vinyloxyethoxybenzene, glycerol trivinyl ether, etc.
As vinyl esters, there are illustrated divinyl succinate, divinyl adipate, divinyl phthalate, divinyl terephthalate, divinylbenzene-1,3-disulfonate, divinylbutane-1,4-disulfonate, etc.
As styrene compounds, there are illustrated divinylbenzene, p-allylstyrene, p-isopropenestyrene, etc.
Those compounds which contain two or more different addition-polymerizable unsaturated bonds such as N-β-hydroxyethyl-β-(methacrylamide)ethyl acrylate, N,N-bis(β-methacryloxyethyl)acrylamide, allyl methacrylate, etc. may also be preferably used in the present invention.
Furthermore, polyfunctional urethane compounds having at least two ethylenically unsaturated groups and being obtained by reacting a reaction product between a polyol compound having at least two hydroxy groups and a slightly excessive amount of a polyisocyanate compound having at least two isocyanato groups with a compound having at least one hydroxy group and at least one ethylenically unsaturated group may also be preferably used in the present invention.
These polyfunctional monomers may be used alone or in combinations of two or more, and are used in a proportion of 5 to 90 wt %, preferably 15 to 60 wt %, of the solid components of the photo-polymerizable composition.
Specific examples of 4,4-bis(dialkylamino)benzophenones to be preferably used in the present invention include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(dicyclohexylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(dihydroxyethylamino)benzophenone.
Of these, 4,4'-bis(diethylamino)benzophenone is a particularly preferable compound.
The amount of 4,4'-bis(dialkylamino)benzophenone to be used in the present invention is preferably 0.01 wt % to 1 wt % based on the solid components of the photo-polymerizable composition, with 0.05 wt % to 0.5 wt % being more preferable.
Specific examples of the aromatic ketones include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenonetetracarboxylic acid or its tetramethyl ester, 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, anthraquinone, 2-tert-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, fluorene, acridone, benzoin and benzoin ethers (e.g., benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether and benzoin phenyl ether), and benzyl dimethyl ketal, with benzophenone being particularly preferable. The aromatic ketone to be used in the present invention is added in an amount of preferably 0.1 wt % to 10 wt %, more preferably 0.5 wt % to 5 wt %, based on the solid components of the photo-polymerizable composition.
As the lophine dimers to be used in the present invention, there are illustrated, for example, those which are described in JP-B-45-37377, JP-B-48-9005 (corresponding to U.S. Pat. No. 3,558,322), JP-B-48-38403 (corresponding to U.S. Pat. No. 3,549,367), JP-B-53 12802 (corresponding to U.S. Pat. No. 3,652,275), JP-B-55-34414 (corresponding to U.S. Pat. No. 3,844,790), JP-A-56-35134 (corresponding to U.S. Pat. Nos. 4,311,783 and 4,252,887), JP-A-56 139508, JP-A-57-21401, JP-A-57-161742 (corresponding to U.S. Pat. No. 4,410,621), JP-A-58-19315, JP-A-59-818, JP-B-59-28329, JP-A-59-56403, JP-A-59-74551 (corresponding to U.S. Pat. No. 4,454,218), etc. Specific preferable examples include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-di(3'-methoxyphenylimidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl)-4,5-ciphenylimidazole dimer, 2-(4'-methoxyphenyl)-4,5-diphenylimidazole dimer, etc.
Of these, 2-(2'-chlorophenyl) 4,5-diphenylimidazole dimer and 2-(2'-chlorophenyl)-4,5-di(3'-methoxyphenyl)imidazole dimer are particularly preferable.
The lophine dimer to be used in the present invention is preferably added in an amount of 0.1 wt % to 10 wt %, more preferably 0.5 wt % to 5 wt %, based on the solid components of the photo-polymerizable composition.
In the present invention, conventionally known photo-polymerization initiators may be used in a proper combination in addition to the foregoing 4,4'-bis(dialkylamino)benzophenone, aromatic ketone and lophine dimer. For example, organic sulfur compounds, peroxides, redox compounds, azo and diazo compound, photoreducible dyes, etc. described in J. Kosar; "Light-Sensitive Systems", chapter 5, etc. may be used. These conventional known photo-polymerization initiators are preferably used in an amount of 0.01 to 5 wt %, based on the solid components of the photo-polymerizable composition.
The organic sulfur compounds include di-n-butyldisulfide, dibenzyldisulfide, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, thiophenol, ethyltrichloromethanesulfenate, 2-mercaptobenzimidazole, etc.
The peroxides include di-t-butyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, etc.
The redox compounds comprise a combination of a peroxide and a reducing agent, and include a combination of ferrous ion and persulfate ion, a combination of ferric ion and a peroxide, etc.
The azo and diazo compounds include α,α'-azobisisobutyronitrile, 2-azobis-2-methylbutyronitrile, p-aminodiphenylamine diazonium salt, etc.
The photo-reducible dyes include Rose Bengale, Erythrosin, Eosine, acriflavine, riboflavin, Thionine, etc.
As the organic halogen compounds to be used in the present invention, compounds selected from the compounds described in JP-A-59 78339 (corresponding to U.S. Pat. No. 4,584,260) and represented by the following general formulae IIIa to IIIe are preferable: ##STR1## wherein A1 r represents a substituted or unsubstituted phenyl or a substituted or unsubstituted naphthyl group, and Z represents a chlorine atom or a bromine atom; ##STR2## wherein A2 r represents a substituted or unsubstituted aryl group, W represents a hydrogen atom or a C1 to C20 alkyl or a C6 to C20 aryl group, and Z represents a chlorine atom or a bromine atom;
A3 r--SO2 CZ3 IIIc
wherein A3 r represents a substituted or unsubstituted phenyl or a substituted or unsubstituted naphthyl group, and Z represents a chlorine atom or a bromine atom; ##STR3## wherein Z represents a chlorine atom or a bromine atom; and ##STR4## wherein R2 represents CZ3 or a substituted or unsubstituted phenyl or a substituted or unsubstituted naphthyl group, R3 represents CZ3, NH2, NHR4, N(R4)2, SR4, OR4 or R4, R4 represents a C1 to C20 alkyl, a C6 to C20 aryl or a C2 to C20 alkenyl group, and Z represents a chlorine atom or a bromine atom.
Compounds of the general formula IIIa include those compounds which are described in JP-A-55-77742 (corresponding to U.S. Pat. No. 4,279,982), and preferable examples thereof include 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-chlorophenyl)1,3,4-oxadiazole, 2-trichloromethyl-5-(1-naphthyl)1,3,4-oxadiazole, 2-trichloromethyl-5-(2-naphthyl)1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5-(2-naphtyl)-1,3,4-oxadiazole, etc., with 2-trichloromethyl-5-(1-naphthyl)-1,3,4-oxadiazole and 2-trichloromethyl-5-(4-chlorophenyl)-1,3,4-oxadiazole being particularly preferable.
Compounds represented by the general formula IIIb include those compounds which are described in JP-A-54-74728, and preferable examples thereof include 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-chlorostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-methoxystyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(1-naphthyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-4-n-butoxystyryl)-1,3,4-oxadiazole, and 2-tribromomethyl-5-styryl-1,3,4-oxadiazole. Of these compounds, 2-trichloromethyl-5-(4-chlorostyryl)-1,3,4-oxadiazole and 2-trichloromethyl-5-(4-n-butoxystyryl)-1,3,4-oxadiazole are particularly preferable.
Specific examples of the compounds represented by the general formula IIIc include phenyl tribromomethyl sulfone, p-nitrophenyl tribromomethyl sulfone, and p-chlorophenyl tribromomethyl sulfone, with phenyl tribromomethyl sulfone being particularly preferable.
Specific examples of the compounds represented by the general formula IIId include 2-trichloromethylquinazolinone and 2-tribromomethylquinazolinone, with 2-trichloromethylquinazolinone being particularly preferable.
Compounds represented by the general formula IIIe are those compounds which are described in JP-A-54-74887 (corresponding to U.S. Pat. No. 4,239,850), and specific examples thereof include 2,4,6-tris(trichloromethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(4-chlorophenyl)4,6-bis(tribromomethyl)-s-triazine, with 2,4,6-tris(trichloromethyl)-s-triazine and 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine being particularly preferable.
Further examples of the organic halogen compounds usable in the present invention include halogenated hydrocarbons, halogenated alcohol compounds, halogenated carbonyl compounds, halogenated ether compounds, halogenated ester compounds and halogenated amide compounds.
Examples of the halogenated hydrocarbons include tetrabromocarbon, iodoform, 1,2-dibromoethane, 1,1,2,2-tetrabromoethane, 1,1-bis(p-chlorophenyl)-2,2,2-trichloroethane, 1,2-dibromo-1,1,2-trichloroethane, 1,2,3-tribromopropane, 1-bromo-4-chlorobutane, 1,2,3,4-tetrabromobutane, tetrachlorocyclopropene, hexachlorocyclopentadiene, dibromocyclohexane, etc.
Examples of the halogenated alcohol compounds include 2,2,2,-trichloroethanol, tribromoethanol, 1,3-dichloro-2-propanol, 1,1,1-trichloro-2-propanol, di(iodohexamethylene)aminoisopropanol, tribromo-tert-butyl alcohol, 2,2,3-trichlorobutane-1,4-diol, etc.
Examples of the halogenated carbonyl compounds include 1,1-dichloroacetone, 1,3-dichloroacetone, hexachloroacetone, hexabromoacetone, 1,1,3,3-tetrachloroacetone, 1,1,1-trichloroacetone, 3,4-dibromo-2-butanone, 1,4-dichloro-2-butanone, dibromocyclohexanone, etc.
Examples of the halogenated ether compounds include 2-bromoethyl methyl ether, 2-bromoethyl ethyl ether, di(2-bromoethyl) ether, 1,2-dichloroethyl ethyl ether, etc.
The halogenated ester compounds may be esters of halogenated carboxylic acids, halogenated esters of carboxylic acids or halogenated esters of halogenated carboxylic acids. Examples of the esters include bromoethyl acetate, ethyl trichloroacetate, trichloroethyl trichloroacetate, homo- and co-polymers of 2,3-dibromopropyl acrylate trichloroethyl dibromopropionate, ethyl α,β-dichloroacrylate, etc.
Examples of the halogenated amide compounds include chloroacetamide, bromoacetamide, dichloroacetamide, trichloroacetamide, tribromoacetamide, trichloroethyltrichloroacetamide, 2-bromoisopropionamide, 2,2,2-trichloropropionamide, N-chlorosuccinimide, N-bromosuccinimide, etc.
Of the organic halogen compounds, those compounds which have one or more halogen atoms bound to the same carbon atom are preferable, with those which have three halogen atoms bound to the same carbon atom being particularly preferable. The organic halogen compounds may be used alone or in combination of two or more.
Of these organic halogen compounds, tribromomethyl phenyl sulfone and 2,4-bis(trichloromethyl)-6-phenyltriazole are particularly preferable.
The organic halogen compounds to be used in the present invention are used in amounts of 0.001 wt % to 5 wt %, more preferably 0.005 wt % to 1 wt %, based on the solid components of the photo-polymerizable composition.
A thermal polymerization inhibitor is preferably further added to the photo-polymerizale composition to be used in the present invention. Examples of thermal polymerization inhibitors include p-methoxyphenol, hydroquinone, alkyl- or aryl-substituted hydroquinones, t-butylcatechol, pyrogallol, cuprous chloride, chloranil, naphthylamine, β-naphthol, 2,6-di-t-butyl-p-cresol, pyridine, nitrobenzene, dinitrobenzene, p-toluidine, Methylene Blue, organic copper, methyl salicylate, etc. These thermal polymerization inhibitors are incorporated in amounts of preferably 0.001 to 5 wt % based on the polyfunctional monomer.
In order to control film properties, a plasticizer may be added to the composition. Typical examples thereof include phthalic acid esters (e.g., dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, octyl capryl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate and diaryl phthalates), glycol esters (e.g., dimethyl glycol phthalate, ethylphthalylethyl glycolate, methylphthalylethyl glycolate, butylphthalylbutyl glycolate, dicaprylic acid ester of triethylene glycol, etc.), phosphoric acid esters (e.g., tricresyl phosphate and triphenyl phosphate), aliphatic dibasic acid esters (e.g., diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sebacate, dioctyl sebacate and dibutyl maleate), amides (e.g., benzenesulfonamide, p-toluenesulfonamide and N-n-butylacetamide), triethyl citrate, triacetyl ester of glycerin, butyl laurate, etc. Of these, p-toluenesulfonamide is particularly preferable.
Typical examples of the leuco dyes to be used in the present invention include aminotriarylmethanes (e.g., tris(p-dimethylaminophenyl)methane, (leucocrystal violet), tris(p-diethylaminophenyl)methane, tris(p-dimethylamino-o-methylphenyl)methane, tris(p-diethylamino-o-methylphenyl)methane, bis(p-dibutylaminophenyl)-[p-(2-cyanoethyl)methylaminophenyl]methane, bis(p-dimethylaminophenyl)-2-quinolylmethane, tris(p-dipropylaminophenyl)methane, etc.), aminoxanthenes (e.g., 3,6-bis(diethylamino)-9-phenylxanthene and 3-amino-6-dimethylamino-2-methyl-9-(o-chlorophenyl)xanthene), aminothioxanthenes (e.g., 3,6-bis(diethylamino)-9-(o-ethoxycarbonylphenyl)thioxanthene and 3,6-bis(dimethylamino)thioxanthene), amino-9,10-dihydroacridines (e.g., 3,6-bis(diethylamino)-9,10-dihydro-9-phenylacridine and 3,6-bis(benzylamino)-9,10-dihydro-9-methylacridine), aminophenoxazines (e.g., 3,7-bis(diethylamino)phenoxazines), aminophenothiazines (e.g., 3,7-bis(ethylamino)phenothiazine), aminodihydrophenazines (e.g., 3,7-bis(diethylamino)-5-hexyl-5,10-dihydrophenazine), aminophenylmethanes (e.g., bis(p-dimethylaminophenyl)anilinomethane), 4-amino-4'-dimethylaminodiphenylamine, aminohydrocinnamic acids (e.g., methyl 4-amino-α,β-dicyanohydrocinnamate), hydrazines (e.g., 1-(2-naphthyl)2-phenylhydrazine), amino-2,3-dihydroanthraquinones (e.g., 1,4-bis(ethylamino)-2,3-dihydroanthraquinone), phenethylanilines (e.g., N,N-diethyl-p-phenethylaniline), acyl derivatives of leuco dyes containing a basic NH group (e.g., 10-acetyl-3,7-bis(dimethylamino)phenothiazine), leuco-like compounds which do not have oxidizable hydrogen but can be oxidized to colored compounds (e.g., tris(4-diethylamino-o-tolyl)ethoxycarbonylmethane), leucoindigoid dyes, organic amines capable of being oxidized to colored forms as described in U.S. Pat. Nos. 3,042,515 and 3,042,517 (typical examples of this type compounds including 4,4'-ethylenediamine, diphenylamine, N,N-dimethylaniline, 4,4'-methylenediaminetriphenylamine, and N-vinylcarbazole). Of these, leuco-crystal violet is particularly preferable.
The leuco dyes to be used in the present invention are used in amounts of 0.01 to 10 wt %, more preferably 0.05 to 5 wt %, based on the solid components of the photo-polymerizable composition.
In the present invention, dyes may be used for the purpose of coloring the photo-polymerizable composition or imparting storage stability. Examples of suitable dyes include Brilliant Green sulfate, Eosine, Ethyl Violet, Erythrosine B, Methyl Green, Crystal Violet, Basic Fuchsine, phenolphthalein, 1,3-diphenyltriazine, Alizarine Red S, Thymolphthalein, Methyl Violet 2B, Quinaldine Red, Rose Bengale, Metanil Yellow, Thymolsulfophthalein, Xylenol Blue, Methyl Orange, Orange IV, diphenylthiocarbazone, 2,7-dichlorofluorescein, Paramethyl Red, Congo Red, Benzopurpurin 4B, α-Naphthyl Red, Nile Blue A, phenacetarin, Methyl Violet, Malachite Green oxalate, Parafuchsine, Oil Blue #603 (made by Orient Kagaku Kogyo), Rhodamine B, Rhodamine 6G, etc.
Of these dyes Malachite Green oxalate is particularly preferable.
In the present invention, so-called adhesion-promoting agents known in the art may be used for improving adhesion. For example, there are illustrated those compounds which are described in JP-B-50-9177 (corresponding to U.S. Pat. No. 3,622,334), JP-B-54-5292 (corresponding to U.S. Pat. No. 3,873,316), JP-B-55-22481, JP-A-51-64919, JP-A-51-64920 (corresponding to U.S. Pat. No. 4,233,395), JP-A-50-63087, JP-A-52-2724 (corresponding to U.S. Pat. No. 4,197,132), JP-A-53-702, JP-A-53-124541, JP-A-53-124594, JP-A-54-133585, JP-A-54-133586, JP-A-55-65947, JP-B-57-46053, JP-B-57-46054, JP-A-56-11904, JP-B-57-21697 (corresponding to U.S. Pat. No. 4,320,189), JP-A-56-75642, JP-A-56-67844, JP-B-57-40500, JP-A-56-99202, JP-A-56-100803, JP-A-57-60327, JP-A-57-62047, DAS 2,448,850, U.S. Patent 4,629,679, JP-B-57-49894, JP-A-57-148392, JP-A-57-192946, JP-A-58-100844, JP-A-59-113432 (corresponding to U.S. Patent 4,572,888), JP-A-59-125725, JP-A-59-125726, JP-A-59-125727, JP-A-59-125728, JP-A-59-152439, JP-A-59-154440, JP-A-59-154441, JP-A-59-165051, JP-A-60-12543 (corresponding to U.S. Pat. No. 4,543,318), JP-A-60-12544 (corresponding to U.S. Pat. No. 4,543,318), JP-A-60-135931, JP-A-60-138540, JP-A-60-146233, JP-A-61-4038, JP-A-61-6644, JP-A-61-6646, JP-A-61-166541 (corresponding to U.S. Pat. No. 4,741,987), JP-A- 61-172139 (corresponding to U.S. Pat. No. 4,657,942), JP-A-61-186952, JP-A 61 190330, JP-A-61-198146, JP-A-61-223836, JP-A-61-282835 (corresponding to U.S. Pat. No. 4,756,994), JP-A-61-360237, JP-A-62-91935, JP-A-62-96939, JP-A-62-180354, JP-A-62-180355, JP-A-62-180356, JP-A-62-180357, JP-A-62-181303, JP-A-62-208042, JP-A-62-240950 (corresponding to U.S. Pat. No. 4,693,959), JP-A-62-277405, JP-A-62-286035, JP-A-62-290702, JP-B-63-13526 (corresponding to U.S. Pat. No. 4,268,610), JP A-63-24243 (corresponding to U.S. Pat. Nos. 4,680,249 and 4,710,262), JP-A-63-57622, amd JP-A-63-61241.
Specifically, there are illustrated benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, 3-morpholinomethyl-5-phenyl-oxadiazole-2-thione, 5-amino3-morpholinomethyl-thiadiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, and the like, with 3-morpholinomethyl-2-phenyltriazole-2-thione being particularly preferable.
In general, the photo-polymerizable composition of the present invention is used in such manner that it is dissolved or dispersed in a solvent, and the resulting coating solution is coated on a support by a proper process and dried and, if necessary, a protective film is provided thereon to form an image-forming material.
As the solvent for the coating solution, there are illustrated, for example, alcohols (e.g., methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and n-hexanol), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and diisobutyl ketone), esters (e.g., ethyl acetate, butyl acetate, n-amyl acetate, methyl formate, ethyl propionate, dimethyl phthalate and ethyl benzoate), aromatic hydrocarbons (e.g., toluene, xylene, benzene and ethylbenzene), halogenated hydrocarbons (e.g., tetrachlorocarbon, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride and monochlorobenzene), ethers (e.g., tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and 1-methoxy-2-propanol), dimethylformamide, dimethylsulfoxide, etc.
The photo-polymerizable composition of the present invention may be coated on a support to use and, if desired, a protective film may be provided on the photo-polymerizable composition layer. As such protective layer, a proper one may be selected from among those which are described to be used as the support for papers (e.g., paper laminated with polyethylene, polypropylene or the like). The thickness of the protective layer is generally 5 to 100 μm, more preferably 10 to 50 μm. In this situation, it is necessary to adjust adhesion force A between the photo-polymerizable composition layer and the support be larger than adhesion force B between the photo-polymerizable composition layer and the protective film (i.e., A>B). Specific examples of the combination of support/protective film include polyethylene terephthalate/polypropylene, polyethylene terephthalate/polyethylene, polyamide (nylon 6)/polyethylene, polyvinyl chloride/cellophane, polyimide/polypropylene, etc.
Supports to be used as the aforesaid support should have a good light-transmitting property and a uniform surface. Specifically, various plastic films such as films of polyethylene terephthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, polyalkyl (meth)acrylate, poly(meth)acrylate copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride-vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoroethylene, etc. A composite material composed of two or more of these films may also be used.
The support to be used has a thickness of generally 5 to 150 μm, preferably 10 to 50 μm, but films with a thickness outside the above-described range may also be used.
Thickness of the aforesaid photo-polymerizable composition to be provided on the support is a thickness that is enough for the finally formed image to exhibit desired functions, but is generally in the range of from 5 to 100 μm, preferably 10 to 80 μm.
Aside from selecting different films as the support and the protective film as described above, the aforementioned relation on adhesion force can be attained by subjecting at least one of the support and the protective film to a surface treatment. Surface treatment of the support is generally conducted for enhancing adhesion force with the photo-polymerizable composition layer, and such surface treatment is conducted by providing a subbing layer or by conducting corona discharge treatment, flame treatment, ultraviolet ray irradiation, high frequency application, glow discharge irradiation, actinic plasma irradiation, laser irradiation, etc.
Surface treatment of the protective film is conducted generally for decreasing adhesion force with the photo-polymerizable composition layer contrary to the above-described surface treatment for the support, and is conducted by, for example, providing a subbing layer of polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene or the like.
Drying after the coating of the photo-polymerizable composition is conducted at a temperature of generally 30� C. to 150� C., particularly 50� C. to 120� C., for 1 to 30 minutes.
When the aforementioned image-forming material has a protective film, the protective film is peeled apart to lay bare the surface of the photo-polymerizable composition layer, and the surface is laminated on a desired and cleaned surface of a base board under pressure.
As the base board, various ones may be used depending upon the end-use of the composition of the present invention. For example, plastic films having a different adhesion force with the photo-polymerizable layer from those used for the support, paper, wood, metal plates, glass plates, etc. are used. In the case of using the composition of the present invention as a resist for forming printed circuits, printed-circuit base boards comprising a plastic plate having laminated or plated thereon a thin film of a metal such as copper, aluminum or silver or comprising a plastic plate having through-holes (holes formed through the plastic plate) and having laminated or plated on the inside surface of the through-holes the thin metal film described above, or base boards comprising a thin plastic film having vacuum-deposited or plated thereon a thin film of metal are used. Further, in the case of using the composition of the present invention for printing plates, an aluminum plate, a plastic film having provided thereon an aluminum layer, and the like are used. In this case, surface of the metal such as aluminum is preferably subjected to silicate treatment, anodizing treatment or the like.
Lamination of the photo-polymerizable composition layer to these base boards may be conducted at room temperature (15� to 30� C.) or under heating (30� to 180� C.), particularly preferably at 80� to 140� C.
The light-sensitive layer and the support thus laminated on the base board is then imagewise exposed through the transparent support and generally though an original mask. As the light source, a light source which emits electromagnetic waves capable of transmitting the transparent support and active on the photo-polymerization initiator used and which as a wavelength of 310 to 700 nm, more preferably, ultraviolet ray-visible light ray of 350 to 500 nm in wavelength, is used. For example, a high-pressure mercury lamp, a xenon lamp, a carbon arc lamp, a tungsten halogen lamp, a fluorescent lamp for copiers, etc. may be used. In addition, laser light, electron beams, X-rays, etc. may be used for the exposure.
After imagewise exposure, the transparent support is removed, and unexposed portions are dissolved away by a developing solution such as an organic solvent, an alkaline aqueous solution containing an organic solvent, an alkaline aqueous solution or the like to obtain a photo-hardened image on the base board.
After the image formation, desired processings may be conducted as the case demands. For example, in the case of forming a printed circuit board, bared metal may be etched using a known etching solution such as an aqueous solution of copper chloride or ferric chloride, or plating may be conducted on bared metals by using a known plating solution such as a solution of copper pyrophosphate or copper sulfate.
In addition, a photoresist may be formed by directly coating a solution of the photo-polymerizable composition of the present invention in an already mentioned solvent on a base board using a spinner, a whirler or the like, and drying the coated solution.
The photo-polymerizable composition of the present invention is particularly adapted for formation of printed-circuit boards and, further, may be used for a wide range of purposes such as formation of lithographic or letter-press printing plates, formation of relief, optical copying photographic pictures, etc.
The present invention is now illustrated in greater detail by reference to the following examples which, however, are not to be construed as limiting the present invention in any way. Unless otherwise indicated, parts are by weight.
The following materials were mixed to prepare a uniform solution (hereinafter referred to as mother liquor).
______________________________________35 wt % solution of methyl meth- 42.9 partsacrylate/methacrylic acid/2-ethylhexyl methacrylate/benzylmethacrylate copolymer (molarratio = 55/28.8/11.7/4.5; weight-average molecular weight: 90,000)(solvent: methyl ethyl ketone/1-methoxy-2-propanol = 2/1 (by weight))Polypropylene glycol diacrylate 6.5 parts(average molecular weight: 822)Tetraethylene glycol dimethacrylate 1.5 partsp-Toluenesulfonamide 0.5 partMalachite Green oxalate (1% 1.625 partsmethanol solution)3-Morpholinomethyl-1-phenyl- 0.01 parttriazole-2-thione______________________________________
To the above-described mother liquor were added 4,4'-bis(diethylamino)benzophenone, benzophenone, phenyl tribromomethyl sulfone, 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, Leuco Crystal Violet, or a compound represented by the formula (1) or (2) in amounts shown in Table 1 as Examples 1 to 4 and Comparative Examples 1 to 7. After further stirring to dissolve, each of the coating solutions was coated on a 23 μm polyethylene terephthalate tentative support, and dried at 100� C. for 2 minutes to obtain light-sensitive materials having about 40-μm thick light-sensitive coated layer. Each of these light-sensitive materials was laminated on a cleaned copper-laminated board (base board) at 105� C., then exposed in a varying exposure amount using a 3-kW super-high pressure mercury lamp (HMW-532D made by ORC) through one of two kinds of negative originals having the characteristic properties to be described hereinafter.
Chart A: line width/space width
(L/S)=1/1; line width=30 μm to 100 μm (10 μm step; five lines with each width)
Chart B: L/S=1/3; the rest being the same as with chart A
Furthermore, in order to evaluate sensitivity, Fuji Step guide P of 0.15 in step different of density was provided on both of the originals.
15 Minutes after the exposure, spray development was conducted for 40 seconds using a 1% sodium carbonate aqueous solution (30� C.) (spray pressure: 2 kg/cm2), followed by washing with 20� C. water for 40 seconds. The thus-obtained resist patterns in conformity with originals A and B were observed under an optical microscope. Evaluation was conducted as follows.
First, patterns obtained by exposing in an exposure amount of 40 mj/cm2 through chart A were observed. Width of the thinnest lines (resolving power) not suffering delamination of the 5 lines or completely free of undeveloped portions was recorded. Then, exposure was repeatedly conducted with increasing the exposure amount at an interval of 20 mj/cm2, and resolving power of each sample was recorded in the same manner. In general, resist patterns are liable to be delaminated in a low exposure amount region, and hence images of a thin line width cannot be obtained in such exposure region. On the other hand, in a high exposure amount region, clogging is liable to take place between lines, with this tendency increasing as the line width decreases. Therefore, the resolving power has a minimum value. Of the resolving powers obtained in a manner described above or respective exposure amounts, the smallest value is here taken as the maximum resolving power.
Number of clear steps in the pattern of step guide obtained by a 100-mj exposure was taken as sensitivity. That is, a greater step number means a higher sensitivity.
A pattern for original B in an exposure amount giving the maximum resolving power was observed to record the thinnest line width not suffering delamination.
A light-sensitive coating film was laminated on both sides of a base board having 6 mmφ through-holes (200 holes), then exposed all over in an exposure amount providing the maximum resolving power, then developed under the already mentioned conditions to form tenting films. Then, an aqueous solution of copper chloride was sprayed over it (35 Be; 45� C.; 2.5 kg/cm2 ; 4 min.), followed by spraying with water (18� C., 2 kg/cm2, 3 min.). After repeating this procedure two times more, the ratio of broken tenting film was recorded.
Results thus obtained are shown in Table 1.
TABLE 1__________________________________________________________________________ Organic 4,4'-Bis 2-(2'- Halogen Compound (diethyl Chloro Phenyl amino)- phenyl)- Aromatic Ketone Tribromo- Leuco benzo- imidazole Benzo- Compound of methyl Compound of Crystal phenone dimer phenone formula (1) sulfone formula (2) VioletExample No. (parts) (parts) (parts) (parts) (parts) (parts) (parts)__________________________________________________________________________Example 1 0.04 0.5 1.0 -- 0.05 -- 0.01Example 2 0.04 0.5 -- 1.0 0.05 -- 0.01Example 3 0.04 0.5 1.0 -- -- 0.1 0.01Example 4 0.04 0.25 1.0 -- 0.15 -- 0.20Comparative 0.04 -- 1.0 -- -- -- 0.20Example 1Comparative 0.04 -- -- -- 0.5 -- 0.20Example 2Comparative 0.04 1.0 -- -- -- -- 0.20Example 3Comparative 0.04 -- 1.0 -- 0.5 -- 0.20Example 4Comparative 0.04 0.5 -- -- 0.05 -- 0.20Example 5Comparative 0.04 0.5 1.0 -- 0.05 -- --Example 6Comparative -- 0.5 1.0 -- 0.05 -- 0.20Example 7__________________________________________________________________________ Maximum Tent- Resolving Sensi- Broken Power Adhesion tivity RatioExample No. (μm) (μm) (steps) (%) Notes__________________________________________________________________________Example 1 40 30 9 0.05 Compound ofExample 2 40 30 9 0.05 formula (1)Example 3 Example 4 40 40 30 40 10 9 0 0.10 ##STR5##Comparative 60 80 8 100 Compound ofExample 1 formula (2)Comparative Example 2 Comparative Example 3 Comparative Example 4Comparative Example 5 Comparative Example 6 Comparative Example 50 50 50 40 40 50 50 30 60 40 40 30 5 8 9 8 7 6 10.5 0.50 4.5 0.93 2.6 0.22 ##STR6##__________________________________________________________________________
As is clear from the results, a combination of the photo-polymerization initiator system, an organic halogen compound, and a leuco dye of the present invention can provide markedly improved resolving power and adhesion, and serves to greatly reduce the tenting film-broken ratio. In addition, the composition provides the advantage of improving sensitivity.
40-μm light-sensitive coating films were obtained in the same manner as in Examples 1 to 4 and Comparative Examples 1 to 7 except for adding those compounds which are shown in Table 2 as photo-polymerization initiator systems to the aforesaid mother liquor.
Each of them was exposed in an exposure amount of 100 mj/cm2 using the aforesaid super-high pressure mercury lamp. After 3 minutes, absorbance at 590 nm was measured using a UV-visible light spectrosensitometer (Shimazu Graphicode UV-240). Printing out density, ΔD, was determined by subtracting an absorbance obtained by measuring absorbance of the coated film before exposure in the same manner from the above-measured absorbance after the exposure. Results thus obtained are shown in Table 2.
TABLE 2__________________________________________________________________________ 4,4'-Bis(di- 2-(2'-Chlorophenyl)- Phenyl Leuco ethylamino)- 4,5-diphenyl- tribromo- Crystal benzophenone imidazole dimer Benzophenone methyl sulfone VioletExample No. (parts) (parts) (parts) (parts) (parts) ΔD__________________________________________________________________________Example 5 0.04 0.5 1.0 0.05 0.20 0.90Example 6 0.04 0.5 1.0 0.10 0.20 1.35Comparative 0.04 1.0 -- -- 0.20 0.55Example 8__________________________________________________________________________
As is clear from the above results, the combination of a photo-polymerization initiator system, an organic halogen compound and a leuco dye in accordance with the present invention can markedly enhance efficiency of printing out.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
|Cited Patent
|Filing date
|Publication date
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|Nov 18, 1969
|Du Pont
|Photopolymerizable compositions and layers containing 2,4,5-triphenylimidazoyl dimers
|Aug 7, 1972
|Jun 4, 1974
|Du Pont
|Crystalline photopolymerizable compositions with improved storage life
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|Nov 27, 1979
|Fuji Photo Film Co., Ltd.
|Light-sensitive photopolymerizable composition
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|Fuji Photo Film Co., Ltd.
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|Nov 22, 1978
|Dec 16, 1980
|Fuji Photo Film Co., Ltd.
|Photopolymerizable composition
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|Apr 28, 1981
|E. I. Du Pont De Nemours And Company
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|E. I. Du Pont De Nemours And Company
|Dimers derived from unsymmetrical 2,4,5,-triphenylimidazole compounds as photoinitiators
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|E. I. Du Pont De Nemours And Company
|Derivatives of aryl ketones as visible sensitizers of photopolymerizable compositions
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|Dec 6, 1983
|Toyo Boseki Kabushiki Kaisha
|Image forming material and method
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|Mar 20, 1984
|Hitachi Chemical Company, Ltd.
|Photosensitive resin composition containing unsaturated monomers and unsaturated phosphates
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|Sep 24, 1985
|Fuji Photo Film Co., Ltd.
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|Apr 22, 1986
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|Dec 16, 1986
|Mitsubishi Rayon Company Ltd.
|Tetrazole compound-containing photopolymerizable resin composition
|Citing Patent
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|Jun 9, 1993
|Apr 5, 1994
|Fuji Photo Film Co., Ltd.
|Photopolymerizable resin material and process for preparing print circuit using the material
|Sep 11, 1991
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|Fuji Photo Film Co., Ltd.
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|Feb 21, 1995
|Morton International, Inc.
|Photoresist processing for improved resolution having a bake step to remove the tackiness of the laminated photosensitive layer prior to contact imagewise exposure
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|Apr 18, 1995
|E. I. Du Pont De Nemours And Company
|Photoimageable compositions containing substituted 1, 2 dihalogenated ethanes for enhanced printout image
|May 2, 1995
|Sep 9, 1997
|Minnesota Mining And Manufacturing Company
|Visible image dyes for positive-acting no-process printing plates
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|Dec 2, 1997
|Agfa-Gevaert Ag
|Process for the production of a multicolored image and photosensitive material for carrying out this process
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|Mar 10, 1998
|Agfa-Gevaert Ag
|Process for the production of a multicolored image and photosensitive material for carrying out this process
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|Mar 23, 1999
|Tokyo Ohka Kogyo Co., Ltd.
|Photosensitive resin composition, photosensitive printing plate using the same and method of manufacturing printing master plate
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|May 4, 1999
|Shipley Company, L.L.C.
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|Ciba Specialty Chemicals Corp.
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|Nov 16, 2004
|Eternal Technology Corporation
|Photoresist composition
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|E. I. Du Pont De Nemours And Company
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|Tokyo Ohka Kogyo Co., Ltd.
|Photosensitive resin compositions and photosensitive dry films using the same
|Oct 5, 2012
|Aug 9, 2016
|Nokia Technologies Oy
|Metallization and anodization of plastic and conductive parts of the body of an apparatus
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|May 8, 2003
|Adrian Lungu
|Photopolymerizable element for use as a flexographic printing plate and a process for preparing the plate from the element
|Jan 12, 2003
|Jul 13, 2006
|Mara Destro
|Polymeric material containing a latent acid
|Jan 31, 2006
|Jul 20, 2006
|Adrian Lungu
|Process for preparing a flexographic printing plate from a photopolymerizable element
|May 25, 2006
|Nov 30, 2006
|Fuji Photo Film Co., Ltd.
|Ink composition for ink jet-recording and method for preparing lithographic printing plate using the same
|May 11, 2006
|Nov 19, 2009
|Tokyo Ohka Kogyo Co., Ltd.
|Photosensitive dry film for production of three-dimensional micro-molded product, and photosensitive resin composition
|Jun 9, 2010
|Mar 17, 2011
|Yukihiko Tanaka
|Photosensitive resin compositions and photosensitive dry films using the same
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|Apr 10, 2014
|Nokia Corporation
|Metallization and anodization of plastic and conductive parts of the body of an apparatus
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|Dec 26, 2012
|Photocurable resin composition, dry film and cured object thereof, and printed circuit board with the same
|Oct 6, 1995
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|Nippon Zeon Co., Ltd.
|Photosensitive elastomer composition and photosensitive rubber printing plate
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|E.I. Du Pont De Nemours And Company
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|Method of making a lithographic printing plate.
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|Tokyo Ohka Kogyo Co., Ltd.
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|Tokyo Ohka Kogyo Co Ltd
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|U.S. Classification
|430/281.1, 430/288.1, 430/925, 430/916, 430/920, 430/907, 430/910
|International Classification
|Cooperative Classification
|European Classification
|Aug 10, 1989
Owner name: FUJI PHOTO FILM CO., LTD., NO. 210, NAKANUMA, MINA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:FUJIKURA, SADAO;IWASAKI, MASAYUKI;MAEDA, MINORU;AND OTHERS;REEL/FRAME:005109/0868
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|Dec 13, 1994
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|Dec 13, 2002
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|Feb 15, 2007
Owner name: FUJIFILM CORPORATION, JAPAN
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:FUJIFILM HOLDINGS CORPORATION (FORMERLY FUJI PHOTO FILM CO., LTD.);REEL/FRAME:018904/0001
Effective date: 20070130
Owner name: FUJIFILM CORPORATION,JAPAN
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:FUJIFILM HOLDINGS CORPORATION (FORMERLY FUJI PHOTO FILM CO., LTD.);REEL/FRAME:018904/0001
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Suds: The Rocking '60s Musical Soap Opera
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Horses Jump for a Spot in the World Cup Finals at Del Mar International Horse Show
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Reviews & Ratings
Featured review from KATHARINE MILLOYRed Velvet
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I've seen this show a few years back, and knew it to be a fun kick, and it was! We had a great evening, outstanding show, amazing voices ... lots of fun! I'd go again! Of course, we knew all the songs ... !
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Fabulous show! Fast-moving and fun cast! Lots of 60's songs you'll love. Very funny. You'll be sorry if you miss this!
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Play was excellent! Great theater and all seats had a good view of the stage. Cast had wonderful singing voices. Could not have been happier with the evening.
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Fun,light entertainment, it's behind the art studio
Quotes & Highlights
"Every line, every note, every step entertains…" —San Diego Reader
Written by Melinda Glib, Steve Gunderson, Will Roberson & Bryan Scott
Directed by Javier Velasco

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music player app - ios and android
This project received 34 bids from talented freelancers with an average bid price of $469 USD.Get free quotes for a project like this
Skills Required
Project Budget$200 - $300 USD
Total Bids34
Project Description
i want to build a music player app for ios and android .
it will be very simple , it will contain 5-10 songs from the app , that means no internet .
it will have two page the music player page , and an about us page .
this is a small sketch for the music player page :
[url removed, login to view]
and the about page will contain a picture and 4 buttons for sharing the app(mail,twitter,facebook,sms) , and 3 buttons for our twitter account and facebook and our website .
i will provide the designs .
devices : iphone 4,5 and ipad , and android .
and also compatible with ios 7
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Hours of OperationMonday 7:00 AM–11:00 PM Tuesday 7:00 AM–11:00 PM Wednesday 7:00 AM–11:00 PM Thursday 7:00 AM–11:00 PM Friday 7:00 AM–11:00 PM Saturday 8:00 AM–9:00 PM Sunday 9:00 AM–9:00 PM
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Reviews for this FedEx Office Print & Ship Center9/24/2016Nick Very helpful with getting my file downloaded for future use. Read more9/22/2016Nick was very helpful and acknowledged me when I walked into the store. He was able to make this quick for me without waiting. Read more9/21/2016Samaria has was amazing. She totally got what we wanted and made it happen. Awesome service!. Read more9/21/2016The team members that helped me this day were very helpful. I interacted with all three and they all remembered me and were eager to help… Read more9/20/2016Nick was very helpful. He was knowledgeable and friendly . I gave this store 10/10 and I plan to come back again and again . Read more9/20/2016I needed to print a presentation and there was a line at the self service printer. Nicholas saw me in a hurry, he came and greated more with… Read more9/17/2016I am uncomfortable with copying equipment and needed copies for an animal rescue group. As I waited in line, I couldn't help but notice how… Read more9/17/2016Looks good. Read more9/16/2016Thanks nick great work u guys should have more guys like hem. Read more9/14/2016Nick did a great job. Read more9/14/2016Train your staff on all options available. All we needed was simple return address labels and the staff member had no clue how to help us… Read more9/14/2016Samairrah did a great job helping me with my order. She was able to recommend the type of paper I needed and gave me an estimate quickly an… Read more9/14/2016Nick and Sameera!. Read more9/14/2016My order was printed right away . Thank you Nick!. Read more9/13/2016Nick took great care of my order and got it done on time !. Read more9/13/2016Helped me create my diy wedding invitations in a complicated order. She took direction well and helped create a fabulous piece I will put… Read more9/13/2016Nick is the person who helped me; and even called me later to make sure to have me resend files separately. Great customer service!. Read more9/11/2016Nick and Melissa were very helpful. Read more9/7/2016Nicholas was very helpful and knowledgeable. He recommended a great selection of products. I plan to come back to fedex in the future. I… Read more9/6/2016Staff member Needed extra help. One person with 6 customers in line. Samairrah was very positive and helpful. She needed help and no one… Read more
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Yesterday I wrote about the initials that people put after their name. It made me think about who chooses to attend certification classes: people with a personal stake in advancing themselves through the certification. 158 more words
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By DIANE KETCHAM
Published: March 10, 1991
Singing on Ice
WHEN Robert Leskody won the Long Island Marriott amateur-singing contest, he was promised two grand prizes, a ski trip to Vail, Colo., and a singing engagement at the Nassau Veterans Coliseum before 10,000 people.
Of course Marriott executives never promised that 10,000 people would be at the coliseum in Uniondale specifically to hear Mr. Leskody sing. The hoteliers just promised that the people would be there.
And so it was that Mr. Leskody, a 30-year-old carpenter from Hauppauge, recently became the first person to sing at an intermission at a New York Islanders hockey game.
Wedged between the first and second periods, Mr. Leskody's performance of "Mack the Knife" was timed so that he would get off the ice before the Zamboni machine got on.
"He's pre-empting the animated Great Puck Race," an Islanders official, Jill Knee, said. "The fans love the race, but tonight the pucks will have to wait."
As a lark Mr. Leskody had entered the Marriott Wednesday night Karaoke sing-a-long contest. Now as the winner he was making his public singing debut. "I'm a nervous wreck," he said. "Last night I dreamed they threw beer at me."
Mr. Leskody worked on the day of his performance. "I spackled," he said. "But my heart wasn't in it." He warmed up his voice by singing the scales on the Southern State Parkway.
"Whatever happens, don't stop," Ms. Knee advised him as he and a small entourage headed through the coliseum tunnels. They passed the two Zamboni ice-clearing machines. "There's your competition," said Jim Bartholomay of the Marriott.
Around a corner, and there was the crowd, thousands of people cheering for their hockey team. Mr. Leskody looked faint. The buzzer sounded, and the teams went off the ice. Mr. Leskody went on.
"And now a special treat," the announcer said. All eyes focused on the carpenter. The music started. He slowly began snapping his finger.
"Oh the shark, babe, has such teeth, babe."
From the upper seats the boo birds started. Mr. Leskody kept singing, and the booing stopped. He got into the song, waving and swaying, snapping two fingers at once.
"Could it be that boy's done something rash?"
He was on. He was hot.
When he finished, there was loud cheering. He left the ice and almost collapsed. "I feel like I've been hit by a truck," he said. "Wow."
"He was very good," said one hockey fan turned music critic, Gloria Romuno, of Bethpage. "It took a lot of courage to sing before this crowd."
"Oh he's the best," added another hockey watcher, Bernard Meyer, of Forest Hills.
"Yes he's marvelous," agreed Mr. Meyer's friend Ralph Cirulnick, of Little Neck. "He's so quick."
Quick? How was the singer quick?
"The singer?" Mr. Meyer replied. "Oh we're talking about the Zamboni driver. He's the best in the league. Look at him out there on the ice." Karate From the Screen
A movie star went to Great Neck last weekend. As a limousine waited outside a small office building on Northern Boulevard, inside, Jeff Speakman, the big screen's newest leading man, met his Long Island public.
He chopped and kicked at the various appendages of Jeff Nortman of Woodbury. He pummeled and poked at the vital organs of Ron Massip of West Babylon. "I hope you don't mind me doing this," Mr. Speakman said to Mr. Massip.
"It's a pleasure," Mr. Massip replied.
Mr. Speakman, a 6-foot-tall 190-pound Patrick Duffy lookalike, is an expert in kenpo karate, "the science of street fighting" as he puts it. His first movie, "The Perfect Weapon," opens this week in movie theaters around the country. To promote the man and the movie, Paramount Pictures sent Mr. Speakman on a publicity tour.
Rather than having him chat with shoppers in Roosevelt Field, they sent him to kick with the karate students at the North Shore Karate Center. As the center's head instructor, Norman Sandler, proudly looked on, Mr. Speakman offered black-, brown- and green-belted students tips on how to "break knees" and "crush biceps."
Kenpo karate is not learned for competition, he told the group, but for survival. "Our goal is to inflict pain by the logical destruction of your opponent's body," he said.
The modernized martial art was perfected by Ed Parker, who taught Bruce Lee and Elvis Presley. Mr. Parker was also Mr. Speakman's teacher and supervised the fight scenes for "The Perfect Weapon." He died a few months ago.
"My commitment is to Mr. Parker," said Mr. Speakman who was a martial-arts expert before becoming an actor.
As black-belt holders like Eric Schwarz of Forest Hills, Guy Pisani of Port Washington and Justin Samarel, 12, of Commack stood at attention, Mr. Speakman demonstrated attack sequences in a blur of speed.
Another student, Don Veritzan of Port Washington, was duly impressed. "The closest I ever came to a celebrity before," he said, "was standing next to Frankie Valli." Cheering for Girls
Can equality in sports be carried too far? Administrators of the Sayville School District are beginning to think so. They have been ordered by the Federal Department of Education Office of Civil Rights to provide cheerleaders for the girls' basketball teams.


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Celebrity Style Bypass Cross Ring - Double Wrap Cross In Sterling Silver or Solid White Gold
Original Design,Blessed Necklace,Gold sideways cross necklace,Initial charm necklace,monogrammed necklace
Brownie in a Cup ~ Wipe the outside of the cup with rubbing alcohol. Use an oil based Sharpie paint marker, then write the instructions onto the cup. Let the Sharpie dry completely for 24 hours. Place your cup in a cold oven, then bake at 450 degrees for 30 minutes. Crack your oven door and let the cup cool down with the oven to prevent cracking. This would be great as a gift, add the dry ingredients and wrap.
Mothers Necklace, Mom Necklace, Family Tree Necklace, 1 2 3 4 5,6,7,8 Initial Necklace, Grandma Necklace
Mothers Necklace,New Mommy to Be,Mothers Jewelry,Mother Birthday Gifts,Baby Shower Gifts,Personalized Necklace, For MOM,Valentines Day Gifts...
Hot Cocoa Mix Ornaments
Hot cocoa balls ; I saw empty ones at the Dollar Tree yesterday!!! Guess I'm going back to get some!


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Low-Maintenance Decks
A guide to Trex, Correctdeck, Timbertech, Veranda and other low-maintenance decking materials.
Required Tools for this Project
Have the necessary tools for this DIY project lined up before you start—you'll save time and frustration.
- Chalk line
- Circular saw
- Cordless drill
- Framing square
- Hammer
- Knee pads
- Posthole digger
- Safety glasses
- Tape measure


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Re: Cox/Brewster/Riley parents
In reply to:
Re: Cox/Brewster/Riley parents
Jane Curci 12/06/04
I wasn't sure if too much information would muddle my question; here's what I have.
Based on a transcription of a Bible record, William Car COX's siblings (all putatively children of Aaron and Elizabeth COX) would have all been born in Bucks County, PA, and are reported to be:
Isaac COX b. 17 Aug 1808
Lacy S. COX b. 1 Apr 1815
Jane COX b. 19 June 1816
Elizabeth COX b. 15 Sep 1820
Anna Maria COX b. 5 Oct 1822
Sarah Ann COX b. 29 Jan 1824
Susan COX b. 15 Feb 1826
Aaron COX, Jr. b. 24 Nov 1827
Timothy COX b. 9 Feb 1829
The following information has been verified through public records searches, census records and family records:
William Car COX m. Rebecca Ann BREWSTER 1842 in Ohio, and they had one surviving child:
Aaron COX, b. 16 May 1843 in Clinton County or Warren County, Ohio.
William Car COX m. Elizabeth RILEY 1849 in Warren County, Ohio.Their children were:
Richard H. COX b. 24 Oct 1852 in Ohio
Alfred N. COX b. 18 Aug 1854 in Ohio
Mary Emiline "Emma" COX b. 04 Dec 1856 in Ohio
William Harrison COX b. 20 Jan 1859 in Ohio
Sarah Amanda Cox b. 21 Aug 1861 in Ohio
Thank you!
More Replies:
Re: Cox/Brewster/Riley parents
Jane Curci 12/06/04


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The Amherst Pelham Regional Schools are excited to announce that free lunches will be provided to students in many of the summer programs from July 6th through July 24th. The programs receiving free lunch are Achievement Academy, LSSE & Vela Scholars.
There will be little or no cost to the District as it has received grants from Project Bread and will be reimbursed for each meal served. The reimbursements are provided by the Department of Elementary & Secondary Education which receives its funding from the United States Department of Agriculture (USDA). The meals will be wholesome and nutritious as they must follow a specific meal pattern set forth by DESE. Please contact James Regan at 413-362-1818 if you have any questions.
Required Notice from USDA: The U.S. Department of Agriculture (USDA) prohibits discrimination against its customers, employees, and applicants for employment on the bases of race, color, national origin, age, disability, sex, gender identity, religion, reprisal and, where applicable, political beliefs, marital status, familial or parental status, sexual orientation, or if all or part of an individual's income is derived from any public assistance program, or protected genetic information in employment or in any program or activity conducted or funded by the Department. (Not all prohibited bases will apply to all programs and/or employment activities.) If you wish to file a Civil Rights program complaint of discrimination, complete the USDA Program Discrimination Complaint Form, found online at http://www.ascr.usda.gov/complaint_filing_cust.html, or at any USDA office, or call (866) 632-9992 to request the form. You may also write a letter containing all of the information requested in the form. Send your completed complaint form or letter to us by mail at U.S. Department of Agriculture, Director, Office of Adjudication, 1400 Independence Avenue, S.W., Washington, D.C. 20250-9410, by fax (202) 690-7442 or email at email@example.com. Individuals who are deaf, hard of hearing, or have speech disabilities and wish to file either an EEO or program complaint please contact USDA through the Federal Relay Service at (800) 877-8339 or (800) 845-6136 (in Spanish). Persons with disabilities, who wish to file a program complaint, please see information above on how to contact us by mail directly or by email. If you require alternative means of communication for program information (e.g., Braille, large print, audiotape, etc.) please contact USDA's TARGET Center at (202) 720-2600 (voice and TDD). USDA is an equal opportunity provider and employer.
-Sean Mangano, Director of Finance


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Yep, that's right! I have a son in college, and I'm preggers again, after almost 20 years. At 38, I feel like I'll be able to enjoy this pregnancy more, appreciate it more! At 19, I felt like it was just a rushed blur.. I don't remember all of it, or even half of it. LOL. Anyone else in this situation where there is a large gap in between children?? :-) Due on October 20 :-)
It may as well be my 1st pregnancy..20 years later!! :-)
An 11 yr old, 1 year old, and baby #3 due Oct 6!
I hear ya. My youngest son will be 22 y/o this summer and will be graduating from college. My oldest son turns 24 this month and is a professional athlete. My OB told me I was a pro....ARE YOU FREAKIN' KIDDING ME?!?!? IT'S BEEN OVER 20 YEARS!!!!!! I remember nothing at all. I don't remember ever having m/s, cramps, feeling weird at all. We're not telling the boys until the end of this month.
T. Redd
My youngest will be REAL Cool about it....even excited for us. My oldest, I'm not sure. He likes the fact hubby and I enjoy life and have the financial freedom to do what we please when we please. I think he has a pretty good idea already, but just not saying anything. He'll be happy for us but will need time to let it marinate.
T. Redd
I hear ya. I love the vacations and the quick get-aways, but we also wanted to be able to bring a child into our/the world as well. This is my second marriage and my husband has no children. We've gone through 3 IVF cycles to get where we are today. We can still travel/vacation, just have to do it with alot more gear. Good Luck to you. keep me posted on your progress.
T. Redd
Thanks PisceanJean. I wish you a very happy and healthy pregnancy as well.
T. Redd
There are more of us out there then you may think. I have 4 children 18-16-13-11 a step daughter who is 14 and now I am prego. It is funny to see how different this pregnancy is from the others. I do feel like I am starting out all over again and my oldest daughter teases me. She says when she has a kid in 5 years that they will be able to play together. I am just hoping that my body goes back quickly the way it did before. And CONGRATS !! I think pregnancy is a beautiful thing.
Heather :)