Photosensitive resin composition and photosensitive element using the same

BACKGROUND OF THE INVENTION
This invention relates to a photosensitive resin composition and a photosensitive element using the same which are excellent in light-transmitting properties and solubility, can be made into a final cured film having excellent heat resistance, adhesive properties, flexibility, electrical properties and mechanical properties by heat treatment, can be formed into a thick film, have a high photosensitivity also when used in the form of a thick film, and are suitable for use in interlaminar insulating films or surface protective films of multilayer circuit board or semiconductor element, pastes for color filter, etc.
Heat-resistant polymers represented by polyimides are excellent in heat resistance, electrical properties and mechanical properties and hence have heretofore been used in interlaminar insulating films or surface protective films (e.g. .alpha.-ray shielding film, passivation film, buffer coat film, etc.) in semiconductor element. They have been widely used also in the field of circuit boards, for example, in resists for forming a circuit pattern on a substrate, or interlaminar insulating films of multilayer circuit board.
In the semiconductor industry, inorganic materials have heretofore been used in interlaminar insulating films and surface protective films, but in recent years, organic materials excellent in heat resistance, such as polyimides, have been used by taking advantage of their characteristics.
A pattern of a surface protective film or interlaminar insulating film of a semiconductor element or multilayer circuit board is formed through troublesome and various steps such as formation of a resist material into a film on the surface of a substrate, exposure of a predetermined portion to light, removal of an unnecessary portion by etching and the like, cleaning of the substrate surface, etc. Therefore, it is desirable to develope a heat-resistant photosensitive material which is such that after forming a pattern by exposure and development, a resist material in a necessary portion can be remained and used as it is as an insulating material.
As such a material, there have been proposed, for example, heat-resistant photosensitive materials obtained by using a photosensitive polyimide, a cyclized polybutadiene or the like as a base polymer. Photosensitive polyimides are particularly noted because of, for example, their excellent heat resistance and easy removal of their impurities.
As such a polyimide, for example, Japanese Patent Publication No. 49-17374 has proposed a system comprising a polyimide precursor and a dichromate, at first. But although this material is advantageous in that it has a practical photosensitivity and a high film-forming ability, it is disadvantageous, for example, in that it is poor in storage stability and that chromium ions remain in polyimide. Therefore, it has not been put into practical use.
Japanese Patent Publication No. 55-100143 and Japanese Patent Appln. Kokai (Laid-Open) No. 60-100143 have proposed processes in which a photosensitive group is given by using an ester linkage or an isocyanate compound, respectively. But the material obtained by the former process has low adhesive properties to a substrate and hence tends to be peeled off, while the material obtained by the latter process has low light-transmitting properties and is difficult to form into a thick film.
SUMMARY OF THE INVENTION
This invention was made in consideration of such problems of prior art and provides a photosensitive resin composition and a photosensitive element using the same which are excellent in light-transmitting properties and solubility, can be made into a final cured film having excellent heat resistance, adhesive properties, flexibility, electrical properties and mechanical properties by heat treatment, can be formed into a thick film, and have a high sensitivity also when used in the form of a thick film.
This invention provides a photosensitive resin composition comprising
(A) a polymer containing a repeating unit represented by the general formula: ##STR1## wherein R.sub.1 is a tetravalent organic group, R.sub.2 is a divalent organic group, at least either R.sub.1 or R.sub.2 being chosen so that the repeating unit contains at least one silicon atom and/or at least one fluorine atom; Y.sub.1 is a monovalent group having an ethylenic unsaturated group; n is zero or 1, m is 1 or 2, n and m being chosen so that n+m=2, and
(B) a photoinitiator
This invention further provides a photosensitive element obtained by laminating said photosensitive resin composition on a substrate.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
According to the present invention, the photosensitive resin composition comprises
(A) a polymer containing a repeating unit of the general formula: ##STR2## wherein R.sub.1 is a tetravalent organic group, R.sub.2 is a divalent organic group, at least either R.sub.1 or R.sub.2 being chosen so that the repeating unit contains at least one silicon atom or/and at least one fluorine atom; Y.sub.1 is a monovalent group having an ethylenic unsaturated group; n is zero or 1, m is 1 or 2, n and m being chosen so that n+m=2, and
(B) a photoinitiator
The polymer containing the repeating unit of the general formula (1) can be a polymer containing a repeating unit of the general formula: ##STR3## wherein R.sub.3 is a tetravalent organic group, R.sub.4 is a divalent organic group, at least either R.sub.3 or R.sub.4 being chosen so that the repeating unit contains at least one silicon atom; Y.sub.1 is a monovalent group having an ethylenic unsaturated group; n is zero or 1, m is 1 or 2, n and m being chosen so that n+m=2.
The polymer containing the repeating unit of the general formula (1) can also be a polymer containing a repeating unit of the general formula: ##STR4## wherein R.sub.5 is a tetravalent organic group, R.sub.6 is a divalent organic group, at least either R.sub.5 or R.sub.6 being chosen so that the repeating unit contains at least one fluorine atom; Y.sub.1 is a monovalent group having an ethylenic unsaturated group; n is zero or 1, m is 1 or 2, n and m being chosen so that n+m=2.
The polymer containing the repeating unit of the general formula (1) can still be a polymer containing a repeating unit of the general formula: ##STR5## wherein R.sub.7 is a tetravalent organic group, R.sub.8 is a divalent organic group, at least either R.sub.7 or R.sub.8 being chosen so that the repeating unit contains at least one silicon atom and at least one fluorine atom; Y.sub.1 is a monovalent group having an ethylenic unsaturated group; n is zero or 1, m is 1 or 2, n and m being chosen so that n+m=2.
The polymer containing the repeating unit of the general formula (1) can further be a polymer containing fluorine atoms and siloxane groups which has a repeating unit of the general formula: ##STR6## wherein R.sub.9 is a tetravalent aromatic group, a fluorine atom containing tetravalent aromatic group, or a siloxane group containing tetravalent aromatic group, R.sub.10 is a divalent aromatic group, a fluorine atom containing divalent aromatic group, or a siloxane group containing divalent organic group, R.sub.9 and R.sub.10 being chosen so that the repeating unit necessarily contains at least one fluorine atom and at least one siloxane group; Y.sub.1 is a monovalent group having an ethylonic unsaturated group; n is zero or 1, m is 1 or 2, n and m being chosen so that n+m=2.
The polymer containing the repeating unit of the general formula (1) can be a photosensitive adduct of an isocyanato compound having at least one ethylenic unsaturated group with a polymer containing a repeating unit of the general formula: ##STR7## wherein R.sub.11 has the same meaning as R.sub.1 in the general formula (1); and R.sub.12 has the same meaning as R.sub.2 in the general formula (1).
The polymer containing the repeating unit of the general formula (1) can be a reaction product of a compound of the general formula (7) and/or a compound of the general formula (8) with a compound of the general formula (9): ##STR8## wherein R.sub.13 and R.sub.14 have the same meaning as R.sub.1 in the general formula (1): R.sub.15 has the same meaning as R.sub.2 in the general formula (1); X.sub.1 is a halogen atom or a hydroxyl group; and Y.sub.1 is a monovalent group having an ethylenic unsaturated group.
The polymer containing the repeating unit of the general formula (1) can be a photosensitive adduct of a polymer containing a repeating unit of the general formula: ##STR9## wherein R.sub.16 is a tetravalent organic group, R.sub.17 is a divalent organic group, at least either R.sub.16 or R.sub.17 being chosen so that this repeating unit contains at least one silicon atom, with an isocyanate compound having at least one ethylenic unsaturated group.
The polymer containing the repeating unit of the general formula (1) can be a reaction product of a compound of the general formula (11) and/or a compound of the general formula (12) with a compound of the general formula (13): ##STR10## wherein R.sub.18 and R.sub.19 are a tetravalent organic group, R.sub.20 is a divalent organic group, at least either R.sub.18, R.sub.19 or R.sub.20 being chosen so that the repeating unit contains at least one silicon atom; X.sub.2 is a halogen atom or a hydroxyl group; and Y.sub.1 is a monovalent group having an ethylenic unsaturated group.
The polymer containing the repeating unit of the general formula (1) can be a photosensitive adduct of a polymer containing a repeating unit of the general formula: ##STR11## wherein R.sub.21 is a tetravalent aromatic group, R.sub.22 is a divalent aromatic group, at least either R.sub.21 or R.sub.22 being chosen so that this repeating unit contains at least one fluorine atom, with an isocyanato compound having at least one ethylenic unsaturated group.
In the general formula (14), R.sub.21 can be a tetravalent aromatic tetracarboxylic acid residue of the general formula: ##STR12##
Further, in the formula (14), R.sub.22 can be a divalent aromatic diamine residue of the general formula: ##STR13## wherein R.sub.42, R.sub.43, R.sub.44 and R.sub.45 are independently a hydrogen atom or an alkyl group.
Further R.sub.22 in the general formula (14) can be a divalent aromatic diamine residue of the general formula: ##STR14## wherein Q.sub.1 is an oxygen atom or a sulfur atom; and R.sub.48, R.sub.49, R.sub.50 and R.sub.51 are independently a hydrogen atom or an alkyl group.
In addition 21 in the general formula (14) can be a tetravalent aromatic tetracarboxylic acid residue of the above general formula (24); and R.sub.22 is at least one aromatic diamine residue selected from the group consisting of divalent aromatic diamine residues of the above general formula (26) and divalent aromatic diamine residues of the above general formula (28).
The polymer containing the repeating unit of the general formula (1) can be a photosensitive adduct of an isocyanate compound having at least one ethyelenic unsaturated group with a polymer containing a repeating unit of the general formula: ##STR15## wherein R.sub.23 is a tetravalent organic group, R.sub.24 is a divalent organic group, R.sub.23 and R.sub.24 being chosen so that the repeating unit necessarily contains at least one silicon atom and at least one fluorine atom.
The polymer containing the repeating unit of the general formula (1) can be a reaction product of a compound of the general formula (16) and/or a compound of the general formula (17) with a compound of the general formula (18): ##STR16## wherein R.sub.25 and R.sub.26 are a tetravalent organic group, R.sub.27 is a divalent organic group, R.sub.25, R.sub.26 and R.sub.27 being chosen so that the repeating unit necessarily contains at least one silicon atom and at least one fluorine atom; X.sub.3 is a halogen atom or a hydroxyl group; and Y.sub.1 is a monovalent group having an ethylenic unsaturated group.
The polymer containing the repeating unit of the general formula (1) can be a polymer containing a repeating unit of the general formula: ##STR17## wherein R.sub.28 is a silicon atom containing tetravalent organic group of the formula; ##STR18## wherein R.sub.30 and R.sub.31 are independently a monovalent hydrocarbon group; R.sub.32 is a hydrogen atom or a monovalent organic group; and l is zero or an integer of 1 to 20, R.sub.29 is a divalent organic group; Y.sub.1 is a monovalent group having an ethylenic unsaturated group; n is zero or 1, m is 1 or 2, n and m being chosen so that n+m=2.
The polymer containing the repeating unit of the general formula (1) can be a polymer containing a repeating unit of the formula; ##STR19## wherein R.sub.33 is a tetravalent organic group, R.sub.34 is a silicon atom-containing divalent organic group of the formula; ##STR20## wherein R.sub.35 and R.sub.36 are independently a monovalent hydrocarbon group; R.sub.37 is a hydrogen atom or a monovalent organic group; and l is zero or an integer of 1 to 20, Y.sub.1 is a monovalent group having as ethylenic unsaturated group; n is zero or 1, m is 1 or 2, n and m being chosen so that n+m=2.
The polymer containing the repeating unit of the general formula (1) can be a polymer containing a repeating unit of the general formula; ##STR21## wherein R.sub.38 is a fluorine atom-containing tetravalent organic group of the formula; ##STR22## R.sub.39 is a divalent organic group; Y.sub.1 is a monovalent group having an ethylenic unsaturated group; n is zero or 1, m is 1 or 2, n and m being chosen so that n+m=2.
The polymer containing the repeating unit of the general formula (1) can be a polymer containing a repeating unit of the general formula: ##STR23## wherein R.sub.40 is a tetravalent organic group, R.sub.41 is a fluorine atom-containing divalent organic group of the formula; ##STR24## wherein R.sub.42, R.sub.43, R.sub.44 and R.sub.45 are independently a hydrogen atom or an alkyl group; Y.sub.1 is a monovalent group having an ethylenic unsaturated group; n is zero or 1, m is 1 or 2, n and m being chosen so that n+m=2.
The polymer containing the repeating unit of the general formula (1) can be a polymer containing a repeating unit of the general formula: ##STR25## wherein R.sub.46 is a tetravalent organic group, R.sub.47 is a fluorine atom-containing divalent organic group of the formula; ##STR26## wherein Q.sub.1 is an oxygen atom or a sulfur atom; and R.sub.48, R.sub.49, R.sub.50 and R.sub.51 are independently a hydrogen atom or an alkyl group; Y.sub.1 is a monovalent group having an ethylenic unsaturated group; n is zero or 1, m is 1 or 2, n and m being chosen so that n+m=2.
The polymer containing the repeating unit of the general formula (1) can be a polymer containing a repeating unit of the general formula: ##STR27## wherein R.sub.52 is a tetravalent aromatic group of the formula (24), R.sub.53 is at least one divalent aromatic group selected from the group consisting of divalent aromatic group of the above general formula (26) and divalent aromatic group of the above general formula (28); Y.sub.1 is a monovalent group having an ethylenic unsaturated group; n is zero or 1, m is 1 or 2, n and m being chosen so that n+m=2.
The polymer containing the repeating unit of the general formula (1) can be a photosensitive adduct of a polymer containing a repeating unit of the general formula (30) and a repeating unit of the general formula (31); ##STR28## wherein R.sub.54 is a tetravalent aromatic group; R.sub.55 and R.sub.57 are independently a divalent organic group; and R.sub.56 is a silicon atom-containing tetravalent organic group of the formula: ##STR29## wherein R.sub.58 and R.sub.59 are independently a monovalent hydrocarbon group; R.sub.60 is a hydrogen atom or a monovalent organic group; and n is zero or an integer of 1 to 20, with an isocyanate compound of the general formula (33) or an isocyanate compound of the general formula (34); ##STR30## wherein R.sub.61, R.sub.62 and R.sub.63 are independently a hydrogen atom or a methyl group; R.sub.64 and R.sub.65 are independently a divalent hydrocarbon group; R.sub.66 is a tetravalent organic group; and Y.sub.2, Y.sub.3 and Y.sub.4 are independently selected from the group consisting of hydrogen atom and monovalent organic groups having an ethylenic unsaturated group, at least one of Y.sub.2, Y.sub.3 and Y.sub.4 being a monovalent organic group having an ethylenic unsaturated group.
The polymer containing the repeating unit of the general formula (1) can be a photosensitive adduct of a polymer containing a repeating unit of the general formula (35) and a repeating unit of the general formula (36): ##STR31## wherein R.sub.67 and R.sub.69 are independently a tetravalent organic group; R.sub.68 is a divalent organic group; and R.sub.70 is a silicon atom-containing divalent organic group of the general formula: ##STR32## wherein R.sub.71 and R.sub.72 are independently a monovalent hydrocarbon group; R.sub.73 is a hydrogen atom or a monovalent organic group; and n is zero or an integer of 1 to 20, with an isocyanate compound of the general formula (33) or an isocyanate compound of the general formula (34): ##STR33## wherein R.sub.61, R.sub.62 and R.sub.63 are independently a hydrogen atom or a methyl group; R.sub.64 and R.sub.65 are independently a divalent hydrocarbon group; R.sub.66 is a tetravalent organic group; and Y.sub.2, Y.sub.3 and Y.sub.4 are independently selected from the group consisting of hydrogen atom and monovalent organic groups having an ethylenic unsaturated group, at least one of Y.sub.2, Y.sub.3 and Y.sub.4 being a monovalent organic group having an ethylenic unsaturated group.
The polymer containing the repeating unit of the general formula (1) used in this invention is obtained, for example, by reacting an isocyanato compound having at least one ethylenic unsaturated group with a polymer containing a repeating unit of the general formula: ##STR34## wherein R.sub.11 has the same meaning as R.sub.1 in the general formula (1) has; and R.sub.12 has the same meaning as R.sub.2 in the general formula (1) has.
The reaction of the isocyanato compound having at least one ethylenic unsaturated group with the polymer comprising recurring units of the general formula (6) is carried out in an inert organic solvent at a temperature of preferably 0.degree. to 100.degree. C., more preferably 20.degree. to 70.degree. C.
As the organic solvent used in the reaction, polar solvents capable of completely dissolving the polymer containing the repeating unit of the general formula (1), and there can be exemplified N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphoric triamide, .gamma.-butyrolactone, N,N-dimethylpropylene urea, N,N-dimethylethylene urea, etc. These polar solvents can be used singly or in combination of two or more thereof.
In addition to these polar solvents, there can also be used common organic solvents such as ketones, esters, lactones, ethers, halogenated hydrocarbons, and hydrocarbons, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, .gamma.-butyrolactone, diethyl ether, ehtylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, etc.
In order to dissolve the polymer containing the repeating unit of the general formula (1) completely, these common organic solvents are used preferably in admixture with the above polar solvents. The using amount of these organic solvents is preferably 90 to 1,900 parts by weight, more preferably 150 to 500 parts by weight per 100 parts by weight of the polymer containing the repeating unit of the general formula (1).
As to the proportion of the isocyanato compound having at least one ethylenic unsaturated group to the polymer containing the repeating unit of the general formula (6), the isocyanato compound is usually reacted with said polymer in an amount of preferably 0.01 to 0.9 equivalent weight, more preferably 0.1 to 0.8 equivalent weight, most preferably 0.2 to 0.5 equivalent weight, per equivalent weight of the carboxyl group in said polymer from the viewpoint of the sensitivity of the photosensitive resin composition and the heat resitance of a final cured film.
The reaction of the isocyanato compound having one or more ethylenic unsaturated groups with the polymer containing the repeating unit of the general formula (6) can be facilitated using, for example, an amine such as triethylamine, 1,4-diazobicyclo[2,2,2]octane, etc., or a tin compound such as dibutyltin dilaurate, dibutyltin diacetate, etc., like a ctalyst. These compounds can be used usually in an amount of about 0.01 to about 5% by weight based on the weight of said isocyanate compound.
The isocyanate compound having at least one ethylenic unsaturated group used in this invention includes isocyanato compounds of the general formula (33) and isocyanato compounds of the general formula (34): ##STR35## wherein R.sub.61, R.sub.62 and R.sub.63 are independently a hydrogen atom or a methyl group; R.sub.64 and R.sub.65 are independently a divalent hydrocarbon group; R.sub.66 is a tetravalent orgnic group; and Y.sub.2, Y.sub.3 and Y.sub.4 are independently a group selected from the group consisting of hydrogen atom and monovalent organic groups having a carbon-carbon double bond, at least one of Y.sub.2, Y.sub.3 and Y.sub.4 being a monovalent organic group having a carbon-carbon double bond.
The isocyanato compounds of the general formula (33) include, for example, isocyanatoethyl acrylate, isocyanatopropyl acrylate, isocyanatobutyl acrylate, isocyanatopentyl acrylate, isocyanatohexyl acrylate, isocyanatooctyl acrylate, isocyanatodecyl acrylate, isocyanatooctadecyl acrylate, isocyanatoethyl methacrylate, isocyanatopropyl methacrylate, isocyanatobutyl methacryalte, isocyanatopentyl methacrylate, isocyanatohexyl methacrylate, isocyanatooctyl methacrylate, isocyanatodecyl methacrylate, isocyanatooctadecyl methacrylate, isocyanatoethyl crotonate, isocyanatopropyl crotonate, methacryloyl isocyanate, acryloyl isocyanate, isocyanatohexyl crotonate, etc. These isocyanato compounds can be used singly or in combiantion of two or more thereof.
Isocyanatoethyl methacrylate is commercially available, for example, from Dow Chemical Co. or Showa Denko K. K.).
The isocyanato compound of the general formula (34) is synthesized using a hydroxy compound having at least one ethylenic unsaturated group and a diisocyanate compound as starting materials.
The hydroxy compound having at least one ethylenic unsaturated group includes, for example, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, trimethylolethane diacrylate, trimethylolethane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, 2-hydroxyethyl acrylate, 2-hdyroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, allyl alcohol, glycerol diallyl ether, trimethylolpropane diallyl ether, trimethylolethane diallyl ether, pentaerythritol diallyl ether, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, diglycerol triallyl ether, crotyl alcohol, vinylphenol, cinnamyl alcohol, alkylphenol, o-cinnamylphenol, ##STR36## wherein n is an integer of 1 to 30, and R is H or CH.sub.3, ##STR37## wherein n is an integer of 2 to 30, and R is H or CH.sub.3, ##STR38## wherein n is an integer of 3 to 30, and R is H or CH.sub.3 ##STR39## wherein R is H or CH.sub.3, ##STR40## wherein R is H or CH.sub.3, etc.
These hydroxy compounds can be used singly or in combination of two or more thereof.
The diisocyanate compound which reacts with hydroxy compound to give an isocyanate compound having a urethane linkage in the molecule, includes for example, 4,4'-diphenylmethane diisocyanate, dianisidine isocyanate, tolidine diisocyanate, hexamethylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, methaxylylene diisocyanate, 1,5-naphthalene diisocyanate, trans-vinylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, ##STR41##
These diisocyanate compounds can be used singly or in combiantion of two or more thereof.
The reaction of the hydroxy compound having at least one carbon-carbon double bond in the molecule with the diisocyanate compound is carried out without a solvent or in an inert organic solvent at a temperature of usually 0.degree. to 100.degree. C., preferably 20.degree. to 70.degree. C. The molar ratio of the hydroxy compound to the diisocyanate compound is preferably 0.8/1-1.2/1. More preferably, they are used in equimolar amounts.
The reaction of the hydroxy compound having at least one carbon-carbon double bond in the molecule with the diisocyanate compound can be facilitated using an amine such as triethylamine, 1,4-diazobicyclo[2,2,2]-octane, etc. or a tin compound such as dibutyltin diacetate, etc., like a catalyst.
These compounds can be used usually in an amount of about 0.01 to 5% by weight based on the diisocyanate compound.
In addition, the isocyanato compounds of the general formula (33) and the isocyanato compounds of the general formula (34) can be used singly or in combination of two or more thereof.
The isocyanato compounds of the general formula (34) include, for example, ##STR42##
The polymer containing the repeating unit of the general formula (6) can be obtained by a conventional method, for example, by using at least one predetermined tetracarboxylic acid dianhydride and at least one predetermined diamine as starting materials.
In detail, the polymer containing the repeating unit of the general formula (6) can be obtained by a conventional method by choosing a combination of the starting tetracarboxylic acid dianhydride and diamine in which
(i) at least either the tetracarboxylci acid dianhydride or the diamine contains one or more silicon atoms,
(ii) at least either the tetracarboxylic acid dianhydride or the diamine contains one or more fluorine atoms, or
(iii) both the tetracarboxylic acid dianhydride and the diamine necessarily contain one or more silicon atoms and one or more fluorine atoms. In this case, the silicon atoms are contained preferably in the form of a siloxane group.
In the above, the reaction of the tetracarboxylic acid dianhydride with the diamine is carried out in an inert organc solvent preferably at 0.degree. to 100.degree. C., more preferably 10.degree. to 80.degree. C.
As the organic solvent used in the reaction of the tetracarboxylic acid dianhydride with the diamine, there can be used the polar solvents and the common organic solvents which are usable in the above reaction of the polymer containing the repeating unit of the general formula (6) with the isocyanato compound having at least one ethylenic unsaturated group.
In order to dissolve the polymer containing the repeating unit of the general formula (6) completely, the common organic solvents are used preferably in admixture with the polar solvents. The using amount of these organic solvents is preferably 90 to 1,900 parts by weight, more preferably 150 to 500 parts by weight per 100 parts by weight of the polymer containing the repeating unit of the general formula (6).
The tetracarboxylic acid dianhydride and the diamine are used preferably in the ratio of 0.8/1-1.2/1 by mole, more preferably in equimolar amounts.
When as the tetracarboxylic acid dianhydride and the diamine which are used in this invention, there are combined at least one starting tetracarboxylic acid dianhydride and at least one starting diamine at least either of which contains one or more silicon atoms, there are the following three cases:
(i) the starting tetracarboxylic acid dianhydride contains one or more silicon atoms,
(ii) the starting diamine contains one or more silicon atoms,
(iii) both the starting tetracarboxylic acid dianhydride and the starting diamine contain one or more silicon atoms. The resulting photosensitive resin composition of this invention contains one or more silicon atoms, so that it is excellent in light-transmitting properties and solubility, can be formed into a thick film, and gives a final cured films having excellent adhesive properties and mechanical properties.
From the viewpoint of, for example, the light-transmitting properties of the photosensitive resin composition of this invention, its solubility in a developing solution, and the heat resistance and adhesive properties of a final cured film, the starting materials are preferably used as follows:
in the case of (i), a tetracarboxylic acid dianhydride containing neither silicon atom nor fluorine atom and a tetracarboxylic acid dianhydride containing one or more silicon atoms are used in this invention so as to adjust the molar ratio of the tetracarboxylic acid dianhydride containing neither silicon atom nor fluorine atom to the tetracarboxylic acid dianhydride containing one or more silicon atoms to preferably 20/1-0.8/1, more preferably 5/1-1.5/1, most preferably 3/1 to 2/1;
in the case of (ii), a diamine containing neither silicon atom nor fluorine atom and a diamine containing one or more silicon atoms are used in this invention so as to adjust the molar ratio of the diamine containing neither silicon atom nor fluorine atom to the diamine conaining one or more silicon atoms to preferably 20/1-0.8/1, more preferably 5/1-1.5/1, most preferably 3/1-2/1;
in the case of (iii), a tetracarboxylic acid dianhydride containing neither silicon atom nor fluorine atom, a diamine containing neither silicon atom nor fluorine atom, a tetracarboxylic acid dianhydride containing one or more silicon atoms, and a diamine containing one or more silicon atoms are used in this invention so as to adjust the molar ratio of the sum of the tetracarboxylic acid dianhydride containing neither silicon atom nor fluorine atom and the diamine containing neither silicon atom nor fluorine atom to the sum of the tetracarboxylic acid dinahydride containing one or more silicon atoms and the diamine containing one or more silicon atoms to preferably 20/1-0.8/1, more preferably 5/1-1.5/1, most preferably 3/1-2/1.
When as the tetracarboxylic acid dianhydride and the diamine which are used in this invention, there are combined at least one starting tetracarboxylic acid dianhydride and at least one starting diamine at least either of which contains one or more fluorine atoms, there are the following three cases:
(i) the starting tetracarboxylic acid dianhydride contains one or more fluorine atoms,
(ii) the starting diamine containing one or more fluorine atoms,
(iii) both the starting tetracarboxylic acid dianhydride and the starting diamine contain one or more fluorine atoms. The resulting photosensitive resin composition of this invention contains one or more fluorine atoms, so that it is excellent in light-transmitting properties and solubility, can be formed into a thick film, and gives a final cured film having excellent electrical properties and mechanical properties.
From the viewpoint of, for example, the light-transmitting properties of the photosensitive resin composition of this invention, its solubility in a developing solution, and the heat resistance and electrical properties of a final cured film, the starting materials are preferably used as follows:
in the case of (i), a tetracarboxylic acid dianhydride containing no fluorine atom and a tetracarboxylic acid dianhydride containing one or more fluorine atoms are used in this invention so as to adjust the molar ratio of the tetracarboxylic acid dianhydride containing two fluorine atom to the tetracarboxylic acid dianhydride containing one or more fluorine atoms to preferably 30/1-0.8/1, more preferably 5/1-1.5/1, most preferably 3/1-2/1;
in the case of (ii), a diamine containing no fluorine atom and a diamine containing one or more fluorine atoms are used in this invention so as to adjust the molar ratio of the diamine containing no fluorine atom to the diamine containing one or more fluorine atoms to preferably 20/1-0.8/1, more preferably 5/1-1.5/1, most preferably 3/1-2/1;
in the case of (iii), a tetracarboxylic acid dianhydride containing neither silicon atom nor fluorine atom, a diamine containing neither silicon atom nor fluorine atom, a tetracarboxylic acid dianhydride containing one or more fluorine atoms, and a diamine containing one or more fluorine atoms are used in this invention so as to adjust the molar ratio of the sum of the tetracarboxylic acid dianhydride containing neither fluorine atom nor silicon atom and the diamine containing neither silicon atom nor fluorine atom to the sum of the tetracarboxylic acid dianhydride containing one or more fluorine atoms and the diamine containing one or more fluorine atoms to preferably 20/1-0.8/1, more preferably 5/1-1.5/1, most preferably 3/1-2/1.
When as the tetracarboxylic acid dianhydride and the diamine which are used in this invention, there are combined at least one starting tetracarboxylic acid dianhydride and at least one starting diamine both of which necessarily contain one or more silicon atoms and one or more fluorine atoms, the resulting photosensitive resin composition contains both silicon atom(s) and fluorine atom(s), so that it is excellent in light-transmitting properties and solubility, can be formed into a thick film, and gives a final cured film having excellent adhesive properties, mechanical properties and electrical properties. Furthermore, the photosensitive resin composition possesses further improved light-transmitting properties and solubility because it contains both silicon atom(s) and fluorine atom(s).
From the viewpoint of, for example, the light-transmitting properties of the photosensitive resin composition of this invention, its solubility in a developing solution, and the electrical properties, heat resistance and adhesive properties of a final cured film, each compound constituting the tetracarboxylic acid dianhydride, i.e., a tetracarboxylic acid dianhydride containing one or more silicon atoms, a tetracarboxylic acid dianhydride containing one or more fluorine atoms, or a tetracarboxylic acid dianhydride containing neither silicon atom nor fluorine atom is used preferably in an amount of 5 to 85 mole %, 5 to 85 mole % or 10 to 90 mole %, respectively, based on the total number of moles of tetracarboxylic acid dianhydrides, more preferably in an amount of 10 to 75 mole %, 10 to 75 mole % or 15 to 80 mole %, respectively, based on the total number of moles of tetracarboxylic acid dianhydride.
The constituent (A), i.e., the polymer containing the repeating unit of the general formula (1), which is used in this invention can be obtained, for example, by polycondensation of a compound of the general formula (7) (hereinafter referred to merely as "compound 1") and/or a compound of the general formula (8) (hereinafter referred to merely as "compound .circle.II ") with a compound of the general formula (9) (hereinafter referred to merely as "compound .circle.III "). ##STR43## wherein R.sub.13 and R.sub.4 have the same meaning as R.sub.1 in the general formula (1) has; R.sub.15 has the same meaning as R.sub.2 in the general formula (1) has; X.sub.1 is a halogen atom or a hydroxyl group; and Y.sub.1 is a monovalent group having an ethylenic unsaturated group.
The reaction of compound I and/or compound with compound .circle.III with compound is carried out in an inert solvent at a temperature of preferably 0.degree. to 100.degree. C., more preferably 5.degree. to 60.degree. C.
Compound I and/or compound .circle.II and compound .circle.III are preferably used so as to adjust the molar ratio of compound I and/or compound .circle.II to compound .circle.III to 0.8/1-1.2/1. More preferably, the using amount of compound I and/or compound .circle.II is substantially equmolar with compound .circle.III .
The reaction of compound I and/or compound .circle.II with compound .circle.III can be accelerated using like a catalyst a carbodiimide type dehydrating-condensation agent such as dicyclohexylcarbodiimide, or a dehydrogenating agent, e.g. an amine such as pyridine or triethylamine.
As the organic solvent used in the above reaction, polar solvents capable of completely dissolving the resulting polymer containing the repeating unit of the general formula (1), i.e., the component (A), are generally preferable, and there can be exemplified N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphoric triamide, .gamma.-butyrolactone, N,N-dimethylpropyleneurea, N,N-dimethylethyleneurea, etc.
In addition to these polar solvents, there can be used the common organic solvents usable in the above reaction of the polymer containing the repeating unit of the general formula (6) with the isocyanato compound having at least one ethylenic unsaturated group.
In order to dissolve the polymer containing the repeating unit of the general formula (1) completely, the common organic solvents are used preferably in admixture with the above polar solvents. The using amount of these organic solvent is preferably 90 to 1,900 parts by weight, more preferably 150 to 500 parts by weight per 100 parts by weight of the polymer containing the repeating unit of the general formula (1).
For isolating the polymer from the reaction mixture as occasion demands, it is preferable to add the reaction mixture in small portions to an alcohol or water.
The solid thus obtained can be purified by repetitions of redissolution in the same organic solvent as used in the reaction and reprecipitation with an alcohol or water.
Compound I or compound .circle.II can be obtained, for example by converting the above-mentioned tetracarboxylic acid dianhydride containing one or more silicon atoms, tetracarboxylic acid dianhydride containing one or more fluorine atoms, or tetracarboxylic acid dianhydride containing neither silicon atom nor fluorine atom, into a half ester by the whole or partial ring opening using a hydroxy compound having at least one ethylenic unsaturated group, and if necessary, converting the half ester into an acid halide by use of thionyl chloride, phosphorus pentachloride or the like. The above reaction of the tetracarboxylic acid dianhydride with a hydroxy compound having at least one ethylenic unsaturated group can be accelerated, for example, by adding pyridine, dimethylaminopyridine, or the like.
As the hydroxy compound having at least one ethylenic unsaturated group, there can be used the hydroxy compounds having at least one ethylenic unsaturated group whcih are usable as a starting material for the isocyanato compound of the general formula (34).
Compounds I and/or compounds .circle.II which are used in this invention are divided into three groups i.e., compounds containing one or more silicon atoms, compounds containing one or more fluorine atoms, and compounds containing neither silicon atom nor fluorine atom. By combining these compounds properly with a diamine containing one or more silicon atoms, a diamine containing one or more fluorine atoms, and/or a diamine containing neither silicon atom nor fluorine atom, there can be obtained any of the following three polymers containing the repeating unit of the general formula (1):
(i) a polymer containing silicon atoms
(ii) a polymer containing fluorine atoms
(iii) a polymer containing silicon atoms and fluorine atoms.
In the case of the polymer containing silicon atoms of (i), the photosensitive resin composition of this invention is excellent in light-transmitting properties and solubility, can be formed into a thick film, and gives a final cured film having excellent adhesive properties.
From the viewpoint of, for example, the light-transmitting properties of the photosensitive resin composition of this invention, its solubility in a developing solution, and the heat resistance and adhesive properties of a final cured film, the compound containing neither silicon atom nor fluorine atom, the diamine containing neither silicon atom nor fluorine atom, the compound containing one or more silicon atoms, and the diamine containing one or more silicon atoms are used so as to adjust the molar ratio of the sum of the compound containing neither silicon atom nor fluorine atom and the diamine containing neither silicon atom nor fluorine atom to the sum of the compound containing one or more silicon atoms and the diamine containing one or more silicon atoms to preferably 20/1-0.8/1, more preferably 5/1-1.5/1.
In the case of the polymer containing fluorine atoms of (ii), the photosensitive resin composition of this invention is excellent in light-transmitting properties and solubility, can be formed into a thick film, and gives a final cured film having excellent electrical properties.
From the viewpoint of, for example, the light-transmitting properties of the photosensitive resin composition of this invention, its solubility in a developing solution, and the electrical properties of a final cured film, the compound containing neither silicon atom nor fluorine atom, the diamine containing neither silicon atom nor fluorine atom, the compound containing one or more fluorine atoms, and the diamine containing one or more fluorine atoms are used so as to adjust the molar ratio of the sum of the compound containing neither silicon atom nor fluorine atom and the diamine containing neither silicon atom nor fluorine atom to the sum of the compound containing one or more fluorine atoms and the diamine containing one or more fluroine atoms to preferably 20/1-0.8/1, more preferably 5/1-1.5/1.
As the diamine containing one or more fluorine atoms, it is preferable from the viewpoint of electrical properties to use a diamine represented by the general formula (28-2): ##STR44## wherein Q.sub.1 R.sub.48, R.sub.49, R.sub.50 and R.sub.51 have the same meanings as defined in the general formula (28).
In the case of the polymer containing silicon atoms and fluorine atoms of (iii), the photosensitive resin composition of this invention is excellent in light-transmitting properties and solubility, can be formed into a thick film, and gives a final cured film having excellent adhesive properties and electrical properties.
From the viewpoint of, for example, the light-transmitting properties of the photosensitive resin composition of this invention, its solubility in a developing solution, and the heat resistance and electrical properties of a final cured film, each compound constituting the tetracarboxylic acid dianhydride, i.e., an aromatic tetracarboxylic acid dianhydride containing one or more fluorine atoms, an aromatic tetracarboxylic acid dianhydride having a siloxane group, or an aromatic tetracarboxylic acid dianhydride is used in this invention preferably in an amount of 5 to 85 mole %, 5 to 85 mole % or 10 to 90 mole %, respectively, based on the total number of moles of tetracarboxylic acid dianhydrides, more preferably in an amount of 10 to 75 mole %, 10 to 75 mole % or 15 to 80 mole %, respectively, based on the total number of moles tetracarboxylic acid dianhydrides.
The tetracarboxylic acid dianhydride containing one or more silicon atoms in this invention includes, for example ##STR45## Needless to say, the benzene rings of these tetracarboxylic acid dianhydrides containing one or more silicon atoms may be substituted by substituents such as alkyl groups, etc. These silicon atom containing tetracarboxylic acid dianhydrides can be used singly or in combination of two or more thereof. Among them, ##STR46## is commercially available from organic synthesis pharmaceutical companies, etc., is easily available, and is preferable from the viewpoint of, for example, the heat resistance of the photosensitive resin composition.
The tetracarboxylic acid dianhydride containing one or more fluorine atoms used in this invention includes, for example, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride, 2,2-bis-[4-(2,3-dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride, (trifluoromethyl)pyromellitic dianhydride, bis(trifluoromethyl)pyromellitic dianhydride, 3,3'-bis(trifluoromethyl)-4,4',5,5'-tetracarboxybiphenyl dianhydride, 2,2',5,5'-tetrakis(trifluoromethyl)-3,3',4,4'-tetracarboxybiphenyl dianhydride, 3,3'-bis(trifluoromethyl)-4,4',5,5'-tetracarboxybiphenyl ether dianhydride, 2,2'-bis(trifluoromethyl)-4,4',5,5'-tetracarboxybiphenyl ether dianhydride, 3,3'-bis(trifluoromethyl)-4,4',5,5'-tetracarboxybenzophenone dianhydride, 2,2'-bis(trifluoromethyl)-4,4',5,5'-tetracarboxybenzophenone dianhydride, 1,4-bis[3-(trifluoromethyl)-4,5-dicarboxyphenoxy]benzene dianhydride, 1,4-bis[2-(trifluoromethyl)-4,5-dicarboxyphenoxy]benzene dianhydride, 4,4'-bis[3-(trifluoromethyl)-4,5-dicarboxyphenoxy]biphenyl dianhydride, 1-trifluoromethyl-2,5-bis[3-(trifluoromethyl)-4,5-dicarboxyphenoxy]benzene dianhydride, 1,1'-bis(trifluoromethyl)-3,3'-bis[3-(trifluoromethyl)-4,5-dicarboxyphenoxy]biphenyl dianhydride, 4,4'-bis[3-(trifluoromethyl)-4,5-dicarboxyphenoxy]biphenyl ether dianhydride, 1-trifluoromethyl-3,5-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,4-bis(trifluoromethyl)-3,5-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,2,4,6-tetrakis(trifluoromethyl)-3,5-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,1'-bis(trifluoromethyl)-3,3'-(3,4-dicarboxyphenoxy)biphenyl dianhydride, 1,1',4,4'-tetrakis(trifluoromethyl)-3,3'-(3,4-dicarboxyphenoxy)biphenyl dianhydride, 2,2-bis[4-(2,3-dicarboxybenzoyloxy)phenyl]hexafluoropropane dianhydride, 2,2-bis[3-methyl-4-(2,3-dicarboxybenzoyloxy)phenyl]hexafluoropropane dianhydride, 2,2-bis[4-(2-trifluoromethyl-3,4-dicarboxybenzoyloxy)phenyl]hexafluoropropane dianhydride, 1,5-bis[4-(3,4-dicarboxybenzoyloxy)phenyl]decafluoropentane dianhydride, 1,3-bis[4-(3,4-dicarboxybenzoyloxy)phenyl]hexafluoropropane dianhydride, 1,6-bis[ 4-(3,4-dicarboxybenzoyloxy)phenyl] dodecafluorohexane dianhydride, 2,2-bis[3,5-dimethyl-4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]octafluorobutane dianhydride, 2,2-bis-[4-(2-trifluoromethyl-3,4-dicarboxy)phenyl]hexafluoropropane dianhydride, 1,3-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride, 1,5-bis[4-(3,4-dicarboxyphenoxy)phenyl]decafluoropentane dianhydride, 1,6-bis[4-(3,4-dicarboxyphenoxy)phenyl]dodecafluoropropane dianhydride, etc. These fluorine atom containing tetracarboxylic acid dianhydrides can be used singly or in combination of two or more thereof. Of these, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride is commercially available from Central Glass Co., Ltd., Hoechst Celanese Corp., etc., is easily available, and is preferable from the viewpoint of the heat resistance of the photosensitive resin composition.
The tetracarboxylic acid dianhydride containing neither silicon atom nor fluorine atom used in this invention includes pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, m-terphenyl-3,3',4,4'-tetracarboxylic dianhydride, p-terphenyl-3,3',4,4'-tetracargoxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 4,4'-sulfonyldiphthalic dianhydride, bis(3,4-dicaboxyphenyl) ether dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, butanetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, 5-(2,5-dioxatetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride, etc. These tetracarboxylic acid dianhydrides containing neither silicon atom nor fluorine atom can be used singly or in combiantion of two or more thereof.
Needless to say, the benzene rings of these tetracarboxylic acid dinhydrides may be substituted by substituents such as alkyl groups, etc.
The diamine containing one or more silicon atoms used in this invention includes, for example, ##STR47##
These silicon atom-containing diamines can be used singly or in combination of two or more thereof.
The diamine containing one or more fluorine atoms used in this invention includes, for example, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2-bis(3-methyl-4-aminophenyl)hexafluoropropane, 2,2-bis(3,5-dimethyl-4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl] hexafluoropropane, 2,2-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis[2-(trifluoromethyl)-4-aminophenoxy]benzene, 4,4'-bis-[2-(trifluoromethyl)-4-aminophenoxy)biphenyl, 4,440 -bis[2-(trifluoromethyl)-4-aminophenoxy]diphenyl sulfone, 4,4'-bis[4-(4-aminophenylthio)-phenyl]biphenyl, 2,2'-bis[4-(4-aminophenylthio)-phenyl]hexafluoropropane, 2,2'-bis[4-(2-trifluoromethyl-4-aminophenoxy)phenyl]phenyl]hexafluoropropane, etc. These fluorine atom-containing diamines can be used singly or in combination of two or more thereof. Of these, 2,2-bis(4-aminophenyl)hexafluoropropane and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluropropane are commercially available from Central Glass Co., Ltd., are easily available, and are preferable from the viewpoint of the heat resistance of the photosensitive resin composition.
The diamine containing neither silicon atom nor fluorine atom used in this invention includes, for example, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 2,2-bis(4-aminophenoxyphenyl)propane, bis(4-aminophenoxyphenyl) sulfone, 4,4'-diaminodiphenylethane, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl 3,4'-diaminobenzanilide, m-xylenediamine, p-xylylenediamine, etc.
These diamines containing neither silicon atom nor fluorine atom can be used singly or in combiantion of two or more thereof.
In addition to them, there can also be used diaminoamide compounds represented by the general formula: ##STR48## wherein Ar is an aromatic group; Z.sub.1 is SO.sub.2 or CO; and one of the amino groups and Z.sub.1 --NH.sub.2 are in ortho positions in relation to each other.
The compounds of the general formula (38) include, for example, 4,4'-diaminodiphenylether-3-sulfonamide, 3,4'-diaminodiphenylether-4-sulfonamide, 3,4'-diaminodiphenylether-3'-sulfonamide, 3,3'-diaminodiphenylether-4-sulfonamide, 4,4'-diaminodiphenylmethane-3-sulfonamide, 3,4'-diaminodiphenylmethane-4-sulfonamide, 3,4'-diaminodiphenylmethane-3'-sulfomamide, 3,3'-diaminodiphenylmethane-4-sulfonamide, 4,4'-diaminodiphenylsulfone-3-sulfonamide, 3,4'-diaminodiphenylsulfone-4-sulfonamide, 3,4'-diaminodiphenylsulfone-3'-sulfonamide, 3,3'-diaminodiphenylsulfone-4-sulfonamide, 4,4'-diaminodiphenylsulfide-3-sulfonamide, 3,4'-diaminodiphenylsulfide-4-sulfonamide, 3,3'-diaminodiphenylsulfide- 4-sulfonamide, 3,4'-diaminodiphenylsulfide-3'-sulfonamide, 1,4-diaminobenzene-2-sulfonamide, 4,4'-diaminodiphenylether-3-carbonamide, 3,4'-diaminodiphenylether-4-carbonamide, 3,4'-diaminodiphenylether-3'-carbonamide, 3,3'-diaminodiphenylether-4-carbonamide, 4,4'-diaminodiphenylmethane-3-carbonamide, 3,4'-diaminodiphenylmethane-4-carbonamide, 3,4'-diaminodiphenylmethane-3'-carbonamide, 3,3'-diaminodiphenylmethane-4-carbonamide, 4,4'-diaminodiphenylsulfone-3-carbonamide, 3,4'-diaminodiphenylsulfone-4-carbonamide, 3,4'-diaminodiphenylsulfone-3'-carboanmide, 3,3'-diaminodiphenylsulfone-4-carbonamide, 4,4'-diaminodiphenylsulfide-3-carbonamide, 3,4'-diaminodiphenylsulfide-4-carbonamide, 3,3'-diaminodiphenylsulfide-4-carbonamide, 3,4'-diaminodiphenylsulfide-3'-sulfonamide, 1,4-diaminobenzene-2-carbonamide, etc.
These diaminoamide compounds can be used singly or in combination of two or more thereof.
If necessary, there can also be used diaminodiamide compounds represented by the general formula: ##STR49## wherein Ar is an aromatic group; Z.sub.2 is SO.sub.2 or CO; and one of the amino groups and one the Z.sub.2 --NH.sub.2 groups are in ortho positions in relation to each other.
The compounds of the general formula (39) include, for example, 4,4'-diaminodiphenylether-3,3'-sulfonamide, 3,4'-diaminodiphenylether-4,5'-carbonamide, 3,3'-diaminodiphenylether-4,4'-sulfonamide, 4,4'-diaminodiphenylmethane-3,3'-carbonamide, 3,4'-diaminodiphenylmethane-4,5'-sulfonamide, etc.
These diaminodiamide compounds can be used singly or in combiantion of two or more thereof.
The constituent (B), the photoinitiator, which is used in this invention includes, for example, Michler's ketone, benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-t-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, anthraquinone, methylanthraquinone, 4,4'-bis(diethylamino)benzophenone, acetophenone, benzophenone, thioxanthone, 2,4-diethylthioxanthone, 1,5-acenaphthene, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-[4-(methylthio)phenyl]2-morpholono-1-propanone, diacetyl, benzil, benzyldimethylketal, benzyldiethylketal, diphenyl disulfide, anthracene, phenanthrenequinone, riboflavin tetrabutyrate, Acryl Orange, Erythrosine, phenanthrenequinone, 2-isopropylthioxanthone, 3,3-carbonyl-bis(7-diethylamino)coumarin, 2,6-bis(p-diethylaminobenzylidene)-4-methyl-4-azacyclohexanone, 6-bis(p-dimethylaminobenzylidene)-cyclopentanone, 2,6-bis(p-diethylaminobenzylidene)-4-phenylcyclohexanone, and aminostryl ketone of the formula: ##STR50##
These photoinitiators of (B) can be used singly or in combination of two or more thereof.
Assistants of photoinitiator (I), such as amines and amino acids can be used together with these photoinitiators of (B).
The amines include, for example, ethyl p-dimethylaminobenzoate, methyl p-diethylaminobenzoate, ethyl p-diethylaminobenzoate, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, p-dimethylaminobenzonitrile, ethyl N,N-dimethylanthranilate, etc.
The amino acids include, for example, N-phenylglycine, N-methyl-N-(p-chlorophenyl)glycine, N-ethyl-N-(p-chlorophenyl)glycine, N-(n-propyl)-N-(p-chlorophenyl)glycine, N-methyl-N-(p-bromophenyl)glycine, N-ethyl-N-(p-bromophenyl)glycine, N-(p-cyanophenyl)glycine, N-(p-chlorophenyl)glycine, N-(p-bromophenyl)glycine, etc.
These photoinitiators can be used singly or in combination of two or more thereof.
Assistants of photoinitiator ( .circle.II ) such as mercaptan compounds and oxime compounds can be used as a third component together with the photoinitiator of (B) and the assistant of photoinitiator (I).
The mercaptan compounds include, for example, 2-mercaptobenzimidazole, 1-phenyl-5-mercapto-1,2,3,4-tetrazole, 2-mercaptobenzothiazole, 2-benzoxazolethiol, thiomalic acid, 3-mercaptopropionic acid, etc.
The oxime compounds include, for example, 1-phenyl-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-butanedione-2-(o-methoxycarbonyl)oximie, 1-phenyl-propanedione-2-(o-benzoyl)oxime, 1,2-diphenylethanedione-1-(o-benzoyl)oxime, 1,3-diphenyl-1,2,3-propanetrione-7-(o-n-propylcarbonyl)oxime, 1-(4'-methoxyphenyl)-3-(4'-nitrophenyl)-1,2,3-propanetrione-2-(o-phenyloxycarbonyl)oxime, 1,3-bis(4'-methoxyphenyl)-1,2,3-propanetrione-2-(o-ethoxycarbonyl)oxime, etc.
The using amount of the above-exemplified assistant of photoinitiator (I) and assistants of photoinitiator ( .circle.II ) is usually preferably 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight per 100 parts by weight of the constituent (A), i.e., the polymer containing the repeating unit of the general formula (1), from the viewpoint of the sensitivity of the photosensitive resin composition, the heat resistance of a coating film.
A conventional thermopolymerization inhibitor can be incorporated into the photosensitive resin composition in order to improve the thermal stability of said composition.
The thermopolymerization inhibitor includes, for example, p-methoxyphenol, hydroquinone, t-butylcatechol, pyrogallol, phenothiazine, chloranil, naphthylamine, .alpha.-naphthol, 2,6-di-t-butyl-p-cresol, pyridine, nitrobenzene, p-toluidine, methylene blue, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), etc.
In this invention, if necessary, various polymerizable unsaturated compounds can be used. Among them, acrylic acid compounds, methacrylic acid compounds, etc. are practical.
Specific examples of the acrylic acid compounds are acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, cyclohexyl acrylate, benzyl acrylate, carbitol acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, butylene glycol monoacrylate, N,N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acryalte, pentacrythritol monoacryalte, trimethylolpropane monoacrylate, allyl acrylate, 1,3-propylene glycol diacrylate, 1,4-butylene glycol diacrylate, 1,6-hexane glycol diacrylate, neopentyl glycol diacrylate, dipropylene glycol diacrylate, 2,2-bis(4-acryloxydiethoxyphenyl)propane, 2,2-bis(4-acryloxypropyloxyphenyl)propane, trimethylolpropane diacrylate, pentacrythritol diacrylate, trimethylolpropane triacrylate, pentacrylthritol triacrylate, triacrylformal, tetramethylolmethane tetraacrylate, acrylic ester of tris(2-hydroxyethyl)isocyanuric acid, ##STR51## wherein n is an integer of 1 to 30, ##STR52## wherein n and m are independently integers and chosen so as to adjust n+m to 2-30, ##STR53##
The methacrylic acid compounds include, for example, methacrylic acid, methyl methylacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, octyl methacrylate, ethylhexyl methacrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate, butoxyethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxypentyl methacrylate, N,N-dimethyl aminomethacrylate, N,N-diethyl aminomethacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, methacryloxypropyltrimethoxysilane, allyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexane glycol dimethacrylate, neopentyl glycol dimethacrylate, 2,2-bis(4-methacryloxydiethoxyphenyl)propane, trimethylolpropane dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol trimethacrylate, tetramethylolmethane tetramethacrylate, methacrylic ester of tris(2-hydroxyethyl)isocyanuric acid, ##STR54## wherein n is an integer of 1 to 30, ##STR55## wherein n and m are independently integers and chosen so as to adjust n+m to 1-30, ##STR56##
These compounds can be used singly or in combination of two or more thereof.
The photosensitive resin composition of this invention may contain other polymers, i.e., organic fillers such s poly(amic acid)s, polyimides, polyamides, polyether imides (or precursors thereof), polyamideimides (or precursors thereof), epoxy resins, acrylic resins, resol resins, novolak resins, urethane resins, melamine resins, polyester resins, silicone resins, etc. In this case, any of these resins may be contained so long as it is miscible with the polymer containing the repeating unit of the general formula (1), and these resins are contained in such an amount that they do not deteriorate the heat resistance, adhesive properties, electrical properties and mechanical properties of a final cured film.
The photosensitive resin composition of this invention may contain organic solvents.
As the organic solvents, there can be used, for example, solvents which are capable of completely dissolving the constituent (A), i.e., the polymer containing the repeating unit of the general formula (1). In this case, the using amount of the organic solvents is preferably 10 to 95% by weight, more preferably 30 to 80% by weight based on the weight of the photosensitive resin composition.
The photosensitive resin composition of this invention can be subjected to pattern formation by a conventional micro-fabrication technique.
The photosensitive resin composition of this invention can be formed into a coating film by coating the same on a base material such as glass substrate, silicon wafer, copper-clad laminate or the like by a means such as spin coating using a spinner, dipping, spraying, printing or the like, and then drying the coating.
The thickness of the coating film can be adjusted by properly choosing a coating means, the solid concentration and viscosity of a varnish of the photosensitive polymer composition of this invention, etc.
A coating film can be formed on a substrate to be coated, also by coating the photosensitive resin composition on a flexible base material, e.g. a polyester film, drying the same, thereby laminating the same on the substrate, optionally forming thereon a cover sheet of polyethylene or the like to produce a photosensitive element having a sandwich structure previously, and peeling off the cover sheet of the photosensitive element.
A cover sheet need not necessarily to be used.
When the coating film is irradiated with actinic rays through a mask having a desired pattern, polymerization occurs in the exposed portion, so that the exposed portion is greatly decreased in solubility as compared with the unexposed portion.
Although ultraviolet rays are usually used as the actinic rays, the same effect on the coating film as in the case of ultraviolet rays can be obtained by irradiating the coating film, if necessary, with ionizing radiation such as electron beams, radiation or the like.
When the coating film treated in the manner described above is treated with a suitable developing solution, the unexposed portion retaining a high solubility is developed and removed, while the exposed portion which has been decreased in solubility by the irradiation with actinic rays remains, whereby a desired resin pattern can be obtained.
As the developing solution, there can be used, for example, polar solvents such as N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphortriamide, dimethylimidazolidinone, N-benzyl-2-pyrrolidone, N-acetyl-.epsilon.-caprolactam, N,N-dimethylpropyleneurea, N,N-dimethylethyleneurea, .gamma.-butyrolactone, etc. These polar solvents can be used alone or as a mixed solution with common organic solvents such as methanol, ethanol, isopropanol, benzene, acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, toluene, xylene, methyl Cellosolve, ethyl acetate, methyl propionate, tetrahydrofuran, dioxane and the like, water, basic compounds, basic aqueous solutions, etc. Basic aqueous solutions alone or solutions prepared by mixing a basic aqueous solution with an alcohol can also be used as the developing solution.
The basic compounds include, for example, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, etc.
As the basic compounds, there can be used hydroxides, carbonates, hydrogencarbonates, silicates, phosphates, pyrophosphates, acetates, amines, etc. of alkali metals and quaternary ammonium.
Specific examples of these basic compounds are lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, trimethylbenzylammonium hydroxide, tetramethylammonium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, sodium silicate, sodium phosphate sodium pyrophosphate, sodium acetate, monoethanolamine, diethanolamine, triethanolamine, etc.
In preparing a basic aqueous solution of the basic compound, the using amount of the basic compound is usually preferably 0.0001 to 30 parts by weight, more preferably 0.05 to 5 parts by weight per 100 parts of water.
The alcohol includes, for example, methanol, ethanol, isopropanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, etc.
Subsequently, the developing solution can be removed by rinsing the relief pattern formed by the development with a rinsing liquid.
As the rinsing liquid, there can be used non-solvents for poly(amic acid) which are highly miscible with the developing solution, for example, methanol, ethanol, isopropanol, benzene, toluene, xylene, methyl Cellosolve, water etc.
The thus obtained resin pattern of thick film can be converted to a semiconductor element having a high heat resistance, an interlaminar insulating film or surface-protective film in a multilayer circuit board or the like, a color filter, etc. by subsequent baking at 150.degree. to 400.degree. C, i.e., post cure, and then if necessary, exposure to actinic rays. Therefore, the photosensitive resin composition of this invention is very useful mainly in the field of the micro-fabrication described above.

This invention is explained below with reference to Examples and Comparative Examples, which are not by way of limitation but by way of illustration.
REFERENTIAL EXAMPLE
In a 200-ml four-necked flask equipped with a thermometer, a nitrogen gas inlet and a stirrer were placed 17.4 g (0.1 mole) of 2,4-tolylene diisocyanate, 100 ml of dried methyl ethyl ketone and 2 mg of dibutyltin dilaurate, and stirred at room temperature while introducing dried nitrogen gas.
Subsequently, 11.6 g (0.1 mole) of 2-hydroxyethyl acrylate was added and the resulting solution was stirred at room temperature for 8 hours, after which the methyl ethyl ketone was removed to obtain an isocyanato compound.
In .sup.1 H-NMR spectrum of the product, there were observed a signal due to --OCH.sub.2 CH.sub.2 O-- at 4.35 ppm and a signal due to --CH.dbd.CH.sub.2 at 5.7-6.4 ppm.
In IR spectrum of the product, an absorption due to amide group carbonyl stretching vibration was observed at 1650 cm.sup.-1. The isocyanato compound obtained was named TD-HEA.
SYNTHETIC EXAMPLE 1
In a 1000-ml flask equipped with a thermometer and a stirrer were placed 133.2 g of 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhdyride (mfd. by Central Glass Co., Ltd.) and 450 g of N-methyl-2-pyrrolidone as solvent, and stirred at room temperature.
Then, 60.1 g of 4,4'-diaminodiphenyl ether (mfd. by Mitsui Toatsu Chemicals, Inc.) was added to the resulting solution, and the resulting mixture was stirred at room temperature for 4 hours to obtain a viscous polymer solution.
Subsequently, 43.5 g of the isocyanato compounds TD-HEA obtained in Referential Example was added to the polymer solution and stirred for 8 hours at room temperature while shutting out the light. Carbon dioxide was generated during the reaction. The photosensitive adduct solution was named PI-1.
SYNTHETIC EXAMPLES 2 TO 42
In the same manner as in Synthetic Example 1, polymers PI-2 to PI-42 having the repeating unit of the general formula (1) were obtained by using tetracarboxylic acid dianhydride(s), diamine(s) and an isocyanato compound having at least one ethylenic unsaturated group, in the blending amounts shown in Table 1. Each of the polymers obtained in Synthetic Examples 27 to 38 was solidified by adding 80 ml of ethanol, followed by stirring for 3 hours and slow pouring into 8 liters of water.
SYNTHETIC EXAMPLE 43
To a mixture of 20.7 g (0.04 mole) of 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 25.6 g (0.06 mole) of 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride and 32.2 g (0.1 mole) of 3,3',4,4'-benzophenonetetracarboxylic dianhydride were added 400 ml of N-methyl-2-pyrrolidone and 520 g (0.4 mole) of 2-hydroxyethyl methacrylate as hydroxy compound having at least one ethylenic unsaturated group, and stirred at room temperature for 12 hours. To the resulting solution was added dropwise 70 g of thionyl chloride with ice-cooling over a period of 1 hour, and stirred at room temperature for 2 hours. To the solution thus obtained was added 40.0 g (0.2 mole) of 4,4'-diaminodiphenyl ether, and stirred for 8 hours.
Subsequently, 80 ml of ethanol was added and then stirred for 3 hours. The resulting solution was slowly poured into 8 liters of water, upon which a polymer was precipitated as a thread-like solid. This polymer was named PI-43.
SYNTHETIC EXAMPLES 44 TO 54
In the same manner as in Synthetic Example 43, polymers PI-44 to PI-54 were obtained by using tetracarboxylic acid dianhydride(s), diamine(s) and a hydroxy compound having at least one ethylenic unsaturated group, according to each recipe shown in Table 1.
EXAMPLE 1 TO 114
A photoinitiator of (B) and if necessary, a polymerizable unsaturated compound were added to each polymer having the repeating unit of the general formula (1) or solution thereof obtained in Synthetic Examples 1 to 54, and stirred and mixed therewith. Thus, there were obtained homogeneous solutions of photosensitive resin composition which were used in Examples 1 to 114.
Each of these solutions was passed through a filter, dropped on a silicon wafer, and spin coated thereon at a revolution rate of 2,000 r.p.m. for 30 minutes.
The coating film thus obtained was dried at 80.degree. C. for 10 minutes and then its thickness was measured.
Next, the surface of the coating film was covered with a pattern mask and exposed to light from a ultra-high pressure mercury lamp (8 mW/cm.sup.2) for 70 seconds.
The coating film was then developed with a mixture of equal amounts of N,N-dimethylacetamide and tetrahydrofuran for 50 seconds by means of a spray type developing machine, rinsed with isopropanol for 5 seconds to leave the portion irradiated by the ultra-high pressure mercury lamp, and dried by nitrogen spraying to obtain a relief pattern.
The cured state of the relief pattern was evaluated by calculating the yield of residual film thickness according to the equation: ##EQU1##
Subsequently, the coating film was heated under nitrogen at 100.degree. C. for 30 minutes, at 200.degree. C. for 30 minutes, and then at 350.degree. C. for 30 minutes to obtain a relief pattern of polyimide. The results obtained are shown in Table 2.
Each solution of photosensitive resin composition obtained in Examples 1 to 107 was coated on a glass substrate, dried, and then heated at 350.degree. C. for 1 hour. The film thus obtained was peeled from the glass substrate and film characteristics after curing were evaluated by the methods described below. The results obtained are shown in Table 2.
(1) Tensile Strength
Measured by making the aforesaid film (thickness: 30 .mu.m) into test pieces having a width of about 1 cm and a length of about 10 cm, and measuring (10 mm/min) S-S curve for five of the test pieces by means of a tensile tester.
(2) Weight Loss Initiation Temperature
Measured in the air at a heating rate of 10.degree. C./min by means of a differential thermobalance by using 10 mg of the aforesaid film.
In addition, each solution of photosensitive resin composition was spin coated on a silicon wafer, formed into a cured film, and subjected to adhesive properties evaluation by the so-called cross-cut test. The cross-cut test comprises cutting the cured film with a cutter knife so as to form 100 squares (1 mm.sup..quadrature. ; each 1 mm.sup.2), peeling off them by use of the cellophane adhesive tape prescribed in JIS K5400, and expressing the adhesive properties in terms of the number of squares peeled off per the 100 squares. The adhesive properties evaluation was carried out by counting the number of squares peeled off in the cross-cut test after treating the cured film for 100 hours by a pressure cooker test (121.degree. C., 2 atmospheres). The results obtained are shown in Table 2.
Comparative Synthetic Examples 55 to 59
In the same manner as in Synthetic Example 43 or Synthetic Example 1 for Comparative Synthetic Examples 55 and 56 or Comparative Synthetic Examples 57 to 59, respectively, polymers were obtained by using a tetracarboxylic acid dianhydride, a diamine, a solvent an isocyanato compound having at least one ethylenic unsaturated group and a hydroxy group having at least one ethylenic unsaturated group in blending amounts shown in Table 1. Each of the polymers thus obtained as PI-55 to PI-59, respectively, was solidified by adding 80 ml of ethanol, followed by stirring for 3 hours and slow pouring into 8 liters of water.
Comparative Examples 1 to 14
Each of the polymers obtained in Comparative Synthetic Examples was stirred together with each photoinitiator, each polymerizable unsaturated compound and the like listed in Table 3, whereby there were obtained homogeneous solutions of photosensitive resin composition which were used in Comparative Examples 1 to 17.
In the same manner as in Examples, each solution was coated on a silicon wafer to obtain a coating film.
Then, the surface of the coating film was covered with a pattern mask, and exposure, development, rinsing, etc. were conducted in the same manner as in Examples to obtain a relief pattern. The cured state of the relief was evaluated in terms of the yield of residual film thickness.
Subsequently, the coating film was heated under nitrogen at 100.degree. C. for 30 minutes, at 200.degree. C. for 30 minutes, and then at 350.degree. C. for 30 minutes, and film characteristics after curing were evaluated in the same manner as in Examples. The results obtained are shown in Table 3.
The photosensitive resin composition and the photosensitive element using the same of this invention have a high solubility, and can give a final cured film having both high heat resistance and high flexibility on the surface of a substrate. Moreover, they are good in light-trnasmitting properties and hence can be formed into a thick film. In addition, a thick film patterns obtained by using them have small dielectric constant and hence are useful as interlaminar insualting materials.
TABLE 1 Isocyanate compound con- Synthetic Tetracarboxylic taining at least one Example acid dianhydride Diamine ethylenic unsaturated group Solvent polymer Synthetic 2,2-Bis(3,4-dicarboxyphenyl)- 2,2-Bis[4-(4-aminophenoxy)- Isocyanatoethyl N-Methyl-2- PI-2 Example hexafluoropropane dianhydride phenyl]hexafluoropropane methacrylate pyrrolidone 2 (133.2 g) (155.4 g) (23.3 g) (720 g) Synthetic 2,2-Bis(3,4-dicarboxyphenyl)- 2,2-Bis(4-aminop henyl)hexa- Isocyanatoethyl N-Methyl-2- PI-3 Example hexafluoropropane dianhydride fluoropropane methacrylate pyrrolidone 3 (133.2 g) (100.2 g) (23.3 g) (590 g) Synthetic 3,3',4,4'-Benzophenonetetra- 2,2-Bis[4-(4-amin ophenoxy)- Isocyanatoethyl N-Methyl-2- PI-4 Example carboxylic dianhydrid e phenyl]hexafluoropropane methacrylate pyrroliidone 4 (96.6 g) (155.4 g) (23.3 g) (635 g) Synthetic 3,3',4, 4'-Benzophenonetetra- 2,2-Bis-(4-am inophenyl)hexa- TD-HEA N-Methyl-2- PI-5 Example carboxylic dianhydride fluoropropane (43.5 g) pyrrolidone 5 (48.3 g) (100.2 g) (600 g) 2,2-Bis(3,4-dicarboxyphenyl)- hexafluoropropane dianhydride (66.6 g) Synthetic 3,3',4, 4'-Benzophenonetetra- 2,2-Bis-(3-amino-4-methyl- TD-HEA N-Methyl-2- PI-6 Example carboxylic dianhydride phenyl)hexafluorop ropane (43.5 g) pyrrolidone 6 (48.3 g) (108.6 g) (575 g) 2,2-Bis(3,4-di carboxyphenyl)- hexafluoropropane dianhydride (96.6 g) Synthetic 3,3',4,4'-Biphenyltetra- 2,2-Bis(3-amino-4-methylphenyl)- Isocyanatoethyl N-Methyl-2- PI-7 Example carboxylic dianhydride hexafluoropropane methacrylate pyrrolidone 7 (88.2 g) (54.3 g) (23.3 g) (510 g) 4,4'-Diam inodiphenyl ether (30.1 g) Synthetic 2,2-Bis[4-(3,4-dicarboxy- 4,4'-Diamino-diphenyl ether Isocyanatoethyl N-Methyl-2- PI-8 Example phenoxy)phenyl]hexafluoro- (60.1 g) methacrylate pyrrolidone 8 propane dianhydride (23.3 g) (630 g) (188.4 g) Synthetic 2,2-Bis[4-(3,4-dicarbo xy- p-Phenylenediamine Isocyanatoethyl N-Methyl-2- PI-9 Example phenoxy)p henyl]hexafluoro- (32.4 g) methacrylate pyrrolidone 9 propane dianhydride (23.3 g) (560 g) (188.4 g) Synthetic 2,2-Bis[3-(4-dicarboxylphenyl)- 2,2-Bis[4-(4-aminophenoxy)- TD-HEA N-Methyl-2- PI-10 Example hexafluoropr opane dianhydride phenyl-]hexafluoropropane (23.3 g) pyrrolidone 10 (66.6 g) (155.4 g) (640 g) m-Terphenyl-3,3',4,4'-tetra- carboxylic dianhydride (55.5 g) Synthetic 2,2-Bis(3,4-dicarboxyphenyl)- 4,4'-Diamin odiphenyl ether Isocyanatoethyl N-Methyl-2- PI-11 Example hexafluoropropa ne dianhydride (60.1 g) methacrylate pyrrolidone 11 (133.2 g) (23.3 g) (560 g) Synthetic 2,2-Bis(3,4-dicarboxyphenyl)- 2,2-Bis[4-(4-aminophenoxy )- Isocyanatoethyl N-Methyl-2- PI-12 Example hexafluorpropane dianhydride phenyl]-hexafluoropropane methacrylate pyrrolidone 12 (133.2 g) (155.4 g) (23.3 g) (780 g) Synthetic 2,2-Bis(3,4-dicarboxyphenyl)- 4,4'-Diaminod iphenyl ether Isocyanato N-Methyl-2- PI-13 Example hexafluoropropane dianhydride (30.05 g) compound pyrrolidone 13 (133.2 g) 2,2-Bis[4-(4-amin ophenoxy)- TD-HEA (763 g) phenyl]hexafluoropropane (43.5 g) (77.7 g) Synthetic 2,2-Bis(2,3-dicarboxyphenyl)- 4,4-Diaminodiphenyl ether Isocyanatoethyl N-Methyl-2- PI-14 Example hexafluoropropane dianhydride (60.1 g) methacrylate pyrrolidone 14 (133.2 g) (23.3 g) (560 g) Synthetic 2,2-Bis(3,4-dicarboxyphenyl)- 4,4'-Diaminodiphenylether- Isocyanatoethyl N-Methyl-2- PI-15 Example hexafluoropropane dianhydride 3-carbonamide methacrylate pyrrolidone 15 (133.2 g) (72.9 g) (23.3 g) (585 g) Synthetic 3,3',4,4'-Benzophenonetetra- 2,2-Bis(4-aminophenyl)hexa - TD-HEA N-Methyl-2- PI-16 Example carboxylic dianhydride fluoropropane (43.5 g) pyrrodidone 16 (96.6 g) (100.2 g) (660 g) Synthetic 3,3'-4,4'-B iphenyltetra- 2,2-Bis(4-aminophenyl)hexa- Isocyanatoethyl N-Methyl-2- PI-17 Example carboxylic dianhydride fluoropropane methacrylate pyrrodido ne 17 (88.2 g) (100.2 g) (23.3 g) (540 g) Synthetic m-Terphenyl-3,3",4"-t etra- 2,2-Bis(3-amino-4-methyl- Isocyanatoethyl N-Methyl-2- PI-18 Example carboxylic dianhydride phenyl)hexafluoropropane methacrylate pyrrolidone 18 (111.0 g) (108.6 g) (23.3 g) (620 g) Synthetic 3,3',4,4'-B enzophenonetetra- 2-2-Bis(4-aminophenyl)-hexa- Isocyanatoethyl N-Methyl-2 - PI-19 Example carboxylic dianhydride fluoropropane methacrylate pyrrolidone 19 (96.6 g) (50.1 g) (23.3 g) (500 g) 4,4'-Diaminodiphenyl ether (30.0 g) Synthetic 3,3',4,4'-Benzophenonetetra- 2,2-Bis[4-(4-amin ophenoxy)- TD-HEA N-Methyl-2- PI-20 Example carboxylic dianhydride phenyl)hexafluoropropane (43.5 g) pyrrolidone 20 (96.6 g) (155.4 g) (680 g) Synthetic 3,3',4,4'-Benzophenonetetra- 2,2-Bis[4-(4-aminophenoxy) - Isocyanatoethyl N-Methyl-2- PI-21 Example carboxylic dianhydride phenylthio)-phenyl]hexa- methacrylate pyrrolidone 21 (48.3 g) fluoropropa ne (23.3 g) (660 g) 2,2-Bis(3,4-dicarboxy)hexa- (165 g) fluoropropane dianhydride (66.6 g) Synthetic 3,3',4,4'-Biphenyltetra- 2,2-Bis[4-(4-ami nophenoxy)- TD-HEA N-Methyl-2- PI-22 Example carboxylic dianhydride phenyl]hexafluoropropane (43.5 g) pyrrolidone 22 (88.2 g) (82.5 g) (680 g) 4,4'-Diaminodiphenyl ether (30.1 g) Synthetic Pyromellitic dianhydride 2,2-Bis[4-(3,5-dimethyl-4- TD-HEA N-Methyl-2- PI-23 Example (65.4 g) aminophenoxy)phenyl]hexa- (43.5 g) pyrrolidone 23 fluoropropane (650 g) (172.2 g) Synthetic 3,3',4,4'-Benzophenonetetra- 2,2-Bis[4-(3 ,5-dimethyl-4- Isocyanatoethyl N-Methyl-2- PI-24 Example carboxylic dianhydride aminophenoxy)phenyl]hexa- methacrylate pyrrolidone 24 (96.6 g) fluorpropane (23.3 g) (670 g) (172.2 g) Synthetic 3,3',4,4'-Benzophe nonetetra- 2,2-Bis[4-(4-aminophenoxy)- Methacryloyl N-Methyl-2- PI-25 Example carboxylic dianhydride phenyl]hexafluoropropane isocyanate pyrrolidone 25 (96.6 g) (46.5 g) (16.7 g) (403 g) 4,4'-Diaminodiphenyl ether (42.0 g) Synthetic 3,3',4,4'-Biphenyltetra- 2,2-Bis[4-(4-aminophe noxy)- Methacryloyl N-Methyl-2- PI-26 Example carboxylic dianhydride phenyl]hexafluoropropane isocyanate pyrrolidone 26 (88.2 g) (123.0 g) (16.7 g) (403 g) Synthetic 2,2-Bis(3,4-dicarboxyphenyl)- 4,4'-Diaminodiph enyl ether Isocyanatoethyl N-Methyl-2- PI-27 Example hexafluoropropane dianhydride (40.0 g) methacrylate pyrrolidone 27 (22.2 g) (15.5 g) (250 ml) 1,3-Bis(3,4-dicarboxyphenyl)- 1,1,3,3-tetramethyldisiloxane dianhydride (21.3 g) 3,3',4,4'-Benzophenonetetra- carboxylic dianhydri de (32.2 g) Synthetic 2,2-Bis (3,4-dicarboxyphenyl)-hexafluoropropane dianhydride(22.2 g)1,3-Bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisilo xanedianhydride(21.3 g)3,3',4,4'-Benzophenonetetra-carboxylic dianhydride( 32.2 g) 4,4'-diaminodiphenyl ether(40.0 g) ##STR57## N-Methyl-2-pyrrolidone(250 ml) PI-28 Example 28 Synthetic 2,2-Bis(3,4-dicarboxyphenyl)- 2,2-Bis(4-aminophenyl )- Isocyanatoethyl N-Methyl-2- PI-29 Example hexafluoropropane dianhydrid e hexafluoropropane methacrylate pyrrolidone 29 (22.2 g) (20.0 g) (15.5 g) (250 ml) 1,3-Bis(3,4-dicarboxyphenyl)- 1,1,3,3-tetramethyldisiloxane dianhydride (21.3 g) 3,3',4,4'-Benzophenonetetra- carboxylic dianhydride (32.2 g) Synthetic 3,3',4,4'-Benzophenonetetra- 2,2-Bis(4-am inophenyl)hexa- Isocyanatoethyl N-Methyl-2- PI-30 Example carboxylic dianhydride fluoropropane (10.0 g) methacrylate pyrrolidone 30 (32.2 g) 1,3-Bis(3-aminophenyl)-1,1,3,3- (7.7 g) (250 ml) tetramethyldisiloxane (6.6 g) 4,4'0-Diaminodiphenyl ether (10.0 g) Synthetic 3,3',4,4'-Be nzophenonetetra- 2,2-Bis[4-(4-aminophenoxy)- Isocyanatoethyl N-Methyl-2- PI-31 Example carboxylic dianhydride phenyl]hexafluoropropane methacryalt e pyrrolidone 31 (32.2 g) (15.5 g) (7.7 g) (250 ml) 1,3-Bis(4-aminophen yl)-1,1,3,3- tetramethyldisiloxane (6.6 g) 4,4'-Diaminodiphenyl ether (10.0 g) Synthetic 2,2-Bis(3,4-dicarboxyphenyl)- 2,2-Bis(4-aminop henyl)hexa- Isocyanatoethyl N-Methyl-2- PI-32 Example hexafluoropropane dianhydride fluoropropane methacrylate pyrrolidone 32 (22.2 g) (10.0 g) (7.7 g) (250 ml) 3,3' ,4,4'-Benzophenonetetra- 1,3-Bis(4-aminophenyl)- carboxylic dianhydride 1,1,3,3-tetramethyldisiloxane (16.1 g) (6.6 g) 4,4'-Diaminodiphenyl ether (10.0 g) Synthetic 2,2-Bis(3,4-dicarboxyphen yl)- 2,2-Bis(4-aminophenyl)hexa- Isocyanatoethyl N-Methyl-2- PI-33 Example hexafluoropropane dianhydride fluoropropane methacrylate pyrrolidone 33 (44.4 g) (10.0 g) (7.7 g) (250 ml) 1,3-Bis(4-aminophenyl )-1,1,3,3- tetramethyldisiloxane (6.6 g) 4,4'-Diaminodiphenyl ether (10.0 g) Synthetic 2,2-Bis(3,4-dicarboxyphenyl)- 4,4'-Diaminodiph enyl ether Isocyanatoethyl N-Methyl-2- PI-34 Example hexafluoropropane dianhydride (14.0 g) methacrylate pyrrolidone 34 (13.3 g) 1,3-Bis(4-amino phenyl)-1,1,3,3- (7.7 g) (260 ml) 3,3',4,4'-Benzophenonetetra- tetrameth yldisiloxane carboxylic dianhydride (9.9 g) (22.6 g) SyntheticExample35 2,2-Bis(3,4-dicarboxyphenyl)-hexafluoropropane dianhydride(13.3 g)3,3',4,4'-Benzophenonetetra-carboxylic dianhydride(22. 6 g) 4,4'-Diaminodiphenyl ether(14.0 g)1,3-Bis(4-aminophenyl)-1,1,3,3-tet ramethyldisiloxane(9.9 g) ##STR58## N-Methyl-2-pyrrolidone(260 ml) PI-35 Synthetic 1,3-Bis(3,4-dicarboxyphenyl)- 2,2-Bis(4-aminophenyl)hexa- Isocyanatoethyl N-Methyl-2- PI-36 Example 1,1,3,3-tetramethyldisiloxane fluoropropane methacrylate pyrrolidone 36 (12.8 g) (10.0 g) (7.7 g) (250 ml) 3,3',4,4'-Benzophenonetetra- 4,4'-Diaminodiphenyl ether carboxylic dianhydride (14.0 g) (22.6 g) Synthetic 1,3-Bis(3,4-dicarboxyphenyl)- 2,2-Bis[4-(4-aminophenoxy)- Isocyanatoethyl N-Methyl-2- PI-37 Example 1,1,3,3-tetramethyldisiloxane phenyl]hexafluoropropane methacrylate pyrrolidone 37 dianhydride (12.8 g) (25.9 g) (7.7 g) (250 ml) 3,3',4,4'- Benzophenonetetra- 4,4'-Diaminodiphenyl ether carboxylic dianhydride (22.6 g) (10.0 g) Synthetic 1,3-Bis(3,4-dicarboxyphenyl)- 2,2-Bis(4-amino phenyl-hexa- Isocyanatoethyl N-Methyl-2- PI-38 Example 1,1,3,3-tetramethy ldisiloxane fluoropropane methacrylate pyrrolidone 38 dianhydride (12.8 g) (33.4 g) (7.7 g) 3,3',4,4'-Benzophenonetetra- carboxylic dianhydride (22.6 g) SyntheticExample39 3,3',4,4'-Benzophenonetetra-carboxylic dianhydride(128.88 g) 4,4'-Diaminodiphenyl ether(40.05 g)1,3-Bis(4-aminop henyl)-1,1,3,3-tetramethyldisiloxane(60.8 g) ##STR59## N,N-dimethyl-acetamide(500 ml) PI-39 Synthetic 3,3',4,4'-Benzophenonetetra- 4,4'-Diaminodiphenyl ether Isocyanaotethyl N,N-dimethyl- PI-40 Example carboxylic dianhydride (40.05 g) methacrylate acetamide 40 (128.88 g) 1,3-Bis(4-aminophenyl)-1,1 ,3,3- (31.0 g) (500 ml) tetramethyldisiloxane (60.8 g) SyntheticExample41 3,3'-Benzophenonetetra-carboxylic dianhydride(64.44 g)1,3-Bis(4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxanedianhydride(85. 2 g) 4,4'-Diaminodiphenyl ether(80.1 g) ##STR60## N,N-dimethyl-acetamide(500 ml) PI-41 Synthetic 3,3'-Benzophenonetetra- 4,4'-Diaminodiphenyl ether Isocyanatoethyl N,N-Dimethyl- PI-42 Example carboxylic dianhydride (80.1 g) methacrylate acetamide 42 (64.44 g) (31.0 g) (500 ml) 1,3-Bis(4-dicarboxyphenyl)- 1,1,3,3-tetramethyldisilo xane dianhydride (85.2 g) Synthetic 2,2-Bis(3,4-dicarboxyphenyl)- 4,4'-Diaminodiphenyl ether 2-Hydroxyethyl N-Methyl-2- PI-44 Example hexafluoropropane dianhydride (40.0 g) methacrylate pyrrolidone 44 (20.7 g) (52.0 g) (400 ml) 1,3-Bis(3,4-dicarboxyphenyl)- 1,1,3,3-tetramethyl disiloxane dianhydride (25.6 g) m-Terphenyl-3,3",4,4"-tetra- carboxylic dianhydride (37.0 g) Synthetic 2,2-Bis(3,4-dicarboxyphenyl)- 2,2-Bis[4-(4-aminophenoxy)- 2-Hydroxyethyl N-Methyl-2- PI-45 Example tetrafluoropane dianhydride phenyl)propane methacrylate pyrrolidone 45 (20.7 g) (82.1 g) (52.0 g) (400 ml) 1,3-Bis(3,4-dicarboxyphenyl)- 1,1,3,3-tetramethyldisiloxane dianhydride (25.6 g) 3,3' ,4,4'-Biphenyl tetra carboxylic dianhydride (29.4 g) Synthetic 3,3',4,4'-Benzophenonet etra- 2,2-Bis(4-aminophenyl)hexa- 2-Hydroxyethyl N-Methyl-2- PI-46 Example carboxylic dianhydride fluoropropane methacrylate pyrrolidone 46 (32.2 g) (10.0 g) (26.0 g) (200 ml) 1,3-Bis(4-aminophenyl)-1,1,3,3- tetramethyldisiloxane (6.6 g) 4,4'-Diaminodiphenyl ether (10.0 g) Synthetic 3,3',4,4'-Biphenyltetra- 2,2-Bis(4-aminophenyl)hexa- 2-Hydroxye thyl N-Methyl-2- PI-47 Example carboxylic dianhydride fluoropropane methacrylate pyrrolidone 47 (37.0 g) (10.0 g) (26.0 g) (200 ml) 1,3-Bis(4-aminophenyl)-1,1,3,3- tetramethyldisiloxane (6.6 g) 4,4'-Diaminodiphenyl ether (10.0 g) Synthetic 3,3',4,4'-Benzophenonetet ra- 2,2-Bis[4-(4-aminophenoxy)- 2-Hydroxyphenyl N-Methyl-2- PI-48 Example carboxylic dianhydride phenyl)hexafluoropropane methacrylate pyrrolidone 48 (32.2 g) (75.5 g) (26.0 g) (200 ml) 1,3-Bis(4-aminopheny l)-1,1,3,3- tetramethyldisiloxane (6.6 g) 4,4'-Diaminodiphenyl ether (10.0 g) Synthetic 2,2-Bis(3,4-dicarboxyphenyl)- 4,4'-Diaminodiph enyl ether 2-Hydroxyethyl N-Methyl-2- PI-49 Example hexafluoropropane dianhydride (14.0 g) methacrylate pyrrolidone 49 (13.3 g) 1,3-Bis(4-amino phenyl)-1,1,3,3- (26.0 g) (200 ml) 3,3',4,4'-Benzophenonetetra- tetramethyldisiloxane carboxylic dianhydride (9.9 g) (22.6 g) Synthetic 2,2-Bis(3,4-dicarboxyphenyl)- 4,4'-Diaminodiphenyl ether 2-Hydroxyethyl N-Methyl-2- PI-50 Example hexafluoropropane dianhydride (14.0 g) methacrylate pyrrolidone 50 (13.3 g) 1,3-Bis(4-aminophenyl)-1,1,3,3- (26.0 g) (200 ml) m-Terphenyl-3,3",4,4"-tetra- tetramethyldisiloxane carboxylic dianhydride (9.9 g) (25.9 g) Synthetic 2,2-Bis(3,4-dicarboxyp henyl)- 2,2-Bis[4-(4-aminophenoxy)- 2-Hydroxyethyl N-Methyl-2- PI-51 Example hexafluoropropane dianhydride phenyl]propane methacrylate pyrrolidone 51 (13.3 g) (28.7 g) (26.0 g) (200 ml) 3,3',4,4'-Benzophenon etetra- 1,3-Bis(4-aminophenyl)-1,1,3,3- carboxylic dianhydride tetrameth yldisiloxane (22.6 g) (9.9 g) Synthetic 1,3-Bis(3,4-dicarboxyphenyl)- 4,4'-Diaminodiphenyl ether 2-Hydroxyethyl N-Methyl-2- PI-52 Example 1,1,3,3-tetramethyldisiloxane (14.0 g) methacrylate pyrrolidone 52 (8.5 g) 2,2-Bis(4-aminophenyl-hexa- (26.0 g) (200 ml) 3,3',4,4'-Benzophenonet etra- fluoropropane carboxylic dianhydride (10.0 g) (25.7 g) Synthetic 1,3-Bis(3,4-dicarboxyphenyl)- 4,4'-Diaminodiphenyl ether 2-Hydroxyethyl N-Methyl-2- PI-53 Example 1,1,3,3-tetramethyldisiloxane (14.0 g) methacrylate pyrrolidone 53 (8.5 g) 2,2-Bis(4-aminophenyl)-hexa- (26.0 g) (200 ml) m-Terphenyl-3,3",4,4"-tetra- fluoropropane carboxylic dianhydride (10.0 g) (29.6 g) Synthetic 1,3-Bis(3,4-dicarboxyphenyl)- 4,4'-Diaminodiphenyl ether 2-Hydroxyethyl N-methyl-2- PI-54 Example 1,1,3,3-tetramethyldisiloxane (10.0 g) methacrylate pyrrolidone 54 dianhydride (8;5 g) 2,2-Bis[4-(4-aminophenoxy)- (26.0 g) (200 ml) 3,3',4,4'-Benzophenonetetra- phenyl)hexafluoropropane carboxylic dianhydride (25.9 g) (25.7 g) Hydroxy compound containing at least one ethylenic unsaturated Comp. group/isocyanate compound Synthetic Tetracarboxylic containing at least one Example acid dianhydride Diamine ethylenic unsaturated group Solvent polymer Comp. Pyromellitic dianhydride 4,4'-Diaminodiphenyl ether 2-Hydroxyethy l N-Methyl-2- PI-55 Synthetic (21.8 g) (20.0 g) methacrylate pyrrolidone Example (26.0 g) (202 ml) 55 Comp. 3,3',4,4'-Benzophenonetetra- 4,4'-Diaminodiphenyl ether 2-Hydroxyethyl N-Methyl-2- PI-56 Synthetic carboxylic dianhydride (20.0 g) methacrylate pyrrolidone Example (32.2 g) (26.0 g) (202 ml) 56 Comp. Pyromellitic dianhydride p-Phenylenediamin e Isocyanatoethyl N-Methyl-2- PI-57 Synthetic (14.0 g) (10.8 g) methacryl ate pyrrolidone Example (15.5 g) (250 ml) 57 Comp. 3,3',4,4'-Benzopheno netetra- 4,4'-Diaminodiphenyl ether Isocyanatoethyl N-Methyl-2- PI-58 Synthetic carboxylic dianhydride (20.0 g) methacrylate pyrrolidone Example (32.2 g) (15.5 g) (250 ml) 58 Comp. 3,3',4,4'-Benzophenonetetra- 4,4'-Diaminodiphenyl ether Isocyanatoethyl N,N-dimethyl- PI-59 Synthetic carboxylic dianhydride (80.10 g) methacrylate acetamide Example (128.88 g) (31.0 g) (500 ml) 59
TABLE 2 Thickness of coating Yield Weight Polymeri- film of loss zable un- before residual initiation Exam- saturated develop- film Tensile temper- ple Polymer Photo-initiator/Assistant of photo-initi ator compound ment thickness strength ature Exam- PI-1 2,4-Diethylthioxanthone (0.6 g)/ Ethylene 28 .mu.m 89% 7.0 400.degree. C. ple 1 (100 g) Ethyl p-dimethylaminobenzoate (0.9 g) glycol kgf/mm.sup.2 diacrylate (4.5 g) Exam- PI-1 2,6-Bis(p-dieth ylaminobenzylidene)-4-methyl-4- Hexane- 27 .mu.m 88% 6.2 405.degree. C. ple 2 (100 g) azacylohexane (0.15 g)/ diol kgf/mm.sup.2 N-(p-chloroph enyl)-glycine (1.5 g) diacrylate (4.5 g) Exam- PI-2 2,4-Diethylthioxan thone (0.6 g)/ Ethylene 31 .mu.m 85% 7.1 408.degree. C. ple 3 (100 g) Ethyl p-dimethylaminobenzoate (4.5 g) glycol di- kgf/mm.sup.2 acrylate (4.5 g) Exam- PI-3 2,4-Diethylthioxanthone (0.6 g)/ -- 30 .mu.m 80% 6.5 405.degree. C. ple 4 (100 g) Ethyl p-dimethylaminobenzoate (0.9 g) kgf/mm.sup.2 Exam- PI-4 2,6-Bis(p-diethylaminobenzylidene)-4-m ethyl-4- Ethylene 29 .mu.m 83% 5.7 398.degree. C. ple 5 (100 g) azacylohexane (0.15 g)/ glycol di- kgf/mm.sup.2 N-Phenyl-glycine (1.5 g) acrylate (4.5 g) Exam- PI-5 2,6-Bis(p-diethyl aminobenzylidene)-4-methyl-4- Ethylene 31 .mu.m 88% 5.5 400.degree. C. ple 6 (100 g) azacylohexane (0.15 g)/ glycol di- kgf/mm.sup.2 N-Phenyl-glycine (1.5 g) acrylate (4.5 g) Exam- PI-6 2,4-Diethylthioxa nthone (0.6 g)/ Hexane- 30 .mu.m 85% 5.9 395.degree. C. ple 7 (100 g) Isoamyl p-diethylaminobenzoate (0.9 g) diol di- kgf/mm.sup.2 acrylate (4.5 g) Exam- PI-7 2,4-Diethylthioxanthone (0.6 g)/ Hexane- 28 .mu.m 83% 5.8 402.degree. C. ple 8 (100 g) Isoamyl p-diethylaminobenzoate (0.9 g) diol di- kgf/mm.sup.2 acrylate (4.5 g) Exam- PI-7 2,6-Bis(p-diethylaminobenz ylidene)-4-methyl-4- Tetraethyl 30 .mu.m 88% 6.5 400.degree. C. ple 9 (100 g) azacylohexanone (0.15 g)/ ene glycol kgf/mm.sup.2 N-(p-chloro phenyl)-glycine (1.5 g) diacrylate (4.5 g) Exam- PI-8 2,6-Bis(p-diethy laminobenzylidene)-4-methyl-4- Tetraethyl 28 .mu.m 86% 7.0 405.degree. C. ple 10 (100 g) azacyclohexanone (0.15 g)/ ene glycol kgf/mm.sup.2 N-(p-chlorophenyl)-glycine (1.5 g) diacrylate (4.5 g) Exam- PI-9 2,6-Bis(p-diethylaminobenzylidene)-4-methyl-4- Tetraethyl 29 .mu.m 83% 7.3 396.degree. C. ple 11 (100 g) azacyclohexanone (0.15 g)/ ene glycol kgf/mm.sup.2 N-(p-chlorophenyl)-glycine (1.5 g) diacrylate (4.5 g) Exam- PI-10 1,4-Diethylthioxanthone (0.6 g)/ A-BPE-10 30 .mu.m 84% 8.0 402.degree. C. ple 12 (100 g) Isoamyl p-dimethylaminobenzoate (0.9 g) (4.5 g) kgf/mm.sup.2 Exam- PI-10 2,6-Bis(p-diethylaminobenzylidene)-4-m ethyl-4- -- 30 .mu.m 85% 6.9 410.degree. C. ple 13 (100 g) azacyclohexanone (0.15 g)/ kgf/mm.sup.2 N-(p-chlo rophenyl)-glycine (1.5 g) Exam- PI-1 2,4-Diethylthioxanthone (0.6 g)/ Ethylene 30 .mu.m 90% 7.0 400.degree. C. ple 14 (100 g) Ethyl p-dimethylaminobenzoate (0.9 g) glycol di- kgf/mm.sup.2 acrylate (4.5 g) Exam- PI-1 2,6-Bis(p-diethylaminobenz ylidene)-4-methyl-4- Hexane- 31 .mu.m 88% 6.2 405.degree. C. ple 15 (100 g) azacyclohexanone (0.15 g)/ diol kgf/mm.sup.2 N-(p-Cyanophenyl)-gly cine (1.5 g) diacrylate (4.5 g) Exam- PI-1 2,6-Bis(p-diethylaminobenzy lidene)-4-methyl-4- -- 29 .mu.m 80% 5.9 397.degree. C. ple 16 (100 g) azacyclohexanone (0.15 g)/ kgf/mm.sup.2 N-(p-Cyanophenyl)-glycine (1.5 g) Exam- PI-11 2,4-Diethylthioxanthone (0.6 g)/ Ethylene 30 .mu.m 92% 7.6 395.degree. C. ple 17 (100 g) Ethyl p-dimethylaminobenzoate (0.9 g) glycol di- kgf/mm.sup.2 acrylate (4.5 g) Exam- PI-11 2,6-Bis(p -diethylaminobenzylidene)-4-methyl-4- -- 30 .mu.m 78% 6.3 398.degree. C. ple 18 (100 g) azacyclohexanone (0.15 g)/ kgf/mm.sup.2 N-(p-Cyano-ph enyl)-glycine (1.5 g) Exam- PI-11 2,6-Bis(p-diethylaminobenzylidene)-4-me thyl-4- A-BPE-10 29 .mu.m 90% 5.7 403.degree. C. ple 19 (100 g) azacyclohexanone (0.15 g)/ (4.5 g) kgf/mm.sup.2 N-(p-Cyano-phenyl)-glycine (1.5 g) Exam- PI-12 2,4-Diethylthioxanthone (0.6 g)/ Ethylene 31 .mu.m 85% 7.1 408.degree. C. ple 20 (100 g) Ethyl p-dimethylaminobenzoate (0.9 g) glycol di- kgf/mm.sup.2 acrylate (4.5 g) Exam- PI-13 2,4-Diethylthioxanthone (0.6 g)/ A-BPE-10 32 .mu.m 90% 6.5 402.degree. C. ple 21 (100 g) Ethyl p-dimethylaminobenzoate (0.9 g) (4.5 g) kgf/mm.sup.2 Exam- PI-14 2,4-Diethylthioxanthone (0.6 g)/ Ethylene 33 .mu.m 86% 3.5 386.degree. C. ple 22 (100 g) Ethyl p-dimethylaminobenzoate (0.9 g) glycol di- kgf/mm.sup.2 acrylate (4.5 g) Exam- PI-15 2,4-Diethylthioxanthone (0.6 g)/ Ethylene 30 .mu.m 90% 6.1 404.degree. C. ple 23 (100 g) Ethyl p-dimethylaminobenzoate (0.9 g) glycol di- kgf/mm.sup.2 acrylate (4.5 g) Exam- PI-15 2,6-Bis(p-diethylaminobenzylidene)-4-methyl-4- Ethylene 31 .mu.m 84% 5.8 405.degree. C. ple 24 (100 g) azazcyclohexanone (0.15 g)/ glycol di- kgf/mm.sup.2 N-(p-Cyanophenyl)-glycine (1.5 g) acrylate (4.5 g) Exam- PI-16 2,4-Diethylthioxanthone (0.6 g)/ Ethylene 28 .mu.m 83% 5.7 401.degree. C. ple 25 (100 g) Ethyl p-dimethylaminobenzoate (0.9 g) glycol di- kgf/mm.sup.2 acrylate (4.5 g) Exam- PI-16 2,6-Bis(p-diethylaminoben zylidene)-4-methyl-4- Hexane- 27 .mu.m 90% 5.5 405.degree. C. ple 26 (100 g) azacyclohexanone (0.15 g)/ diol di- kgf/mm.sup.2 N-(p-Chlorop henyl)-glycine (1.5 g) acrylate (4.5 g) Exam- PI-16 2,6-Bis(p-diethyla minobenzylidene)-4-methyl-4- -- 28 .mu.m 82% 6.4 397.degree. C. ple 27 (100 g) azacyclohexanone (0.15 g)/ kgf/mm.sup.2 N-(p-Chlorophenyl)-g lycine (1.5 g) Exam- PI-17 2,4-Diethylthioxanthone (0.6 g)/ Ethylene 30 .mu.m 90% 6.8 395.degree. C. ple 28 (100 g) Ethyl p-dimethylaminobenzoate (0.9 g) glycol di- kgf/mm.sup.2 acrylate (4.5 g) Exam- PI-17 2,6-Bis(p-diethylaminoben zylidene)-4-methyl-4- -- 31 .mu.m 84% 6.2 408.degree. C. ple 29 (100 g) azacyclohexanone (0.15 g)/ kgf/mm.sup.2 N-Phenyl glycine (1.5 g) Exam- PI-17 2,6-Bis(p-diethylaminobenzylidene)-4-methyl-4- A-BPE-10 30 .mu.m 92% 5.7 410.degree. C. ple 30 (100 g) azacyclohexanone (0.15 g)/ (4.5 g) kgf/mm.sup.2 N-Phenyl glycine (1.5 g) Exam- PI-18 2,4-Diethyl thioxanthone (0.6 g)/ Ethylene 29 .mu.m 84% 3.3 378.degree. C. ple 31 (100 g) Ethyl p-dimethylaminobenzoate (0.9 g) glycol di- kgf/mm.sup.2 acrylate (4.5 g) Exam- PI-18 2,4-Diethylthioxanthone (0.6 g)/ A-BPE-10 27 .mu.m 86% 3.2 370.degree. C. ple 32 (100 g) Ethyl p-dimethylaminobenzoate (0.9 g) (4.5 g) kgf/mm.sup.2 Exam- PI-19 2,4-Diethylthioxanthone (0.6 g)/ Ethylene 30 .mu.m 82% 5.0 405.degree. C. ple 33 (100 g) Ethyl p-dimethylaminobenzoate (0.9 g) glycol di- kgf/mm.sup.2 acrylate (4.5 g) Exam- PI-5 2,4-Diethylthioxanthone (0.6 g)/ Ethylene 29 .mu.m 84% 5.1 408.degree. C. ple 34 (100 g) Ethyl p-dimethylaminobenzoate (0.9 g) glycol di- kgf/mm.sup.2 acrylate (4.5 g) Exam- PI-5 2,6-Bis(p-diethylaminobenzylidene)-4-methyl-4- Ethylene 31 .mu.m 88% 5.5 400.degree. C. ple 35 (100 g) azacyclohexanone (0.15 g)/ glycol di- kgf/mm.sup.2 N-(p-Cyanophenyl)-glycine (1.5 g) acrylate (4.5 g) Exam- PI-4 2,4-Diethylthioxanthone (0.6 g)/ Ethylene 33 .mu.m 83% 5.5 400.degree. C. ple 36 (100 g) Ethyl p-dimethylaminobenzoate (0.9 g) glycol di- kgf/mm.sup.2 acrylate (4.5 g) Exam- PI-4 2,6-Bis(p-diethylaminobenz ylidene)-4-methyl-4- Ethylene 30 .mu.m 85% 5.7 398.degree. C. ple 37 (100 g) azacyclohexanone (0.15 g)/ glycol di- kgf/mm.sup.2 N-Phenyl glycine (1.5 g) acrylate (4.5 g) Exam- PI-4 2,6-Bis(p-diethylaminobenz ylidene)-4-methyl-4- -- 29 .mu.m 80% 5.6 395.degree. C. ple 38 (100 g) azacyclohexanone (0.15 g)/ kgf/mm.sup.2 N-Phenyl glycine (1.5 g) Exam- PI-20 2,6-Bis(p-diethylaminobenzylidene)-4-methyl-4- Hexanediol 30 .mu.m 85% 6.5 405.degree. C. ple 39 (100 g) azacyclohexanone (0.15 g)/ diacrylate kgf/mm.sup.2 N-(p-Chlorophenyl)-glycine (1.5 g) (4.5 g) Exam- PI-20 2,6-Bis(p-diethylaminobenzylidene)-4-methyl-4- -- 30 .mu.m 80% 6.2 403.degree. C. ple 40 (100 g) azacyclohexanone (0.15 g)/ kgf/mm.sup.2 N-(p-Chlorophenyl)-glycine (1.5 g) Exam-PI-20 2,4-Diethylt hioxanthone (0.6 g)/ Hexanediol 32 .mu.m 87% 5.9 400.degree. C. ple 41 (100 g) Ethyl p-dimethylaminobenzoate (0.9 g) diacrylate kgf/mm.sup.2 (4.5 g) Exam- PI-21 2,4-Diethylthioxanthone (0.6 g)/ Hexanediol 30 .mu.m 88% 5.4 410.degree. C. ple 42 (100 g) Ethyl p-dimethylaminobenzoate (0.9 g) diacrylate kgf/mm.sup.2 (4.5 g) Exam- PI-21 2,6-Bis(p-diethylaminobenzylidene)-4- methyl-4- Ethyl 29 .mu.m 83% 6.7 404.degree. C. ple 43 (100 g) azacyclohexanone (0.15 g)/ glycol kgf/mm.sup.2 N-(p-Cyanophenyl)-glycine (1.5 g) diacrylate (4.5 g) Exam- PI-22 2,6-Bis(p-diethylaminobenzylidene)-4-methyl-4- Ethylene 29 .mu.m 84% 5.5 405.degree. C. ple 44 (100 g) azacyclohexanone (0.15 g)/ glycol kgf/mm.sup.2 N-Phenyl-glycine (1.5 g) diacrylate (4.5 g) Exam- PI-23 2,6-Bis(p-diethylaminobenzylidene)-4-methyl-4- Ethylene 30 .mu.m 90% 5.7 410.degree. C. ple 45 (100 g) azacyclohexanone (0.15 g)/ glycol kgf/mm.sup.2 N-Phenylglycine (1.5 g) diacrylate (4.5 g) Exam- PI-23 2,4-Diethylthioxanthone (0.6 g)/ -- 30 .mu.m 80% 5.1 402.degree. C. ple 46 (100 g) Ethyl p-dimethylaminobenzoate (0.9 g) kgf/mm.sup.2 Exam- PI-24 2,4-Diethylthioxanthone (0.6 g)/ -- 29 .mu.m 82% 5.8 408.degree. C. ple 47 (100 g) Ethyl p-dimethylaminobenzoate (0.9 g) kgf/mm.sup.2 Exam- PI-24 2,6-Bis(p-diethylaminobenzylidene)-4-methyl-4- Ethylene 31 .mu.m 80% 6.1 403.degree. C. ple 48 (100 g) azacyclohexanone (0.15 g)/ glycol kgf/mm.sup.2 N-Phenylglycine (1.5 g) diacrylate (4.5 g) Exam- PI-25 2,6-Bis(p-diethylaminobenzylidene)-4-methyl-4- -- 35 .mu.m 81% 5.1 388.degree. C. ple 49 (100 g) azacyclohexanone (0.2 g)/ kgf/mm.sup.2 N-(p-Cyanophenyl)-glycine (2.0 g) Exam- PI-25 2,4-Diethylt hioxanthone (0.8 g)/ 2,2-Bis(4- 33 .mu.m 90% 7.1 415.degree. C. ple 50 (100 g) Ethyl N,N-diethylaminobenzoate (1.1 g) acryloxy- kgf/mm.sup.2 penta- ethoxy- phenyl)- propane (6.0 g) Exam- PI-25 2,4-Diethylthioxanthone (0.8 g)/ Tetraethy- 30 .mu.m 84% 6.2 395.degree. C. ple 51 (100 g) Isoamyl N,N-diethylaminobenzoate (1.2 g) lene kgf/mm.sup.2 glycol diacrylate (6.0 g) Exam- PI-26 2,4-Diethylth ioxanthone (0.8 g)/ -- 30 .mu.m 80% 6.4 393.degree. C. ple 52 (100 g) Ethyl N,N-dimethylaminobenzoate (1.3 g) kgf/mm.sup.2 Exam- PI-26 2,6-Bis(p-diethylaminobenzylidene)-4-methyl-4- 2,2-Bis- 35 .mu.m 84% 6.8 398.degree. C. ple 53 (100 g) azacyclohexanone (0.2 g)/ (4-acryl- kgf/mm.sup.2 N-(p-Cyano-phenyl)-glycine (2.2 g) oxypenta- ethoxy- phenyl)- propane (6.5 g) Exam- PI-26 2,6-Bis(p-diethylaminobenzyli dene)-4-methyl-4- Tetra- 40 .mu.m 80% 6.1 402.degree. C. ple 54 (100 g) azacyclohexanone (0.2 g)/ ethylene kgf/mm.sup.2 N-(p-Cyanophenyl)-gly cine (2.2 g) glycol diacry- late (6.0 g) Thickness Yield Weight Polymeri- of coating of loss zable un- film before residual initiation Exam- Poly- saturated develop- film Tensile temper- ple mer Photoinitiator/Assistant of photoinitiator compound Solvent ment thickness strength ature Exam- PI-43 2,4-Diethylthioxyanthone (0.3 g)/ Tetra- N-Methyl- 30 .mu.m 84% 6.0 410.degree. C. ple 55 (10 g) Ethyl N,N-diethylaminobenzoate (0.4 g) ethylene 2-pyr- kgf/mm.sup.2 glycol di- rolidone acrylate (23.5 g) (1.6 g) Exam- PI-43 2,4-Diethylthioxyanthone (0.3 g)/ 1,6- N-Methyl- 28 .mu.m 85% 5.2 400.degree. C. ple 56 (10 g) Ethyl N,N-diethylaminobenzoate (0.4 g) Hexane- 2-pyr- kgf/mm.sup.2 diol di- rolidone acrylate (24 g) (1.5 g) Exam- PI-44 2,4-Diethylthioxyanthone (0.3 g)/ -- N-Methyl- 31 .mu.m 85% 6.2 415.degree. C. ple 57 (10 g) Ethyl N,N-diethylaminobenzoate (0.4 g) 2-pyr- kgf/mm.sup.2 rolidone (25 g) Exam- PI-44 2,4-Diethylthioxyanthone (0.3 g)/ Tetra- N-Methyl- 29 .mu.m 83% 5.7 398.degree. C. ple 58 (10 g) Ethyl N,N-diethylaminobenzoate (0.4 g) ethylene 2-pyr- kgf/mm.sup.2 glycol rolidone dimeth- (25 g) acrylate (1.7 g) Exam- PI-45 2,6-Bis(p-diethylaminobenzylidene-4-methyl-4- Tetra- N-Methyl- 28 .mu.m 85% 5.6 395.degree. C. ple 59 (10 g) azacyclohexanone (0.1 g)/ ethylene 2-pyr- kgf/mm.sup.2 N-(p-cyanophenyl)-glycine (0.6 g) glycol di- rolidone acrylate (24 g) (1.6 g) Exam- PI-45 2,6-Bis(p-diethylamino benzylidene-4-methyl-4- -- N-Methyl- 30 .mu.m 82% 6.4 412.degree. C. ple 60 (10 g) azacyclohexanone (0.1 g)/ 2-pyr- kgf/mm.sup.2 N-(p-cyanoph enyl)-glycine (0.6 g) rolidone (24 g) Exam- PI-27 Benzophenone (0.1 g)/ 1,6- N-Methyl- 30 .mu.m 88% 5.5 395.degree. C. ple 61 (10 g) Michler's ketone (0.1 g) Hexane- 2-pyr- kgf/mm.sup.2 diol di- rolidone acrylate (24 g) (1.5 g) Exam- PI-27 2,4-Diethylthioxanthon e (0.3 g)/ Tetra- N-Methyl- 29 .mu.m 85% 6.0 405.degree. C. ple 62 (10 g) Isoamyl N,N-diethylaminobenzoate (0.4 g) ethylene 2-pyr- kgf/mm.sup. 2 glycol rolidone diacrylate (24 g) (1.6 g) Exam- PI-28 2,4-Diethylthioxanthone (0.3 g)/ Tetra- N-Methyl- 31 .mu.m 86% 6.1 410.degree. C. ple 63 (10 g) Isoamyl N,N-diethylaminobenzoate (0.4 g) ethylene 2-pyr- kgf/mm.sup.2 glycol rolidone diacrylate (25 g) (1.6 g) Exam- PI-28 2,4-Diethylthioxanthone (0.3 g)/ -- N-Methyl- 32 .mu.m 80% 6.7 400.degree. C. ple 64 (10 g) Isoamyl N,N-diethylaminobenzoate (0.4 g) 2-pyr- kgf/mm.sup.2 rolidone (25 g) Exam- PI-29 2,4-Diethylthioxanthone (0.3 g)/ Tetra- N-Methyl- 30 .mu.m 82% 6.5 400.degree. C. ple 65 (10 g) Isoamyl N,N-diethylaminobenzoate (0.4 g) ethylene 2-pyr- kgf/mm.sup.2 glycol rolidone diacrylate (25 g) (1.7 g) Exam- PI-46 2,4-Diethyl thioxanthone (0.3 g)/ Tetra- N-Methyl- 30 .mu.m 83% 5.5 410.degree. C. ple 66 (10 g) Ethyl N,N-diethylaminobenzoate (0.5 g) ethylene 2-pyr- kgf/mm.sup.2 glycol rolidone diacrylate (24 g) (1.5 g) Exam- PI-46 2,4-Diethylthioxanthone (0.3 g)/ -- N-Methyl- 32 .mu.m 85% 5.9 400.degree. C. ple 67 (10 g) Ethyl N,N-diethylaminobenzoate (0.4 g) 2-pyr- kgf/mm.sup.2 rolidone (24 g) Exam- PI-47 2,4-Diethylthio xanthone (0.2 g)/ Tetra- N-Methyl- 34 .mu.m 80% 6.0 398.degree. C. ple 68 (10 g) Ethyl N,N-diethylaminobenzoate (0.5 g) ethylene 2-pyr- kgf/mm.sup.2 glycol rolidone diacrylate (24 g) (1.6 g) Exam- PI-47 2,6-Bis(p-diethylaminobenzylidene)-4-methyl-4- -- N-Methyl- 30 .mu.m 86% 6.3 410.degree. C. ple 69 (10 g) azacyclohexanone (0.1 g)/ 2-pyr- kgf/mm.sup.2 N-Phenyl-glycine (0.6 g) rolidone (24 g) Exam- PI-48 2,6-Bis(p-diethylaminobenzylidene)-4-methyl-4- Tetra- N-Methyl- 29 .mu.m 88% 6.1 402.degree. C. ple 70 (10 g) azacyclohexanone (0.1 g)/ ethylene pyrrolidone kgf/mm.sup.2 N-(p-cyanophenylglycine (0.6 g) glycol (24 g) dimeth- acrylate (1.5 g) Exam- PI-48 2,6-Bis(p-diethylaminobenzylidene)-4-methyl-4- 1,6- N-Methyl- 28 .mu.m 84% 5.8 395.degree. C. ple 71 (10 g) azacyclohexanone (0.1 g)/ Hexane 2-pyr- kgf/mm.sup.2 N-(p-cyanophenylglycine (0.6 g) diol di- rolidone acrylate (24 g) (1.0 g) Exam- PI-30 Benzophenone (0.3 g)/ -- N-Methyl- 32 .mu.m 80% 6.4 405.degree. C. ple 72 (10 g) Michler's ketone (0.1 g) 2-pyr- kgf/mm.sup.2 rolidone (24 g) Exam- PI-30 2,4-Diethylthioxanthone (0.2 g)/ Tetra- N-Methyl- 30 .mu.m 83% 5.4 403.degree. C. ple 73 (10 g) Isoamyl N,N-diethylaminobenzoate (0.4 g) ethylene 2-pyr- kgf/mm.sup.2 glycol rolidone diacrylate (24 g) (1.2 g) Exam- PI-31 2,4-Diethylthioxanthone (0.3 g)/ Tetra- N-Methyl- 28 .mu.m 87% 6.0 395.degree. C. ple 74 (10 g) Isoamyl N,N-diethylaminobenzoate (0.5 g) ethylene 2-pyr- kgf/mm.sup.2 glycol rolidone diacrylate (24 g) (1.2 g) Exam- PI-31 2,4-Diethylthioxanthone (0.3 g)/ -- N-Methyl- 29 .mu.m 80% 6.5 400.degree. C. ple 75 (10 g) Isoamyl N,N-diethylaminobenzoate (0.5 g) 2-pyr- kgf/mm.sup.2 rolidone (24 g) Exam- PI-32 2,4-Diethyl thioxanthone (0.3 g)/ 1,6- N-Methyl- 30 .mu.m 85% 6.0 405.degree. C. ple 76 (10 g) Isoamyl N,N-diethylaminobenzoate (0.5 g) Hexane 2-pyr- kgf/mm.sup.2 diol di- rolidone acrylate (24 g) (1.6 g) Exam- PI-33 2,4-Diethylthioxanthone (0.3 g)/ 1,6- N-Methyl- 30 .mu.m 84% 6.1 410.degree. C. ple 77 (10 g) Isoamyl N,N-diethylaminobenzoate (0.5 g) Hexane 2-pyr- kgf/mm.sup.2 diol di- rolidone acrylate (25 g) (1.5 g) Exam- PI-14 2,6-Bis(p-diethylaminobenzylidene)-4-methyl-4- Tetra- N-Methyl- 30 .mu.m 85% 6.0 402.degree. C. ple 78 (10 g) azacyclohexanone (0.1 g)/ ethylene 2-pyr- kgf/mm.sup. 2 N-(p-cyanophenyl)-glycine (0.6 g) glycol rolidone diacrylate (24 g) (1.4 g) Exam- PI-49 2,6-Bis(p-diethylaminobenzylidene)-4-methyl-4- Tetra- N-Methyl- 29 .mu.m 86% 6.0 398.degree. C. ple 79 (10 g) azacyclohexanone (0.1 g)/ ethylene 2-pyr- kgf/mm.sup. 2 N-(p-cyanophenyl)-glycine (0.6 g) glycol rolidone dimeth- (24 g) acrylate (1.2 g) Exam- PI-50 2,6-Bis(p-diethylaminobenzylidene)-4-me thyl-4- Tetra- N-Methyl- 30 .mu.m 85% 5.5 400.degree. C. ple 80 (10 g) azacyclohexanone (0.1 g)/ ethylene 2-pyr- kgf/mm.sup.2 N-(p-cyanophen yl)-glycine (0.6 g) glycol rolidone dimeth- (24 g) acrylate (1.2 g) Exam- PI-50 2,4-Diethylthioxanthone (0.3 g)/ -- N-Methyl- 31 .mu.m 78% 5.6 402.degree. C. ple 81 (10 g) Ethyl N,N-diethylaminobenzoate (0.5 g) 2-pyr- kgf/mm.sup.2 rolidone (24 g) Exam- PI-51 2,4-Diethylthioxanthone (0.3 g)/ Tetra N-Methyl- 30 .mu.m 87% 6.2 405.degree. C. ple 82 (10 g) Ethyl N,N-diethylaminobenzoate (0.5 g) ethylene 2-pyr- kgf/mm.sup.2 glycol rolidone diacrylate (24 g) (1.0 g) Exam- PI-51 2,4-Diethylth ioxanthone (0.3 g)/ -- N-Methyl- 30 .mu.m 79% 5.7 410.degree. C. ple 83 (10 g) Ethyl N,N-diethylaminobenzoate (0.5 g) 2-pyr- kgf/mm.sup.2 rolidone (24 g) Exam- PI-34 Benzophenone (0.4 g)/ 1,6-Hexane- N-Methyl- 29 .mu.m 88% 6.2 396.degree. C. ple 84 (10 g) Michler's ketone (0.1 g) diol di- 2-pyr- kgf/mm.sup.2 acrylate rolidone (1.5 g) (24 g) Exam- PI-34 2,6-Bis(p-diethylaminobenzylidene)-4-methyl-4- -- N-methyl- 31 .mu.m 80% 5.6 415.degree. C. ple 85 (10 g) azacyclohexanone (0.1 g)/ 2-pyr- kgf/mm.sup.2 N-(p-cyanophenyl)-glycine (0.6 g) rolidone (24 g) Exam- PI-35 2,6-Bis(p-diethylaminobenzylidene)-4-meth yl-4- 1,6-Hexane- N-methyl- 28 .mu.m 85% 5.8 394.degree. C. ple 86 (10 g) azacyclohexanone (0.1 g)/ diol di- 2-pyr- kgf/mm.sup.2 N-(p-cyanop henyl)-glycine (0.6 g) acrylate rolidone (1.0 g) (24 g) Exam- PI-35 2,6-Bis(p-diethylaminobenzylidene)-4-methyl-4- Tetra- N-methyl- 30 .mu.m 85% 6.0 398.degree. C. ple 87 (10 g) azacyclohexanone (0.1 g)/ ethylene 2-pyr- kgf/mm.sup.2 N-(p-cyanophenyl)-glycine (0.6 g) glycol rolidone diacrylate (24 g) (0.9 g) Exam- PI-52 2,6-Bis(p-diethylami nobenzylidene)-4-methyl-4- Tetra- N-methyl- 34 .mu.m 80% 5.5 398.degree. C. ple 88 (10 g) azacyclohexanone (0.1 g)/ ethylene 2-pyr- kgf/mm.sup.2 N-(p-cyanophenylglycine (0.6 g) glycol rolidone diacrylate (24 g) (1.6 g) Exam- PI-52 2,6-Bis(p-diethylaminobenzylidene)-4-methyl-4- -- N-methyl- 32 .mu.m 84% 6.8 400.degree. C. ple 89 (10 g) azacyclohexanone (0.1 g)/ 2-pyr- kgf/mm.sup.2 N-(p-cyanophenylglycine (0.6 g) rolidone (24 g) Exam- PI-53 2,6-Bis(p-diethylaminobenzylidene)-4-meth yl-4- Tetra- N-methyl- 31 .mu.m 85% 5.6 395.degree. C. ple 90 (10 g) azacyclohexanone (0.1 g)/ ethylene 2-pyr- kgf/mm.sup.2 N-(p-cyanophen ylglycine (0.6 g) glycol rolidone diacrylate (24 g) (1.7 g) Exam- PI-53 2,4-Diethylthioxanthone (0.3 g)/ -- N-methyl- 30 .mu.m 80% 6.5 405.degree. C. ple 91 (10 g) Ethyl N,N-diethylaminobenzoate (0.5 g) 2-pyr- kgf/mm.sup.2 rolidone (25 g) Exam- PI-54 2,4-Diethylthio xanthone (0.3 g)/ Tetra- N-Methyl- 34 .mu.m 85% 5.9 400.degree. C. ple 92 (10 g) Ethyl N,N-diethylaminobenzoate (0.5 g) ethylene 2-pyr- kgf/mm.sup.2 glycol rolidone dimeth- (25 g) acrylate (1.5 g) Exam- PI-54 2,4-Diethylthioxanthone (0.3 g)/ -- N-Methyl- 27 .mu.m 78% 6.7 403.degree. C. ple 93 (10 g) Ethyl N,N-diethylaminobenzoate (0.5 g) 2-pyr- kgf/mm.sup.2 rolidone (24 g) Exam- PI-36 Benzophenone (0.4 g)/ Tetra- N-Methyl- 30 .mu.m 86% 5.6 398.degree. C. ple 94 (10 g) Michler's ketone (0.1 g) ethylene 2-pyr- kgf/mm.sup.2 glycol rolidone dimeth- (24 g) acrylate (1.6 g) Exam- PI-36 2,6-Bis(p-d iethylaminobenzylidene)-4-methyl-4- 1,6-Hexane- N-Methyl- 30 .mu.m 84% 5.4 394.degree. C. ple 95 (10 g) azacyclohexanone (0.1 g)/ diol di- 2-pyr- kgf/mm.sup.2 N-(p-cyanophenyl)-glycine (0.6 g) acrylate rolidone (1.5 g) (24 g) Exam- PI-37 2,6-Bis(p-diethylaminobenzylidene) -4-methyl-4- 1,6-Hexane- N-Methyl- 30 .mu.m 85% 6.0 403.degree. C. ple 96 (10 g) azacyclohexanone (0.1 g)/ diol di- 2-pyr- kgf/mm.sup.2 N-(p-cyanophenyl)-glycine (0.6 g) acrylate rolidone (1.5 g) (24 g) Exam- PI-37 2,6-Bis(p-diethylaminobenzylidene)-4-methyl-4- Tetra- N-Methyl- 28 .mu.m 87% 6.2 405.degree. C. ple 97 (10 g) azacyclohexanone (0.1 g)/ ethylene 2-pyr- kgf/mm.sup.2 N-(p-cyanophenyl)-glycine (0.6 g) glycol rolidone diacrylate (24 g) (1.6 g) Exam- PI-38 2,6-Bis(p- diethylaminobenzylidene)-4-methyl-4- Tetra- N-Methyl- 30 .mu.m 85% 6.0 400.degree. C. ple 98 (10 g) azacyclohexanone (0.1 g)/ ethylene 2-pyr- kgf/mm.sup.2 N-(p-cyanophenyl)-glycine (0.6 g) glycol rolidone diacrylate (24 g) (1.5 g) Thickness of coating Yield Weight Polymeri- film of loss zable un- before residual Develop- initiation Exam- Poly- saturated develop- film ment Tensile temper- ple mer Photoinitiator/Assis tant of photoinitiator compound ment thickness time strength ature Exam- PI-39 2,6-Bis(p-diethylaminobenzylidene)-4-methyl-4- Ethylene 28 .mu.m 80% 90 sec 5.9 392.degree. C. ple 99 (100) azacyclohexanone (0.18)/ glycol kgf/mm.sup.2 N-(p-Cyanophenyl)-glycine (1.8) dimeth- acrylate (7.1) Exam- PI-39 2,6-Bis(p-diethylaminobenzylidene)-4-met hyl-4- Tetra- 28 .mu.m 78% 90 sec 5.8 395.degree. C. ple 100 (100) oxocyclohexanone (0.18)/ ethylene kgf/mm.sup.2 N-(p-Chlorophenyl)-gl ycine (1.8) glycol dimeth- acrylate (7.1) Exam- PI-30 2,6-Bis(p- diethylaminobenzylidene)-4-methyl-4- 2,2-Bis- 30 .mu.m 82% 100 sec 6.3 402.degree. C. ple 101 (100) oxocyclohexanone (0.18)/ (4-acryl- kgf/mm.sup.2 N-Ethyl-N-(p-chlorophenyl)-glycine (1.8) oxypenta- ethoxy- phenyl)- propane (7.1) Exam- PI-39 2,6-Bis(p-dimethyl-am inobenzylidene) Tris(2- 29 .mu.m 79% 95 sec 6.4 408.degree. C. ple 102 (100) cyclopentanone (0.18)/ acryloyl- kgf/mm.sup.2 N-(p-Cyanophenyl )-glycine (1.8) ethyl)- isocyanu- rate (7.1) Exam- PI-40 2,6-Bis(p-dimethylaminobenzylidene) Ethylene 30 .mu.m 83% 115 sec 6.0 396.degree. C. ple 103 (100) cyclopentanone (0.18)/ glycol kgf/mm.sup.2 N-(p-Cyanophenyl)-glycine (1.8) dimeth- acrylate (7.1) Exam- PI-40 2,6-Bis(p-diethylaminobenzylidene)-4- Tetra- 29 .mu.m 82% 100 sec 6.3 395.degree. C. ple 104 (100) oxocyclohexanone (0.18)/ ethylene kgf/mm.sup.2 N-Ethyl-N-(p-chlorophenyl)-glycine (1.8) glycol dimeth- acrylate (7.1) Exam- PI-40 2,6-Bis(p-diethylaminobenzyliden e)-4-methyl-4- Tris(2- 28 .mu.m 84% 90 sec 6.7 405.degree. C. ple 105 (100) azacyclohexanone (0.18)/ acryloyl- kgf/mm.sup.2 N-(p-Cyanophen yl)-glycine (1.8) ethyl)- isocyanu- rate (7.1) Exam- PI-40 2,6-Bis(p-dimethylaminobenzylidene)- 2,2-Bis(4- 30 .mu.m 85% 110 sec 6.6 410.degree. C. ple 106 (100) cyclopentanone (0.18)/ acryloxy- kgf/mm.sup.2 N-Ethyl-N-(p-chlorophenyl)-glycine (1.8) penta- ethoxy- phenyl)- propane (7.1) Exam- PI-41 2,6-Bis(p-diethylamin obenzylidene)-4-methyl-4- Ethylene 28 .mu.m 82% 95 sec 6.0 390.degree. C. ple 107 (100) azacyclohexanone (0.18)/ glycol kgf/mm.sup.2 N-(p-Cyanophenyl)-glycine (1.8) dimeth- acrylate (7.1) Exam- PI-41 2,6-Bis(p-diethylaminobenzylidene)-4-methyl-4- Diethylene 28 .mu.m 80% 95 sec 6.0 392.degree. C. ple 108 (100) azacyclohexanone (0.18)/ ethylene kgf/mm.sup.2 N-(p-cyclorophenyl)-glycine (1.8) glycol dimeth- acrylate (7.1) Exam- PI-41 2,6-Bis(p-diethylaminobenzyliden e)-4-methyl-4- 2,2-Bis- 29 .mu.m 83% 95 sec 6.2 400.degree. C. ple 109 (100) azacyclohexanone (0.18)/ (4-acryl- kgf/mm.sup.2 N-(p-cycloroph enyl)-glycine (1.8) oxypenta- ethoxy- phenyl)- propane (7.1) Exam- PI-41 2,6-Bis(p-dimethylaminobenzylidene)- Tris(2- 27 .mu.m 80% 90 sec 6.3 405.degree. C. ple 110 (100) cyclopentanone (0.18)/ acryloyl- kgf/mm.sup.2 N-Ethyl-N-(p-cyanophenyl)-glycine (1.8) ethyl) isocyanu- rate (7.1) Exam- PI-42 2,6-Bis(p-dimethylaminobenzylidene )- Ethylene 29 .mu.m 84% 100 sec 6.1 395.degree. C. ple 111 (100) cyclopentanone (0.18)/ glycol kgf/mm.sup.2 N-(p-cyanophenyl)-glycine (1.8) dimeth- acrylate (7.1) Exam- PI-42 2,6-Bis(p-dimethylaminobe nzylidene)-4- Diethylene 28 .mu.m 85% 90 sec 6.2 398.degree. C. ple 112 (100) phenylcyclohexanone (0.18)/ ethylene kgf/mm.sup.2 N-Ethyl-N-(p -chlorophenyl)-glycine (1.8) glycol dimeth- acrylate (7.1) Exam- PI-42 2,6-Bis(p-diethylaminobenzylidene)-4-methyl- Tris(2- 28 .mu. m 86% 95 sec 6.5 410.degree. C. ple 113 (100) azacyclohexanone (0.18)/ acryloyl- kgf/mm.sup.2 N-(p-cyanophenyl)-glycine (1.8) ethyl) isocyanu- rate (7.1) Exam- PI-42 2,6-Bis(p-dimethylaminobenzylidene )- 2,2-Bis- 30 .mu.m 85% 105 sec 6.4 406.degree. C. ple 114 (100) cyclopentanone (0.18)/ (4-acryl- kgf/mm.sup.2 N-Ethyl-N-(p-chlorophe nyl)-glycine (1.8) oxypenta- ethoxy- phenyl)- propane (the unit of the figures in parentheses: gram) Note: ##STR61##
TABLE 3__________________________________________________________________________ Photoinitiator/ Polymerizable Thickness of Yield of Weight lossComp. Assistant of unsaturated coating film residual film Tensile initiationExample Polymer photoinitiator compound before development thickness strength temperature__________________________________________________________________________Comp. PI-59 2,4-Diethylthioxanthone A-BPE-10 32 .mu.m 48% 8.1 kgf/mm.sup.2 405.degree. C.Example 1 (100 g) (0.6 g)/ (4.5 g) Ethyl p-dimethylamino- benzoate (0.9 g)Comp. PI-59 2,4-Diethylthioxanthone -- 30 .mu.m 38% 7.8 kgf/mm.sup.2 413.degree. C.Example 2 (100 g) (0.6 g)/ Ethyl p-dimethylamino- benzoate (0.9 g)Comp. PI-59 2,6-Bis(p-diethylamino- Ethylene glycol 33 .mu.m 50% 8.0 kgf/mm.sup.2 410.degree. C.Example 3 (100 g) benzylidene)-4-methyl- diacrylate 4-azacyclohexanone (4.5 g) (0.15 g)/ N-Phenylglycine (1.5 g)Comp. PI-59 2,4-Diethylthio- Ethylene glycol 31 .mu.m 56% 7.9 kgf/mm.sup.2 410.degree. C.Example 4 (100 g) xanthone (0.6 g)/ diacrylate Ethyl p-dimethylamino- (4.5 g) benzoate (0.9 g)Comp. PI-59 2,6-Bis(p-diethylamino -- 32 .mu.m 48% 7.7 kgf/mm.sup.2 408.degree. C.Example 5 (100 g) benzylidene)-4-methyl- 4-azacyclohexanone (0.15 g)/ N-(p-Cyano-phenyl)- glycine (1.5 g)Comp. PI-59 2,6-Bis(p-diethylamino Ethylene glycol 33 .mu.m 50% 8.0 kgf/mm.sup.2 410.degree. C.Example 6 (100 g) benzylidene)-4-methyl- diacrylate 4-azacyclohexanone (4.5 g) (0.15 g)/ N-(p-Cyano-phenyl)- glycine (1.5 g)__________________________________________________________________________ Thickness of Yield of Photoinitiator/ Polymerizable coating film residual film Weight lossComp. Assistant of unsaturated before thickness after Tensile initiationExample Polymer photoinitiator compound Solvent development development strength temperature__________________________________________________________________________Comp. PI-55 2,6-Bis(p-diethyl- Tetraethylene N-Methyl-2- 30 .mu.m 55% 7.0 415.degree. C.Example (10 g) aminobenzylidene)- glycol di- pyrrolidone kgf/mm.sup.28 4-methyl-4-azacyclo- methacrylate (34 g) hexanone (0.1 g)/ (1.5 g) N-(p-Cyano- phenyl)glycine (0.6 g)Comp. PI-56 2,6-Bis(p-diethyl- Tetraethylene N-Methyl-2- 28 .mu.m 52% 7.5 409.degree. C.Example (10 g) aminobenzylidene)- glycol di- pyrrolidone kgf/mm.sup.29 4-methyl-4-azacyclo- methacrylate (35 g) hexanone (0.1 g)/ (1.5 g) N-(p-Cyano- phenyl)glycine (0.6 g)Comp. PI-57 2,4-Diethyl- 1,6-Hexanediol N-Methyl-2- 28 .mu.m 48% 6.8 410.degree. C.Example (10 g) thioxanthone (0.3 g)/ diacrylate pyrrolidone kgf/mm.sup.210 Ethyl N,N- (1.6 g) (36 g) diethylaminobenzoate (0.5 g)Comp. PI-58 2,4-Diethyl- 1,6-Hexanediol N-Methyl-2- 28 .mu.m 48% 7.8 420.degree. C.Example (10 g) thioxanthone (0.3 g)/ diacrylate pyrrolidone kgf/mm.sup.211 Ethyl N,N- (1.6 g) (35 g) diethylaminobenzoate (0.5 g)__________________________________________________________________________ Thickness of Yield of Photoinitiator/ Polymerizable coating film residual Weight lossComp. Assistant of unsaturated before film Develop- Tensile initiationExample Polymer photoinitiator compound development thickness ment time strength temperature__________________________________________________________________________Comp. PI-59 2,6-Bis(p-dimethylamino- Ethylene glycol 28 .mu.m 45% 215 sec 7.8 405.degree. C.Example 12 (100) benzylidene)-4-methyl-4- dimethacrylate kgf/mm.sup.2 azacyclohexanone (0.18)/ (7.1) N-Ethyl-N-(p-chloro- phenyl)glycine (1.8)Comp. PI-59 2,6-Bis(p-diethylamino- Diethylene glycol 29 .mu.m 43% 210 sec 7.5 400.degree. C.Example 13 (100) benzylidene)-4-methyl-4- dimethacrylate kgf/mm.sup.2 azacyclohexanone (0.18)/ (7.1) N-Ethyl-N-(p-chloro- phenyl)glycine (1.8)Comp. PI-59 2,6-Bis(p-dimethylamino- 2,2-Bis(4- 28 .mu.m 48% 215 sec 7.6 410.degree. C.Example 14 (100) benzylidene)- acryloxypenta- kgf/mm.sup.2 cyclopentanone (0.18)/ ethoxyphenyl)- N-Ethyl-N-(p-chloro- propane (7.1) phenyl)glycine (1.8)__________________________________________________________________________ (the unit of the figures in parentheses: gram) Note: ##STR62##

Number	Date	Country
63-318813	Dec 1988	JPX
63-318814	Dec 1988	JPX
1-099168	Apr 1989	JPX
1-134383	May 1989	JPX

Number	Name	Date	Kind
4416973	Goff	Nov 1983
4654415	Ahne et al.	Mar 1987

Photosensitive resin composition and photosensitive element using the same

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