JPS63163452A - Image formation - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an imaging method useful in the manufacture of printing plates and printed circuits.

In conventional positive imaging methods, a solid layer of positive photoresist is formed by applying a solution of the photoresist in a volatile organic solvent to a support and then evaporating the solvent. The solid photoresist, such as a phenolic novolak resin containing a quinonediazide moiety or a mixture of a coating resin and a quinonediazide compound, is then exposed to actinic radiation in a predetermined pattern, usually through an imagewise transparency;
This causes the areas exposed to the radiation to become soluble in the developer, while the areas shielded from the radiation remain essentially incorrigible. The exposed areas are removed with a solvent developer, usually an alkaline aqueous solution, which dissolves the exposed areas but does not dissolve the unexposed areas during the period of processing, leaving a positive image.

There is a need for a method for forming positive photoresists that are solid, non-tacky, and amenable to imaging irradiation without the need to evaporate the 1-total organic solvent. Such a method would avoid the use of solvents which pose toxicity and flammability problems and which require expense to recover. 1. It would also be easier to manufacture on a continuous basis a support coated with a photoresist that is easy to imagewise expose, such as a coated copper-coated laminate.

European Patent Publication AO 155231 proposes forming a positive image by imagewise exposing a solid positive photoresist layer formed by electrodeposition. Although the requirements of this process include the use of very small amounts of organic solvents, it requires the use of materials with salt-forming groups, which limits its applicability. What is needed is a method that does not require evaporation of organic solvents and has wide applicability.

Accordingly, the present invention provides: (1) a support comprising: a cationically polymerizable or free radically polymerizable resin; a radiation-activated polymerization initiator for (BI CA); ) applying a layer of a liquid composition containing a component that is soluble in radiation; (4) radiation having a wavelength that activates said CB) but substantially activates said (C); A/31
is applied to the composition, followed by heating if desired,
1ii) polymerizing the Q so as to solidify a layer of the liquid composition; 1ii) said solidifying such that the solidified layer is more soluble in developer in Kashima areas than in unfinished areas; exposing the treated layer in a predetermined pattern to radiation having a wavelength that activates said component (C), different from the radiation used in step (n), and (iv) developing said IT region. The object of the present invention is to provide a method for forming an image, which is characterized in that the image is removed by treatment with a chemical agent.

The expression ``applying radiation in a predetermined pattern'' refers to exposing the radiation through a transparency having an image consisting of opaque and transparent areas, and exposing radiation in a predetermined manner, e.g., as directed by a computer, to form an image. Both include applying a beam of actinic radiation that moves in a pattern. The liquid composition used in the method of the invention comprises @a radiation-activated polymerization initiator and a substance having at least one polymerizable component (5) and at least one (activating Bl). mixtures with substances having a possible component (C) that becomes soluble with radiation activated by radiation of a different wavelength than the 5
) and (B) a difunctional substance having a radiation-soluble component (Q) that is activated by radiation of a different wavelength than that which activates the component, or ■ at least one polymerizable (5) and/or at least one radiation-soluble component (at least one of the above-mentioned 2 with a substance having Q')
It can contain functional substances.

Component (C) can be activated with short wavelength radiation (as well as activating Bl). In this case, the exposure in step (1) and the exposure in step (in) both involve ultraviolet light. Alternatively, the first exposure may be carried out using radiation in the visible spectrum and the second exposure using ultraviolet radiation.

Alternatively, (C) can be activated with radiation of a longer wavelength than that which activates @. Like this stage (Ol)
can be carried out by the use of radiation having a shorter or longer wavelength than the radiation used in step (11).

The polymerization initiator (8 is the component (C
) can also absorb long or short wavelength radiation. (When Bl absorbs at longer wavelengths, the component (C
) preferably does not absorb radiation at wavelengths exceeding 500 nm. Free radically polymerized components suitable for use as component (5), i.e. groups and combinations of groups, are well known and include ethylenically unsaturated groups or mixtures of ethylenically unsaturated and thiol groups. can do.

Suitable substances having a component of ethylenically unsaturated groups include styrene, substituted styrenes, vinyl substituted aromatics such as α-methylstyrene, 4-methylstyrene and 4-bromostyrene, vinyl acetate. vinyl esters such as diallyl maleate and dimethallyl fumarate, vinyl heterocycles such as 2-16-0 or 4-vinylpyridine and 2- or 5-vinylpyrrolidone.

Preferred ethylenically unsaturated substances are esters of ethylenically unsaturated monocarboxylic acids, represented by the following formula (%) (wherein R1 is hydrogen, chlorine or bromine or an alkyl group having 1 to 4 carbon atoms, particularly A hydrogen atom or a methyl group is preferred.

Preferred such esters are acrylates and 2-substituted acrylates of monohydric alcohols such as 2-methoxyethanol, 2-chloroethanol, furfuryl alcohol, glycol, and hiscyclohexanol, and butanediol, pentaerythritol, Full or partial esters of polyhydric alcohols such as dipentaerythritol, tri- or tetraethylene glycol, trimethylolpropane, and glycerol. Also suitable are esters formed by the reaction of alkylene oxides, especially ethylene oxide or propylene oxide, with acrylic acid, typically 2-hydroxyethyl and 2-hydroxyglobyl acrylates and methacrylates. Compounds containing one or more Grindyl groups, especially one
Esters formed by reaction of hydrohydric or polyhydric alcohols or N-grindylhydantoin with acrylic or methacrylic acid may also be used. Other suitable compounds are formed by the reaction of dieboxides with adducts of hydroxyalkyl acrylates or methacrylates with saturated or unsaturated dicarboxylic anhydrides, such as succinic, maleic or phthalic anhydrides. It's ester.

Representative such compounds include poly(2-hydroxy-6-acryloyloxyprobyl) ether of 1,4-bis(2-hydroquine-3-acryloyloxyprobyl)butane, bisphenol or phenol formaldehyde novolak, 2 .2-bis(4-(2-hydroxy-5-(2-acryloyloxyneethquin)succinyloquinebroboxy)phenyl)furopane, neopentyl diacrylate, trimethylolgloban trisacrylate, pentaerythritol, tetra acrylate, bis(2-hydroxy-6-acryloyloxyprobyl) adipate and their corresponding methacrylates.

Lylic acid, 1-(2-hydroxy-3-acryloyloxypropoxy)-butane, -octane and heattecan, 2
- monoacrylates such as hydroxy-6-acryloyl oxidipropyl propionate, 6-phenoquine-2-hydroquine propyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate and their corresponding methacrylates; It is monomethacrylate.

Polyfunctional acrylates and methacrylates are generally used together with monofunctional acrylates and methacrylates.

The polyene mixed with polythiol and used to supply component (A) has the following formula % formula % (in (2) and (2), the groups R2 may be the same or different and contain hydrogen, fluorine and chlorine atoms. and furyl, chenyl, pyridyl, phenyl, substituted phenyl, benzyl and substituted benzyl, alkyl, substituted alkyl,
selected from alkokenes and substituted alkokenes having 1 to 9 carbon atoms, cycloalkyl and substituted cycloalkyl groups having 3 to 8 carbon atoms, in which the substituents are chlorine and fluorine atoms, acetoxy, nitro, acetamide, phenyl, benzyl, alkyl, alkoxy and cycloalkyl groups, r is an integer from 1 to 9, and X is -NR2-, -0- or -84-. ) includes those having at least two groups represented by. This polyene usually has a molecular weight of 50 to 5000,
Contains two or more ethylene bonds that have the ability to participate in free radical polymerization reactions. Preferred polyenes include the reaction product of 1 mol of tolylene diincyanate and 2 mol of dialkenyl ether of trimethylolpropane, the reaction product of 1 mol of polymeric diincyanate and 2 mol of allyl alcohol, 1 mol reaction product of polyethylene glycol with 2 moles of tolylene-2,4-diincyanate and 2 moles of allyl alcohol, polyimblene, polybutadiene and unsaturated polymers in which the unsaturation occurs primarily within the backbone of the molecule. , a compound having a reactive carbon-carbon unsaturated bond conjugated with an adjacent unsaturated group, e.g.
polyethylene ether glycol diacrylate with a molecular weight of 50, polytetramethylene ether glycol dimethacrylate with a molecular weight of about 1175, triacrylate of the reaction product of trimethylolpropane with 20 moles of ethylene oxide, and polyepoxide with an amine, Includes reaction products with alcohols, thioalcohols or acids with aliphatic unsaturation, such as the reaction products of bisphenol A diglycidyl ether with triamine or diallylamine. Particularly preferred polyenes are phenols, particularly bisphenols, substituted with two or more allyl or methallyl groups.

Polythiols that can be mixed with these polyenes and used as moiety (8) are of the general formula % (wherein R3 is a polyvalent organic compound containing no reactive carbon-carbon unsaturation). (t represents 2 or more).

Preferably, the organic group R3 is an aliphatic chain having 2 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkarylene group having 7 to 16 carbon atoms, a cyclocarbon group having 5 to 10 carbon atoms. Alkylene group or 6 carbon atoms
to 16 cycloalkylalkylene groups, any of which may contain an oxygen atom or an ester group in the substituted cycloalkylene chain. Examples of particularly preferred polythiols are ethylene glycol bis(thioglycolate), ethylene glycol bis(β-mercaptopropionate), and <fo-yab. Puff )-1 (Gaogarime vomit), Trimethylolpropane, Tris (β
-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), pentaerythritol tetrakis (β-mercaptopropionate) and thioglycolate, polypropylene ether glycol bis(β-mercaptopropionate) and glycerol. β-mercaptopropionate and 3-mercapto-2-hydroxyglobyl ether of polyoxypropylene triolno-3-mercapto-2-hydroxyglobyl ether of polyoquine alkylene glycols and triols.

The molar ratio of ene groups:thiol groups is chosen to give a solid product on exposure to radiation, preferably in the range 1:0.5-2.

Suitable polymerization initiators for use when (5) is a free radically polymerizable component will be sensitive to visible or ultraviolet light.

Such initiators are known and include benzoin ether,
Acilloin ethers, halokenated alkyl or aryl derivatives, aromatic carbonyl derivatives, metallocenes, mixtures of Group 1 VA organometallic compounds and photoreductive dyes, quinones and aliphatic amines with a hydrogen atom bonded to an aliphatic alpha carbon atom; a mixture of, optionally an amine as described above,
Includes 3-ketocoumarins, acylphosphine oquindos, aliphatic dicarbonyl compounds mixed with metal carbonyls, and mixtures of photoreductive dyes and reducing agents. Preferred radiation-activated catalysts (13) are tertiary amines and camphorquinones having a hydrogen atom attached to an aliphatic alpha carbon atom, such as bis(4-dimethylamino)benzophenone and triethanolamine, biacetyl, Dimangane decacarbonyl, benzyl dimethyl ketal, inbutyl benzoin ether, 2゜2.2-)sacrolo 4'-tert-butylacetophenone, Shedquin acetophenone;
Coumarins having a carbocyclic or heteroaromatic ketone group in the 3-position, such as 3-benzoyl-7-medoxycoumarin or 3-(4-7anobenzoyl)-5,7-
Diproboxyzocoumarin; a photoreducible dye, typically methylene blue or rose bengal and a stannane such as trimethylbenzylstannane, tributylbenzylstannane, tributyl-4-methylbenzylstannane or dibutyldibenzylstannane. a mixture of an electron donor such as sodium benzenesulfinate or benzenesulfinic acid and a photoreducible dye;
and bis(pi(pimethylclopentadienyl)his(
titanium metallocenes such as sigma hexyloxytetrafluorophenyl) titanium (rV).

The compounds described, in which the initiator (B) is a mixture of a metallocene or a Group IA organometallic compound and a photoreducible dye, are new in themselves. (5) a component polymerizable by free radicals; (B) a metallocene or
Consisting of a mixture of group A organometallic compounds and photoreducible dyes (5
) and a radiation-activated polymerization initiator for (C
) It may also be a radiation-solubilized component, said component (C) used in the described method being activatable with radiation at a wavelength different from that at which said (B) is activatable. The present invention provides new compositions suitable for

Preferred metallocenes used in said new compositions are of the following formula: (wherein each group R4 is independently selected from the group R<4, optionally substituted ncrobentacyenyl and L< is selected from indenyl groups, or they are taken together) C2 -C12 alkylidene groups, cycloalkylidene groups having 5 -7 carbon atoms in the ring, -3i (R7), - or -3n (R1), optionally substituted (XI represents a methylene group, an ethylene group, or a 1°3-propylene group), and R5 represents a 6-membered aromatic carbon R or a 5- or 6-membered aromatic heterocycle; In the ring, at least one of the two positions ortho to the metal-carbon bond is substituted with a fluorine atom, or the ring may be further substituted depending on the case, or R5 and R6 are a group -Q-Y- Q- represents a 5- or id'6 negative aromatic carbocycle or aromatic heterocycle in which the two bonds are ortho to the Q-Y bond, and whereas each meta position is substituted by a fluorine atom, the group Q is optionally further substituted, yFi methylene group, alkylidene group having 2 up to 12 carbon atoms, having 5 to 7 carbon atoms in the ring Cycloalkylkylidene group, direct bond, group N)1,7, oxygen atom or sulfur atom, or group -5O2-1 group -C
O-1 group -3i(R))2-, R6 is an optionally substituted alkynyl group or phenylalkynyl group, an azide group or a 7-ano group, or -5
a group represented by i(R7)2- or -3n(R')2-, or has the same meaning as the group R5, and R7 is an alkyl group having 1 to 12 carbon atoms, 5 to 12 carbon atoms; cycloalkyl group, aryl group having 6 to 16 carbon atoms, or aralkyl group having 7 to 16 carbon atoms).

Preferably, the radicals R,4 are identical. Examples of preferred substituents for R4 are straight-chain or branched alkyl groups,
Alkoxy groups and preferably alkenyl groups having up to 18 carbon atoms, particularly up to 12 carbon atoms, most preferably up to 6, such as methyl, ethyl, propyl, inopropyl, n-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group,
dodecyl, tetradecyl, hexadecyl, octadecyl and the corresponding alkenyl and hyalkoxy groups; cycloalkyl and preferably cycloalkenyl groups containing 5 to 8 carbon atoms in the ring, e.g. evacyclopentyl, cyclohexyl, cyclohebutyl, methylcyclobentyl and methylcyclohexyl; preferably C6 -C16 aryl and preferably C7 -C16 aralkyl, such as phenyl, naphthyl, piphenyl, benzyl and phenylethyl groups; nitro groups, halogen atoms, preferably fluorine, chlorine and bromine atoms, and also amine groups, straight-chain or branched, having 1 to 12 carbon atoms
The alkyl groups, preferably having 1 to 1 carbon atoms, but especially the methyl or ethyl groups or the phenyl and benzyl groups, such amino groups can also be quaternized, particularly preferably having 1 to 12 carbon atoms. Straight chain or branched halogenated alkyl groups, preferably halogenated methyl groups or halogenated ethyl groups; straight chain or branched chain aminoalkyl groups, preferably especially halogenated alkyl groups, quaternized More preferably, a tertiary aminoalkyl group and an alkylene group in the aminoalkyl group are straight or branched and have 1 carbon atom.
2 is preferred, and 1 to 6 carbon atoms are most preferred;
and especially preferably those containing α-branched C1 -C12 alkyl groups.

The radical R4 may contain substituents having 1 to 5 carbon atoms, but preferably has one substituent. Both substituents R4 are preferably cyclopentadienyl O' groups or methylcyclopentadienyl O groups.

Preferably, the alkylidene radicals Xi and Y have 2 to 6 carbon atoms. Examples of alkylidene groups and cycloalkylidene groups XI and Y include ethylidene groups, 2.2-
They are a glopylidene group, a butylidene group, a hexylidene group, a phenylmethylene group, a diphenyl-methylene group, a cyclopentylidene group, and a cyclohequinylidene group. Most preferably, XI is a methylylene group. As an alkyl group, R7 preferably has 1 to 6 carbon atoms, for example methyl, ethyl, propyl, butyl or hekynyl; H as an chloroalkyl group, ? Preferably, the aryl group is a phenyl group; and the aralkyl group is preferably a benzyl group.

Preferably, R5 is substituted with fluorine atoms at both ortho positions.

R6 as an aromatic carbocyclic ring and a fluorine-substituted ring is an indene group, an indane group, a fluorene group, a naphthalene group and preferably a phenyl group, Example t-4, 6-difluoroinden-5-yl group, 5.7 -difluoroinden-6-yl group, 2,4-difluorofluorene-3
-yl group, 1,3-difluoronaphth-2-yl group and 11, (z, 6-cyfluorophen-1-yl group).

As a 5-membered heteroaromatic ring, l(, 5 preferably has one heteroatom, and as a 6-membered ring it preferably has 1 or 2 heteroatoms. With 2 fluorine atoms Examples of such substituted rings are 2,4-difluoropyrrol-6-yl, 2,4-difluoroflu-3-yl, 2,4-difluorothiophen-3-yl M,2,
They are 4-difluoropyrid-3-yl group, 3.5-difluoropyrid-4-yl group and 4.6-cyfluoropyrimid-5-yl group.

The group represented by the formula -Q-Y-Q- represented by R5 and R6 together is the following formula: (In the formula, E represents 10-, -S- or -NH-. Y is a methylene group , ethylidene group, 2.2=propylidene group, direct bond or 10- is preferred).

The group R5 and the group Q in the group -Q-Y-Q- can be partially or completely substituted by further groups. Preferred groups are, for example, straight-chain or branched alkyl or alkoxy groups, each preferably having 1 to 18 carbon atoms, most preferably having 1 to 6 carbon atoms, such as methyl, ethyl, globyl, butyl. , pentyl group, hekynyl group and the corresponding alkoxy group, preferably methyl group, methoxy group, hekynluo group; cycloalkyl group preferably having 5 to 6 carbon atoms in the ring, preferably 1 carbon atom Aryl groups of 6 to 16 and preferably aralkyl groups of ei 7 to 16 carbon atoms, such as ncrobentyl, nclohexol, phenyl or benzyl: hydroxyl, carboxyl, cyano, fluorine, chlorine or halogen atoms such as bromine atoms and amino groups, such as methyl chloride, methyl bromide, or halogenated alkyl groups such as methyl iodide, such as methylamine, ethylamino, dimethylamino, diethylamino, A tertiary amino group which may be quaternized with a pyrrolidyl group, piperidyl group, piperazyl group, morpholyl group, or N-methylpiperazyl group is preferred. ; an alkoxycarbonyl group preferably having 1 to 18 carbon atoms, most preferably having 1 to 6 carbon atoms in the alkoxy moiety;
an aminocarbonyl group having one or two C1-C12 alkyl groups in the amine group, or multicyclic amines, such as pyrrolidine, piperidine, piperazine, N-methylbiperazine and morpholine groups; Aminocarbonyl group; preferably contains an aminoalkyl group, especially an alkyl group having 1 to 6 carbon atoms, and a tertiary aminoalkyl group which may be quaternized with an alkyl halide, most preferably an alkyl group having 1 to 6 carbon atoms; Tertiary aminoalkyl groups which may be substituted by 6 alkyl groups, such as dimethylaminomethyl group and trimethylammoniummethyl iodide.

As an alkynyl group, R6 is, for example, a 2-butynyl group and preferably a propargyl group.

Examples of substituents for R6 as phenylalkynyl groups include halogen atoms such as fluorine, chlorine, and bromine, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and carboxyl groups. , hydroxyl group and cyano group. R6 preferably has the same meaning as 几5.

In a preferred embodiment of the invention, R5 and 1 in formula V (16 is unsubstituted or substituted 2,6-difluorophen-1-yl or R5 and 6 together are of the formula: and in particular a direct bond, the group -CH2
- or a group -0-).

A preferred group of metallocenes of formula V is a π-cyclopentagenyl group in which each R4 is substituted by a C1 -C4 alkyl group, preferably a methyl group, and each R5 and R5 is of the formula: In the formula, Ql, Q2 and Q3 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a tertiary amino group, preferably a morpholino group, or an alkoxy group, preferably a methoxy group or a hekylene group. ) It consists of a compound that is a group represented by An amino group or an alkoxy group is a free bond.
), it is preferable to add it at the distal position. Preferred subgroups include R4 representing a π-methylchlorpentadienyl mosyl group or a π-7 clobentadienyl group, and R5 and R6 each representing a hydrogen atom, a fluorine atom, a salt atom, or a hydrogen atom, and a hydrogen atom, a fluorine atom, a salt atom, or an industrial atom. , and Ql is a formula ■ representing a hydrogen atom, a fluorine atom, or an alkoxy group.
It consists of a metallocene represented by the formula (■) representing the group a.

Preferably, Q'' and Q3 each independently represent a hydrogen atom or a fluorine atom, and Ql represents a fluorine atom or a hekynluoki7 group.

Compounds of formula V and methods for their preparation are described in US Pat. No. 4,590,287.

The preferable Group ⅠA organometallic compound used in the new composition has the following formula ①.

(In the formula, R8 represents an alkyl group having 1 or 4 carbon atoms, or an alkenyl group or alkynyl group having 2 to 4 carbon atoms, and R9 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 carbon atom. 4 represents an alkyl group or an alkoxy group.

) is an organostannane represented by

Preferred compounds represented by the formula (3) are those in which R8 represents an alkyl group having 1 to 4 carbon atoms, and R9 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

These organostannanes were prepared by Grignard coupling reaction between trialkyltin halide and pendylmagneneum halide in an inert solvent, followed by filtration.
It is produced by washing with water and distilling the product.

Preferred photoreducible dyes for use with these organostannanes are methylene blue and rose bengal.

Substances with cationically polymerizable components suitable for use as component (5) of liquid compositions are known and include sb, cyclic ethers such as oxetane or tetrahydrofuran; cyclic esters such as lactones; or episulfides such as ethylene sulfide. It may also be a cationically polymerizable heterocyclic compound such as. Preferable (5)
id, 1,2-epoxide, vinyl ether or mixtures thereof. Suitable 1,2-epoxides include ethylene oxide, propylene oxide and shrimp chlorohydrin. Preferred 1,2-epoxides are glycidyl esters of monohydric alcohols or phenols, such as n-butyl glycidyl ether, inoctyl cricidyl ether, phenyl cricidyl ether and hycresyl glycidyl ether; alpha-pinene oxide. Epoxy resins such as monoepoxides and 3,4-epoxycyclohexylmethyl-3/,41-epoxycyclohexanecarboxylate and their 6.
Cycloaliphatic epoxides, including 6'-dimethyl derivatives, and glycidyl esters, especially of monocarboxylic acids such as propionic acid, cyclohexanecarboxylic acid, and benzoic acid.

Suitable vinyl ethers include cyclic vinyl ethers containing a dihydropyran component and preferably vinyloxyne alkyl ethers of alcohols and phenols.

(5) A wide range of polymerization initiators can be used. For example, the initiator for the cationically polymerizable component (5) is at least one of the following formula (■:[R1o]+an-
CLTm]-q('lID [wherein L represents a divalent to heptavalent metal or nonmetal, T represents a halogen atom, or one of the T represents a hydroxyl group, and q represents 1 to 3. represents an integer, m represents an integer corresponding to the valence of L + q, a represents 1 or 2, n represents an integer from 1 to 3, and RIO represents the following formula: % formula % (wherein, Ar and Ar' represent a substituted or unsubstituted aromatic group; (11) the following formula: %formula%)) (wherein G represents an arene or dianium group,
Z is selected from titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, niobium, molybdenum, ruthenium, rhodium, ) (radium, silver, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold) - represents an atom of a transition element of the block;
and X represents a positive integer such that Z is a closed shell electron configuration. ); (fil) aromatic diazonium ion; (jy) ((13,11)(R1
2M) a) + an (wherein a represents 1 or 2, n represents an integer of 1 to 3, M times 1 from Groups 1yb to 2b, Group 1 or Group 2b of the periodic table) value or 3
R11 represents a π-arene, and 1%12 represents a π-arene or an anion of a π-arene. ): (V) aromatic sulfonium ion; or (V)
It may also be a compound represented by an aromatic sulfoquinium ion (vi represents an ion selected from iodosyl ions).

When RIO is an iodonium salt, the initiator has the following formula CI
'm: CArh -1-Ar'i 3"3 [L', ['m)
(k-1) (Vln) (wherein Ar represents a monovalent aromatic group, Ar' represents a divalent aromatic group, h represents 0 or 2, and 1 is 0 or 11r) , represents, the sum of h + i is 2, or the valence of ■ represents -1 for j-, the valence of L is 1, and k represents an integer greater than 1 and up to 8, and T and m have the meanings defined above.

The groups included in Ar are the same or different, preferably 1 to 4 monovalent alkoxy groups having 1 to 8 carbon atoms, alkyl groups having 1 to 8 carbon atoms, nitro groups, or chlorine atoms. It can be an allyl group or an aromatic heterocyclic group having 5 to 20 carbon atoms which can be substituted with a group. Ar ld % is a phenyl group, a chlorophenyl group, a nitrophenyl group, a methquinphenyl group, or a pyridyl group. Groups included in Ar' are represented by the following formula: (wherein n represents 1 to 6, preferably 1 or 2).

), preferably an arylene group having 12 carbon atoms
to 20 dinuclear groups.

Iodonium salts are used in combination with dye sensitizers (when Bl is activated by radiation in the visible spectrum).

Dyes that can be used in combination with the above-described aryliodonium salts in the practice of the present invention are cationic dyes, such as the Kirk-Osmer Encyclopedia (Kirk-O
thmer Encyclopedia), Part 2 [1
969, John Wiley & Sons
Wiley and 5ons), New York, Vol. 20, pp. 194-7. Some examples of cationic dyes that can be used are: Acridine Orange; C, 1,46005 Acridine Yellow; C1I, 46035 Phosphine R: C,
I, 46045 Benzofurapine; C0■, 46065
'Cetoflavin T: C0I, 49005.

In addition to the above, basic dyes may also be used.

Some of these basic dyes are described in the above-mentioned Kirkoosmer Encyclopedia, Volume 7, pages 532-4, and include: hematoporphyrin, 4,4-bisdimethylaminobenzophenone, and 4,4'- Includes bisdiethylaminobenzophenone.

)(, 10 is a cation represented by formula U),
The initiator has the following formula (■): CG-Z-(CO)X 3+[:Lm ]C'ff,)
(In the formula, G, Z, x, L, T and m have the meanings defined above.)

When G is an arene group, ie a six-electron ligand itself, this may be a mononuclear or polynuclear group containing a fused ring group. Preferred are hydrocarbon groups, optionally substituted by one or more alkoxy groups, preferably benzene, toluene, mesitylene, naphthalene, biphenyl, phenanthrene,
Containing 6 to 18 carbon atoms such as fluorene and anthracene.

When 0 represents a dienylium group, preferably the formula and 12 carbon atoms 1
represents an alkyl group containing p represents 0, 1.2 or 3, Z preferably represents chromium, cobalt, nickel,
Especially represents iron or manganese. ) is one of the cyclic groups represented by

Particularly preferred individual salts of the formula (wherein G represents an arene group) include π-toluentricarbonylmanganese, π-benzenetricarbonylmanganese, π-benzenetricarbonylmanganese,
Mesitylenetricarbonylmanganese, π-1-methfk-
5,6,7°8-Tetrahydronaphthalenetricarbonylmanganese, π-hexylbenzenetricarbonylmanganese, π-methoxybenzenetricarbonylmanganese and π-hexoloxybenzene IJ Includes hexafluorophosphate of carbonylmanganese.

These salts are such that the central atom (manganese) has 18 electrons in its valence shell, the monovalent manganese in the single positive cation provides 6 electrons, and the arene group provides 6 electrons. and the three carbonyl groups each donate two electrons to satisfy the closed-shell electronic configuration requirement.

Salts of the formula (1) in which G represents an arene group or a dienylium group are generally known and can be prepared as described in European Patent Application No. 94,914.

Particularly preferred individual salts of the formula (wherein G represents a cyclic dienylium group) are tricarbonyl (
cyclohexa-1,3-dienylium) iron tetrafluoroborate, tricarbonyl (1-methylcyclohe-?
1--2,4-Dienylium) iron hexafluorophosphate, tricarbonyl (1-methyl-4-methoxycyclohexa-2,4-dienylium) iron hexafluorophosphate, tricarbonyl (2-methquinvinco[4,4 ,0] ]Deca2.4-dienylium iron hexafluorophosphate, tricarbonyl(1-(acetoxy-methyl)-2-(methoxycarbonylacetoxy)ethylcyclohex-2,4-dienylium)-
Iron hexafluorophosphate, tricarbonyl (1-
Ethyl-4-impropoxycyclohex-2,4-dienylium)iron hexafluorophosphate, tricarbonyl(1-(methoxycarbonyl)-4-methoxosoclohexar2,4-dienylium)iron tetrafluoroborate and ( (π-cyclohexagenyl) tricarbonyl iron (If) hexafluoroarsenate.

These salts also meet the requirement that the central atom (iron) has a closed-shell electronic configuration, with the iron providing 7 electrons, the dienylium group providing 5 electrons, and the carbonyl group providing 5 electrons. , each providing 2 electrons (i.e. 18 in total).

The aromatic group is unsubstituted or has one or more arylthio groups,
It may be substituted with an aryloxy group, a dialkylamine group, an alkyl group or a skeletalkoxy group.

When RIO is a metallocenium ion, the initiator is
The following formula X: [(l(,11)(l(,uM)a)+an −(L
Tm)-q (X) (wherein a represents 1 or 2, n and q independently represent integers from 1 to 3, M, L, T and m are; , ° defined above R11 represents π-arene, and R'' represents π-arene or an anion of π-arene).

Possible π-arenes R11 and R12 are in particular C6 -C24 aromatic radicals or C3 -C30 aromatic heterocyclic radicals which are unsubstituted or contain halogen atoms, preferably chlorine atoms. or a bromine atom, or an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a cyano group, an alkylthio group having 1 to 8 carbon atoms, or a monocarboxylic acid alkyl ester having 2 to 8 carbon atoms. They may be mono- or polysubstituted by the same or different monovalent groups, such as phenyl, C2-C5 alkanoyl or benzoyl. These π-arene groups are
It may be a mononuclear, fused polynuclear or non-fused polynuclear system, in the last mentioned system the nucleus is directly or -S-, -
They may be bonded via a bridge member such as 〇- or 〇=C-.

R112 as an anion of a π-arene is an anion of a π-arene of the type mentioned above, such as an indenyl anion, in particular an unsubstituted or C 1 -C 8 alkyl group, a C 2 -C 6 monoanion. A cyclopentadienyl anion which may be mono- or polysubstituted with the same or different monovalent groups such as a carboxylic acid alkyl ester group, a cyanide group, an alkanoyl group having 2 to 5 carbon atoms, or a benzoyl group; good.

The alkyl, alkoxy, alkylthio, monocarboxylic acid alkyl ester and alkanoyl substituents may be straight chain or branched. typical alkyl,
Alkoxy, alkylthio, monocarboxylic acid alkyl ester modules or alkanoyl substituents include: methyl group, ethyl group, n-propyl group, inpropyl group, n-butyl group, nibutyl group, tertiary butyl group, n-pentyl group. base, n
- hequinyl group, n-octyl group, methoxy group, ethoxy group, n-broboxyl group, impropoxy group, n-butquine group, n-hexyloxy group, n-octyloxy group,
Methylthio group, ethylthio group, n-propylthio group, inpropylthio group, n-butylthio group, n-pentylthio group, n-hexylthio group, carboxylic acid methyl ester group, n-pentyl ester group, acetyl group, globionyl group, They are butyryl group and valeroyl group. Alkyl groups, alkokyne groups, alkylthio groups and monocarboxylic acid alkyl ester groups containing 1 to 4, especially 1 or 2 carbon atoms in the alkyl moiety, and alkanoyl groups containing 2 or 3 carbon atoms; preferable.

Preferred substituted π-arenes or substituted π
-Arene anions include the above-mentioned substituents, especially chlorine atom, bromine atom, methyl group, ethyl group, methoxy group, ethoxy group, anno group, carboxylic acid methyl group or ethyl ester group, and acetyl group '11f: 2 It contains.

R11 and )112 may be the same or different π-arenes. A suitable aromatic heterocycle π-arene is S-
It is a system containing 5N- and/or O atoms. Aromatic polycyclic π-arenes containing S- and/or O atoms are preferred. Examples of suitable π-arenes include benzene, toluene, xylene, ethylbenzene, cumene, methoxybenzene, ethoxybenzene, dimethoxybenzene, p-
Chlorotoluene, chlorobenzene, bromobenzene, dichlorobenzene, acetylbenzene, trimethylbenzene, trimethquinbenzene, naphthalene, 1,2-dihydronaphthalene, methoxynaphthalene, ethoxynaphthalene, chloronaphthalene, bromonaphthalene, biphenyl, stilbene, indene, biphenylene, Fluorene, phenanthrene, anthracene, 9.10-dihydroanthracene, triphenylene y1 pyrene, naphthacene,
Coronene, thiophene, chromene, xanthine, thioxanthine, benzothiophene, naphthothiophene, thianthrene, diphenylene oxide, diphenylene sulfide, acridine and carbazole.

When a is 2, each R112 is preferably an anion of π-arene, and each M is the same metal atom. Examples of substituted π-arean anions include methyl-, ethyl-1n-fo l:l'JL
/- and anion of n-phthylzochlorobentadiene,
anion of dimethylcyclopentadiene, anion of cyclopentadienecarboxylic acid methyl ester and ethyl ester, anion of acetylcyclopentadiene, anion of propionyl-cyclopentadiene, an anion of cyanocyclopentadiene, and an anion of benzoylcyclopentadiene. be.

Preferred anions are those of unsubstituted indene, especially those of unsubstituted cyclopentadiene.

Preferably, when a is 1, 几11 is benzene, toluene, xylene, cumene, methoxybenzene, chlorobenzene, p-chlorotoluene, naphthalene, methylnaphthalene, chloronaphthalene, methquinnaphthalene, biphenyl, indene, pyrene, or diphenylene sulfide. and R12 is an anion of hanclobentadiene, acetyl-cyclopentadiene or indene, an anion of benzene, toluene, xylene, trimethylbenzene, naphthalene or methylnaphthalene. Particularly preferable ones are where a represents 1, Bit is cumene, and η6
- represents pyrene or η6-naphthalene, R1” represents an anion of η5-cyclopentadiene, and n is 1
or 2, in particular 1, and q preferably represents 1. M is, for example, Ti”, T
i”, Ti”, Zr”, Zr2”, Zr”,
Hf”.

Hf2+, Hf”, Nb”, Nb2”, N
bt, Cr+, Mo”.

Mo”, W”, W2+, Mn”, Nm”
, Re+, Fe2”.

Co', Co'', Ni2+ or Cu2+. Preferably L<!-1, M is chromium, cobalt, manganese,
A tungsten or morizonium cation, especially an iron cation, most preferably Fe2+.

The compound represented by the formula
] -Q (XOq compound and [LTm]-q (in these formulas, a, m, n, q, R11
, R12°M and L have the same meanings as defined in formula X, and [X]-q represents an anion different from CLTm]-q. ) can be produced by reacting with

The compound represented by 2■ and the following formula % formula % () (wherein a and M represent the meanings defined above;
'll' (represents an anion of dπ-arene or π-arene, and R12 represents an anion of π-arene.) Both compounds represent the same or different π-arenes from group sb of the periodic table. ■B group, ■group or Ib group
It can be produced by reacting with a group metal salt in the presence of a Lewis acid. When combined with a of the formula In these cases, n is preferably 2, particularly preferably 1.

Compounds of the formula , zircosilam, chromium, manganese salts, especially iron salts. Finally, the compound of formula
It can be converted into a complex represented by

In a preferred embodiment, unexchanged π-complexes of the formula
η5-Idenyl) iron (It) are used as starting materials, which are converted into the complex represented by the formula by ligand exchange and subsequently reacted with a salt of the anion CLTm]''. In this reaction, the intermediate The complex of formula X obtained as a complex is usually not isolated.

Suitable salts of the anion [LTm]-q include, for example, alkali metal salts, alkaline earth metal salts, or ammonium salts. Alkali metal salts are preferred, most preferably sodium or potassium salts.

Lewis acids suitable for the above reaction include, for example, All
Cl! 3, AJBr3, BF3, 5nC14
and TiCJ4, with preference given to Al (J!3). The ligand exchange reaction is advantageously carried out by adding a reducing agent, such as aluminum or magnesium, to the reaction mixture, or by subsequently adding a reducing agent, such as Na2SO3 or ascorbic acid. can be done.

Aluminum is the preferred reducing agent. Ligand exchange reactions are usually carried out in an inert organic solvent. Examples of suitable solvents include aliphatic or cycloaliphatic hydrocarbons such as octane, nonane, decane and nclohexane.

If desired, excess π-arene can also be used as a solvent.

The reaction of the compound represented by 2M with a salt of the anion [LTm]-q and the anion exchange transformation of the compound represented by formula It is done in solution. The salt of the anion [LTm)-q is used in at least a chemical equivalent amount, but an excess amount is preferred.

Examples of suitable metals or non-metals in the ions [LQm]-q of all the above compounds are Sb, Fe.

8n, Bi, Al, Ga, In, Ti, Zr, S
c, V, Cr.

Mn and Cu: lanthanides such as Ce, Pr and Nd (7) or actinides such as Th, Pa, U or Np. Suitable nonmetallic atoms are in particular B.

P and As. Preferably L is P, As, B or sb, with P and sb being most preferred.

Examples of complex anions [LTm]-q are BF4-, PFe
−.

AsF6-, 5bF6-, 8bF5(OH),
FeCl4-, 8nC16.

8bC/6, BiC/6-. The most preferred complex anion is SbF6. BF4''-, AsF6- and PF6-.

When a compound of formula X is used as a polymerization initiator, this compound can be used together with an organic peroxide or hydrogen peroxide or a quinone.

The range of organic peroxides is 2゜5-dimethyl-2,5-bis(penzoylberooquine)hexane, 2,5-dimethyl-2,5-bis(tert-butylberooquine)hexane, di-tert-butyl peroxide, dihequinlene glycol beroquine, tert-butergumyl bereoquine, imptyl methyl ketone bereoquine, as well as perbenzoic acid, tert-butyl peracetate, tert-butyl perbenzoate and tert-butyl perphthalate. Peracids and peresters may also be used. Organic hydroperoxides which may be used include alkyl, aryl or alkyl hydroperoxides having up to 18 carbon atoms. Jl-class nahydroberokinds include methyl ethyl ketone hydroperoxide, tert-butyl hydroperoxide, cumene hydroperoxide as well as hydroperoxides produced by the oxidation of cetine or cyclohexene;
Tert-butyl hydroperoxide and cumene hydroperoxide are particularly effective. Suitable quinones include benzoquinone.

When (5) is a cationically polymerizable component, a suitable polymerization initiator (including onium salts and iodosyl salts) can be used to form a total polymerizable mixture when combined with the epoxide resin and/or other cationically polymerizable material. Onium salts are known; for example, suitable aromatic onium salts include those described in U.S. Pat. No. 4,058,400 and 4,058,401. Quinium salts are disclosed in U.S. Pat.
3025 and 4398014. Suitable aliphatic and cycloaliphatic sulfoquinium salts for this purpose are described in European Patent Publication A EP-A-01.
Including those described in No. 64314.

Aromatic iodonium salts which can be used for this purpose include British Patent Specifications Nos. 1,516,351 and 153.
Including those described in No. 9192. Aromatic iodosol salts that can be used include U.S. Pat.
Including those described in No. 8676.

The initiators (B) restored above include some that are more useful when irradiated with radiation in or near the visible range of the spectrum, and others that are more useful when irradiated with ultraviolet light at shorter wavelengths. It will be obvious to those familiar with photopolymerization technology that this includes: (Bl
The choice of (8) depends on whether (8) is polymerized at a wavelength longer or shorter than the wavelength at which (C) is to be solubilized; It also depends on the specific wavelength. This selection can be easily determined by experiment.

Hydroxy compounds copolymerizable with the cationically polymerizable component (5), such as diethylene glycol or 1.4
- Diols such as butanediol can also be included in the liquid composition.

When the liquid composition is a cationically polymerizable component (8) and its initiator (contains Bl, in particular the initiator is a metallocenium ion represented by the formula %), it is possible to polymerize to a non-stick solid state. For completion, it may be necessary to heat the composition in the absence of peroxide, hydrogen peroxide or quinone, followed by step (f) irradiation. This heating is carried out at a temperature of 150.degree. C. for less than 30 minutes, and usually heating at 80 to 120.degree. C. for less than 10 minutes is sufficient.

(Photo-solubilized substances that can be used as Q include O-nitrobenzaldehyde, U.S. Pat.
Polyoxymethylene polymers described in US Pat. No. 91,033, Nitrocarbonyl esters, described in US Pat. No. 3,849,137, US Pat.
O-nitrophenyl acetals and polyesters thereof described in No. 6210, as well as end-capped derivatives, sulfonate esters of aromatic alcohols containing a carbonyl group in the alpha or beta position relative to the sulfonate ester group, and aromatic amides. , aromatic imides, aromatic oxime sulfonates, 1N-sulfonyloxy derivatives of quinone diazide, and resins containing salt benzoyl groups in the chain as described in U.S. Pat. No. 4,368,253.

Preferred photo-solubilized materials that can be used as component (Q) include quinone diazides.

Photosensitive O-quinonediazide compounds are well known,
Examples include compounds having a hydroxyl or amino group in each case, in particular the aromatic compounds o-benzoquinonediazidesulfonyl or 0-naphthoquinonediazidesulfonyl esters or amides. Preferably the 1/'1o-quinonediazide is a combination of 0-benzoquinonediazide sulfonic acid or 0-naphthoquinonediazide sulfonic acid with a -valent phenol and especially 2,2-bis(hydroxyphenyl)propane, dihydroxydiphenyl, two or three Esters of phenols, including polyhydric phenols such as benzophenone substituted with hydroxyl groups, and phenolic resins, such as phenol-aldehyde resins and polymers of phenol having polymerizable unsaturated substituents. Phenol-aldehyde resins suitable for deriving esters include phenol itself or 0-, m- or p-cresol, 0
Alkyl-substituted phenols such as -lm- or p-tert-butylphenol, o-, m- or 1tip-octylphenol, or bisphenols such as 2,2-bis(4-hydroquinphenyl)propane, or two of these phenols. Included are mixtures of the above and novolaks made from aldehydes such as acetaldehyde, benzaldehyde, glyoxylic acid or, preferably, formaldehyde. Polymers of unsaturated phenols suitable for deriving esters include p-vinylphenol and U p-
Includes homopolymers and copolymers of impropenylphenol.

Preferred 0-quinonediazide sulfonyl esters of phenols are 0-naphthoquinonediazide sulfonyl esters of polyhydroxybenzophenones or novolac resins derived from formaldehyde and alkyl-substituted phenols, or mixtures thereof with phenols. Particularly preferred esters are dihydroquine benzophenone, trihydroquine benzophenone, 1,2-naphthoquinone of novolaks derived from formaldehyde and mixtures of o-, m- and p-cresols or mixtures of phenol and p-tert-butylphenol. -2-diazide-5-sulfonyl ester.

The photosensitive quinonediazide described above can be used as a commercially available product, or can be prepared by esterifying, for example, an ester-forming derivative of phenol and O-quinonediazide sulfonic acid, usually its sulfonic acid chloride, under normal conditions. It can also be produced by reaction.

Other suitable photo-solubilizable substances that can be used as (C) are O-nitrophenyl acecure prepared from O-nitrobenzaldehyde and a dihydric alcohol, acetals and polycarboxylic acids, or acetals and carboxylic acids. Bonyl esters, prepared by reacting acetals with their reactive derivatives such as anhydrides, and terminal-capped acetals, prepared by reacting acetals with their reactive derivatives, such as carboxylic acids. derivatives, etc.

Among them, 0-nitrobenzaldehyde and linear alkylene glycols having an alkylene group having 4 to 15 carbon atoms optionally interrupted by at least one acid atom, also L<a cycloalkylene glycols or tahcycloalkylene alkylene Acetals derived from glycols containing C4-C7 alicyclic rings such as glycols, polyesters and end-capped derivatives of these acetals are preferred. Linear glycols that can induce acetals include 1,4-butanediol, 1,5-bentanediol, 1.6-hexanediol, 1,7-hebutanediol, diethylene and dibutene glycol. Triethylene glycol and tripropylene glycol are preferred. As the glycol having an alicyclic ring, 2,2,4,4-tetramethyl-
1°3-cyclobutanediol, bis(4-hydroxycyclohexyl)methane, 1,4-hexanediol, 1,2-bis(hydroquinemethyl)-cyclohexane, and especially 1,4-bis(hydroquine) Methyl)cyclohexane is preferred.

The polyester acetals include the above-mentioned preferred acetals, aromatic dicarboxylic acids or tricarboxylic acids, or their anhydrides, such as phthalic acid, terephthalic acid, and trimellitic acid, and their anhydrides, as well as mixtures of two or more of these. Preferably, those produced by the reaction of Particularly preferred polyester acetals include those formed by reacting acetals derived from 0-nitrobenzaldehyde and 1°4-bis(hydroquinemethyl)cyclohexane with trimellitic anhydride.

End-capped polyacetals include those prepared by reacting the preferred acetals described above with monobasic carboxylic acids or reactive derivatives thereof, such as acetic acid and benzoic acid and their chlorides.

Additionally (preferred photo-solubilizable materials used as Q include resins containing benzoin groups in the chain, such as those described in U.S. Pat. No. 4,368,253;
Mention may especially be made of epoxy resins, polyurethanes and polyesters. Among these benzoin-containing resins, preferred are benzoin groups in which the hydroxyl group attached to the carbon atom adjacent to the carbonyl group is etherified, resulting in a benzoin alkyl ether group having 1 to 4 carbon atoms in the alkyl group. Includes: Particularly preferred is an epoxy resin produced by reacting dihydroxybency 7-furkyl ether with a diglycyl compound, particularly a dihydric alcohol (L<), or diglycidyl ether of phenol or diglyndyl hydantoin. Epoxy resins containing benzoin groups can be used as bifunctional materials in the process of the invention, in which case the epoxy groups carry out the cationic polymerization in step (n) and the benzoin groups carry out the prior solubilization in step (4++). Do the following.

(Other preferred photo-solubilizable substances used as Q include the α- or β-position of the sulfonate ester group.
Sulfonic acid esters of aromatic alcohols containing a carbonyl group at the position thereof and aromatic N-sulfonyloxyimides may be mentioned. Preferred of these esters and imides are described in U.S. Pat. sulfonyloxy)-2-hydroxy-2-phenyl-1-phenyl-1-propane, as well as N-sulfonyloxy derivatives of 18-naphthalimide, especially N-benzenesulfonyloquine and N
-(p-dodecylbenzenesulfonyloxy)-1,8
- Naphthalimide is preferred. Other preferred such esters and imides include (a) additions via its oxygen atom to an aliphatic carbon atom in the alpha or beta position to a carbonyl group and the alpha or beta position to an aromatic group; or (b) via its carbonyl group or via its sulfur atom. Preferred such polymers include at least one of the following formulas %() [where m' and rI'' represent 1 and the other represents 0 or
, Zl is a group represented by the following formula % formula % () and bonded to the aromatic carbon atom of Ar'' through a carbonyl group, or a group represented by the following formula and bonded to Arl through a carbonyl group. a group bonded to the aromatic carbon atom of When Pl is 1, R113 represents a hydrogen atom, a hydroxyl group, an etherified hydroxyl group, an alkoxy group, an alkyl group, or a phenyl-substituted alkyl group, and R14 represents a hydrogen atom or a monovalent alkyl group. represents an aliphatic group, a cycloaliphatic group, a multicyclic group, an aromatic group, or an aromatic aliphatic group, Ar'' represents a monovalent, divalent or trivalent aromatic group, and Ar2 represents a monovalent or divalent aromatic group. represents an aromatic group, Ar3 represents a monovalent aromatic group, and Ll and L2 are -CO-, -COO-, and -CONH-, respectively.

-0COO-, -NHCONH-, -0CONH-, -
C8S-.

-0C8S-, -08O2-, -CH2-, -cH=
, -0-.

-8 or -N=. ). ] Examples include those containing components represented by:

Preferred such polymers include at least four dominant phenolic hydroxyl groups, one of m' and nl represents 1 and the other represents zero, and Zl is Arl and Ar
2 each represents a phenyl group or a phenylene group,
At least one of A r '' and Ar2 represents a phenylene group, Ar3 represents a phenyl group, and R13 represents -H
, -0H1 represents an alkyl group having 1 to 4 carbon atoms, and when R14 is present, R11
4 is -H or a group represented by formula XIV representing an alkyl group having 1 to 4 carbon atoms, or Zl is a group represented by formula XIV representing an alkyl group having 1 to 4 carbon atoms; or 2.4-) represents a lyl group,
Examples include phenolic novolac resins substituted by a fractional component of formula X2, wherein Ar2 is a group represented by formula X2 representing a phenyl group, p-tolyl group, or m- or p-phenylene group.

A polymer containing a component represented by the formula represents zero or one, and Zl, Ar' and Arz
represents the same meaning as above. ) can be produced by reacting with a carboxylic acid represented by A particularly preferred polymer is N-(4-carboxyphenylsulfonyloxo)-1°8- obtained by reacting a phenol novolak with N-hydroxy-1,8-naphthalimide and 4-chlorosulfonylbenzoic acid. Obtained by reacting acid chloride of naphthalimide.

Further preferred photo-solubilizable materials for use as (C) are those described in European Patent Publication No. 199672 or non-reactive derivatives of reactive oxime sulfonates described in said publication. be. Particularly preferred oxime sulfonates include those of the following formula %() (where one of R15 and R16 represents a monovalent aromatic group, particularly a phenyl group or a 4-methoxyphenyl group, and the other represents a cyano group). or R15 and R116 together with the carbon atoms to which they are attached form a carbocyclic or heterocyclic group, in particular a fluorene or anthrone ring system, and R17 represents an aliphatic group, an aliphatic A cyclic group, a heterocyclic group or an aromatic aliphatic group, especially a 4-tolyl group, a 4-chlorophenyl group V
*u represents a 4-dodecylphenyl group. ).

Oxime Sulfophor 1-14 European Patent No. 199/
It can be manufactured according to the description in No. 172. Particularly suitable materials are oximes represented by the following formula % and the following formula 11.1780. CI! It can be produced by reacting a sulfonyl chloride represented by the following in the presence of a tertiary amine, usually in an inert organic liquid medium.

As already explained, the polymerizable component (5) and the radiation-solubilizable component (C) can both be present in the same molecule, ie, be a bifunctional substance. Suitable bifunctional substances include acrylic groups and O-quinonediazide sulfonyl ester groups, such as amino-1- or carboxy-substituted phenols whose amine or carboxyl groups are respectively unarylated or esterified with components containing an acrylic group. -quinone diazide sulfonyl ester. Suitable such esters include the O- The quinone diazide sulfonyl ester is l'. Preferred such esters are 4-(.

- acryloylamino such as (naphthoquinonediazide sulfonyloxy) methacryloylaniline - is still an O-quinonediazide sulfonyl ester of a methacryloylamino substituted phenol.

Polymers of bifunctional materials containing acrylic groups and quinonediazide sulfonyl ester groups further constitute a preferred class of solubilizable quinonediazide materials useful as C). These polymers may be homopolymers or may contain one or more polymerizable ethylenically unsaturated materials, preferably acrylic acid, methacrylic acid, alkyl and hyhydroquine alkyl acrylates, and It may also be a copolymer with an acrylic monomer such as acrylate. Preferred examples of such polymers include copolymers of O-quinonediazide sulfonyl esters of the above-mentioned acryloylamino- or methacryloylamino-substituted phenols, acrylic acid or methacrylic acid, and methyl methacrylate or 2-hydroxyethyl methacrylate. can be mentioned.

The photo-solubilizable materials include the above-mentioned aromatic alcohols, N
- a sulfonyloquine derivative iJ, an oxime sulfonate or a sulfonate ester of a quinone diazide, in the case where the material itself is not a film-forming polymer, the aqueous base-soluble film-forming polymer is Included in the liquid composition if no coalescence is produced by the polymerization of step (11). Preferably, the aqueous base-soluble film-forming polymer is included in the liquid composition even if such polymer is formed in step (li).

Suitable aqueous base-soluble film-forming polymers are those containing phenolic hydroxyl or carboxyl groups or sulfonic acid groups. Examples of these polymers include carboxyl-terminated polyesters, ethylenically unsaturated phenol homopolymers and copolymers, and vinylsulfonic acid homopolymers and copolymers.

Preferred aqueous base-soluble film-forming polymers include acetaldehyde, furfuraldehyde, L<fd an aldehyde such as benzaldehyde, preferably formaldehyde, and phenol itself, 1 to 2 chlorine atoms such as p-chlorophenol. Phenols, o-, m-, and p-cresols, xylenol, p-substituted with
-phenols substituted with one or more alkyl groups each having 1 to 9 carbon atoms, such as tert-butylphenol and p-nonylphenol, p-phenylphenol, resorcinol, bis(4-hydroxyphenyl)methane, 2.2 -bis(4-hydroquinphenyl)propane, or a mixture of these phenols.

Other preferred film-forming materials are homopolymers and copolymers of ethylenically unsaturated carboxylic acids and carboxylic acid anhydrides. Such polymers include homopolymers of acrylic acid, methacrylic acid and maleic anhydride, as well as monopolymers of these monomers and one or more other ethylene-saturated materials, such as fats such as ethylene and propylene. Included are copolymers with group unsaturated compounds, esters of acrylic acid and methacrylic acid, vinyl esters such as vinyl acetate, and vinyl aromatic compounds such as styrene and substituted styrenes.

Cationically polymerizable material or free radically polymerizable material for photo-solubilizable component (C) (2)
The weight ratio of (8):(C) is not limited as long as the effective amounts of both components are used, but when (g) and 0 are in separate molecules, the weight ratio (8):(C) is generally 10: 1 to 1:10
It is preferably within the range of 5:1 to 1:2. The amount of polymerization initiator (Bl) used is also not limited as long as it is sufficient to initiate polymerization of (5) during the first exposure to actinic radiation, but typical amounts of (B) are , f) Within the range of 0.1 to 50 parts by weight, preferably within the range of 5 to 10 parts by weight, per 100 parts by weight.

The liquid compositions used in the present invention may further include conventional additives known in the imaging art. Examples of such additives include pigments, dyes,
Included are fillers, reinforcing agents, flame retardants, antibanding agents, leveling agents, antioxidants, light stabilizers and surfactants.

Philic polymers can be included in the liquid composition to facilitate formation of images that are developable in water. Suitable hydrophilic polymers include polyethylene glycol, polyacrylamide, polyvinylpyrrolidone, preferably polyvinyl alcohol (hydrolyzed polyvinyl acetate).
Includes polyalkylene glycols such as

When used, the hydrophilic polymer generally comprises [1] of the composition.
, 5 to 20 weight percent.

Suitable radiation sources include carbon arcs, metal halide lamps, mercury vapor arcs, ultraviolet-emitting phosphorous-containing fluorescent lamps, argon and xenon glow lamps, tungsten lamps, and photographic flood lamps. 1st
It is important that the irradiation is carried out using radiation of a different wavelength than that used in the second irradiation. The use of filters to block radiation at unwanted wavelengths may prove advantageous in that a single broadly illuminating spectral source can be used in this manner. When using such a single radiation source, the first exposure is by filtering component (C).
radiation at wavelengths that activate the composition is prevented from reaching the composition. In the second exposure, the full unfiltered spectrum of radiation is used, so that radiation which solubilizes component (C) reaches the composition.

As is well understood by those skilled in the art of optical imaging, these radiation sources emit a small amount of radiation over a full range of wavelengths, while a large amount of radiation at a distinct wavelength, i.e., the wavelength of maximum intensity. emit a line.

When referring herein to the use of radiation having different wavelengths, it will be understood that the maximum wavelength intensities of the radiation used in stage (n) and stage (Il+) should be different. The overlap of the spectral regions used in steps (11) and (lit) in which the source emits a small amount of radiation will generally not impair the successful operation of the method of the invention. .

The first exposure (step C++) only needs to be long enough to activate the polymerization initiator (B), and usually a few minutes is sufficient. The time required for activation can be easily determined by simple experiments.

The activated initiator (B) polymerizes component (5), optionally in the presence of an organic peroxide or hydrogen peroxide.

When using compounds of the formula X as initiators CB), heating may be necessary to assist the polymerization. In this case, the composition can be heated at a temperature of, for example, 80°C to 120°C in order to polymerize component (8).

However, it is not necessary to heat for longer than necessary to polymerize component (5); a few minutes is sufficient.

The temperature and time required for activation can also be easily determined by simple experimentation.

The described compositions can be applied as liquids to supports such as steel, aluminum, copper, paper, silicone or plastic. After application, a first exposure is performed, with heating if necessary to solidify the composition. and the coated support is stable,
(C1?, can be stored for long periods of time away from dissolving radiation. If desired, the coated support can be subjected to imagewise exposure to actinic radiation of a different wavelength than that used for the first exposure. The coated areas that have undergone the second exposure can then be removed by washing with a suitable organic solvent or, preferably, a basic aqueous solution such as a dilute aqueous sodium carbonate solution or a dilute aqueous sodium hydroxide solution.

The coated areas not subjected to the second exposure remain on the support;
Forms a positive image. The method of the invention can thus be used for manufacturing printing plates and printed circuits using known techniques.

EXAMPLES The present invention is illustrated by the following examples. Here, parts refer to parts by weight unless otherwise noted.

The polymerizable and photo-solubilizable materials used in the examples and represented by resins (1) to (2) are as follows.

Resin 1. Novola 7 prepared from 6 moles of phenol, 1 mole of p-tert-butylphenol and formaldehyde.
A resin having a molecular weight of 1450 made by reacting with 2-naphthoquinone-2-diazido-5-sulfonyl chloride to esterify 12% of the phenolic hydroxyl groups.

Resin (1) Ester of 1 mol of 2,3,4-)IJ hydroxybenzophenone and 2.5 mol of 1,2-naphthoquinone-2-diazido-5-sulfonyl chloride.

Resin I A mixture of n-butanol (14.5 g) and powdered sodium hydroxide (8 g) was heated at 70° C. for 1 hour under nitrogen. 2-chloroethyl vinyl ether (21.3g
) was added dropwise with stirring over a period of 11/2 hours, and stirring was continued for a further 5 hours at 70-80°C. The resulting mixture was cooled and filtered to obtain 21 g of 2-ptoxyethyl vinyl ether as a brown liquid.

IR (liquid, ash) 2965.2'940, 2880°1
621.1328,1211,1080,968°82
8cm-”: NMR (DMSO-d6) 0.5-
1.2 (m-7H), 3.3-4.4 (m-8H),
&5(C)-IH)δ.

Resin ■ 0-Nitrobenzaldehyde (10a6g), 1.4-
Bis(hydroxymethyl)cyclohexane (1q2g)
, p-toluenesulfonic acid (0.2 g) and dichloromethane (600 fl) were heated at reflux temperature for 41/2 hours, during which time Dean and Stark et al.
The water was azeotroped and discharged using a Tark apparatus.

The mixture is then distilled at a temperature of 140°C,
Thereafter, the mixture was stirred at 140°C for 16 hours. The resulting mixture was distilled at 140°C under reduced pressure to obtain
The solid content was made to be 66 qb by diluting with. To one part (40 g) of the obtained solution was added trimellitic anhydride (1
2g) and heating at 150°C for 4 hours, the mixture was then distilled under reduced pressure at 150°C to give a yield of 33.
g of the desired polyester acetal product was obtained.

Resin ■ A mixture of p-aminophenol (20g), p-methoxyphenol (0.2g), acetone (200g) and pyridine (15g) was cooled to below 0°C, and then amethacryloyl chloride (zig) was added dropwise. Garoe,
The temperature was kept below 0°C. After the addition was complete, the mixture was stirred at 0° C. for 2 hours and then at room temperature for 2 hours. The resulting mixture was concentrated to reach 1/6 of the original volume and then poured into dilute hydrochloric acid (500 rnl, p)], = 1).

The formed precipitate was collected by filtration, dissolved in methanol, and reprecipitated with dilute hydrochloric acid (5001 nl, pH 1).

Recrystallization of the product from aqueous ethanol yielded j) 8 g of p-hydroxymethacryloylanilide.

Chlorosulfonic acid (67,8 g) 'k O-naphthoquinonediazide-5-sulfonic acid sodium salt (13,6
It was added dropwise at room temperature. The mixture was heated at 50° C. for 1 hour and then slowly added to crushed ice (500 g). The resulting precipitate was collected and dioxane (40d)
dissolved in This solution was mixed with p-hydroxymethacryloylanilide (8g) and triethylamine (4,95+
) and dioxane (60 mJ) were added slowly while keeping the temperature below 0°C. After the addition was complete, stirring was continued for an additional 2 hours below 0°C. The mixture was then diluted with concentrated hydrochloric acid (
5,9y) in water (1000g). By filtering the obtained precipitate and drying it, 104
The desired product, 4-(0-naphthoquinonediazidosulfonyloxy)methacryloylanilide, was obtained.

Resin■ Methyl methacrylate (9g), methacrylic acid (5g)
A mixture of g), resin v (6 g), azobis(imbutyronitrile) (Q, 2p) and tetrahydrofuran (60 g) was heated at 60° C. for 6 hours under nitrogen atmosphere. The mixture was then poured into hexane (300 m/s) and the resulting precipitate was collected and dried to obtain 7.8 g of the desired polymerization product.

Different radiation sources were used in the following examples: 1) 500W tungsten lamp: it emits radiation above 450° C.m, and radiation at shorter wavelengths is filtered out.

2) 5 kW metal halide lamp: This emits radiation with a wavelength of 340 to 450° C.m, with a maximum wavelength intensity at 435° C.m.

3) Medium pressure mercury arc lamp: This has a wavelength of 20 to 4
It emits radiation having a maximum wavelength intensity at 365°Cm between 00°Cm and 365°Cm.

Example 1 Resin I (3 parts), 2-hydroxy7ethyl methacrylate (7 parts) and bis(π-methylcyclopentadienyl)-bis(sigmahexaneoxytetrafluorophenyl)titanium (fV) ([12 parts) ) were mixed until homogeneous.

This mixture was coated onto a copper coated laminate to a thickness of 36 microns. The applied laminate was then heated under nitrogen for 4
50 fitted with a filter that blocks irradiation below 50℃m
Using a 0W tungsten-halogen lamp,
Irradiation was performed for 10 minutes at a distance of nm. After that, a 5 kW metal halide lamp was used to pass the transparent film through the solidified paint film, and 75! Irradiation was performed for 2 minutes at a distance of . A positive image corresponding to a transparent image was obtained by gentle rubbing and development with a [15% hydroxide solution] IJum aqueous solution.

Example 2 Resin i (s part), neopentyl glycol diacrylate (5 parts), 1,4-butanediol (2,5 parts) and baboon (π-methylcyclopentagenyl)-bis-(
Sigmahexaneoxytetrafluorophenyl)titanium(IV) (o, 2 parts) was mixed until homogeneous.

This mixture was coated onto a copper coated laminate to a thickness of 36 microns. The coated laminate was then irradiated for 5 minutes under nitrogen using a 500 W tungsten-halogen lamp similar to Example 1. The cured coating was then irradiated for 2 minutes at a distance of 75 cm using a 5 kW metal halide wrap through a transparency. It is difficult to obtain a positive image that corresponds to a transparent image by rubbing it with an aqueous solution of α5% sodium hydroxide and developing it.

Example 3 Resin 1 (5 parts), α-pinene oxide (5 parts), 1,4-butanediol (2.5 parts), (π-2°4-cyclopentadien-1-yl) ((1 ,2゜3.4,5.6-π
)-(1-methylethyl)-benzene)iron hexafluorophosphate (B-3s parts) and cumene hydroperoxide (0.35 parts) were mixed until homogeneous.

This mixture was coated onto a copper coated laminate to a thickness of 36 microns. The applied laminate was then irradiated for 5 minutes using a 500 W tungsten-halogen lamp similar to that used in Example 1. Thereafter, the hardened coating was irradiated for 2 minutes at a distance of 75 cWt using a 5 kW metallized lamp through the transparency.

A positive image corresponding to a transparent image was obtained by gentle rubbing and development with a 0.5 ml aqueous sodium hydroxide solution.

Example 4 Resin f (3 parts), 2-hydroxyethyl methacrylate (7 parts) and DL-camphoroquinone (n, 5 parts)
were mixed at 1 until homogeneous. This mixture was coated onto a copper coated laminate to a thickness of 36 microns. The applied laminate was then exposed to 500 W under nitrogen as in Example 1.
Irradiation was performed for 10 minutes using a tungsten-halogen lamp. After that, a 5 kW metal/ride lamp was used to pass the transparent film through the hardened paint film, and
Irradiation was performed for 2 minutes at a distance of ctn. A positive image corresponding to a transparent image was obtained by gently rubbing and developing with a sodium hydroxide aqueous solution of ratio 1.5.

Example 5 tM fat 1 (6 parts), 2-hydroxyethyl methacrylate (2 parts), acrylic acid (2 parts) and baboon (π-
Methylonclopentadienyl)-bis(sigmahexaneoxytetrafluorophenyl)titanium (α15 parts)
were mixed.

This mixture was coated onto a copper coated laminate to a thickness of 66 microns. The coated laminate was then irradiated for 5 minutes under nitrogen using a 500 W tungsten-halogen lamp similar to Example 1. Thereafter, the solidified coating was irradiated for 2 minutes at a distance of 75 cm using a 5 k'W metallized lamp through the transparency. A positive image corresponding to a transparent image was obtained by gentle rubbing with an aqueous solution of IJ (0.5% hydroxide) and development.

Example 6 Resin 1 (5 parts), α-pinene oxide (5 parts), diphenyliodonium hexafluorophosphate (α35 parts)
and acridine orange (α05 parts) were mixed.

This mixture was spread onto a copper coated laminate to a thickness of 36 microns. The applied laminate was then irradiated for 5 minutes using a 500 W tungsten-halogen lamp similar to that used in Example 1. The solidified coating was then irradiated for 2 minutes at a distance of 75 crn using a 5 kW metal halide lamp through the transparency. 0.
A positive image corresponding to the transparency was obtained by immersing and developing with a 5% aqueous sodium hydroxide solution.

Example 7 Resin I (5 parts), diallylbisphenol A (3.5 parts), ethylene glycol bisthioglycoleide (A5 parts) and bis(π-methyl-cyclopentadienyl)-bis(ngmahexane) (oxytetrafluorophenyl) titanium (0.2 parts) was mixed.

This mixture was coated onto a copper coated laminate to a thickness of 66 microns. The coated laminate was then irradiated for 10 minutes under nitrogen using a 500 W tungsten-halogen lamp similar to Example 1. Thereafter, the solidified coating film was irradiated for 2 minutes at a distance of '7 scYn using a 5 kW metal halide lamp through the transparency. A positive image corresponding to a transparent image was obtained by gentle rubbing with a 5% aqueous sodium hydroxide solution and development.

Example 8 Resin r (part a), α-pinene oxide (5 parts), 1,4-butanediol (5 parts), (π-2°4-cyclopentadien-1-yl) ((1,2゜3.4.5.6-π)
-(1-methylethyl)-hensen)iron hexafluorophosphate (0.35 parts) was mixed until homogeneous.

This mixture was coated onto a copper coated laminate to a thickness of 12 microns. The coated laminate was then irradiated for 1° under nitrogen using a 500 W tungsten-halogen lamp similar to that used in Example 1. The solidified coating was then irradiated for 2 minutes at a distance of 75 crn using a 5 kW metal halide lamp through the transparency. By gently rubbing and developing with a 1% aqueous sodium hydroxide solution, a positive image corresponding to a transparent image was obtained.

Example 9 W fat 11 (5 parts), 2-hydroquine ethyl methacrylate (6 parts) and bis(π-methylcyclopentadienyl)-bis(sigmahexaneoxotetrafluorophenyl)titanium (IY) (02 parts) ) was stirred until homogeneous.

This mixture was coated onto a copper coated laminate to a thickness of 12 microns. The coated laminate was then irradiated for 5 minutes under nitrogen using a 500 W tungsten-halogen lamp similar to Example 1. Thereafter, the solidified coating film was irradiated for 3 minutes at a distance of 75 m using a 5 kW metal halide lamp through a transparency. By gently rubbing and developing with a 0.5% aqueous sodium hydroxide solution, a positive image corresponding to a transparent image was obtained.

Example 10 Resin 1 (3 parts), Resin 1 (7 parts) and (π-2,4-cyclopentadien-1-yl) ((1°2.3,4,5
．． 6-π)=(1-methylethyl)-benzene)iron■hexafluorophosphate (0.35 parts) was mixed until homogeneous.

This mixture was coated onto a copper coated laminate to a thickness of 66 microns. The coated laminate was then irradiated for 2 minutes using the same 500 W tungsten-halogen lamp as in Example 1. Thereafter, the solidified coating was irradiated for 2 minutes at a distance of 75 ctrL using a 5 kW metal halide lamp through the transparency. 0
．． A positive image corresponding to a transparent image was obtained by rubbing and developing with a 5-component aqueous sodium hydroxide solution.

Example 11 'fldmrv (s part), 2-hydroxyethyl methacrylate (5 parts) and bis(π-methylcyclopentagenyl)-bis(sigmahexaneoxotetrafluorophenyl)titanium (Q, 2 parts) Mixed until homogeneous.

This mixture was coated onto a copper coated laminate to a thickness of 36 microns. The coated laminate was then irradiated for 10 minutes under nitrogen using a 500 W tungsten-halogen lamp similar to Example 1. Thereafter, the solidified coating was irradiated for 4 minutes at a distance of 75 crrL using a 5 kW metal halide lamp through the transparency. By rubbing and developing with a 2% aqueous sodium carbonate solution, a positive image corresponding to a transparency was obtained.

Example 12 Resin I (5 parts), 6,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate (5 parts), 1,4-butanediol (2,s part L
Triphenylsulfonium hexafluoroantimonate (α5 parts) and propylene carbonate (cL5 parts)
It was mixed in a trench until it was completely homogeneous. This mixture was coated onto a copper coated laminate to a thickness of 24 microns. The coated laminate was then irradiated for 15 seconds at a distance of 20 steps under a medium pressure mercury arc lamp with maximum wavelength intensity at 365 nm to harden the coating. Thereafter, a 5K film having a maximum wavelength intensity at 435 nm was passed through a transparency through the solidified coating.
Irradiation was performed for 3 minutes at a distance of 75 cm using a W metal halide lamp. [A positive image corresponding to a transparent image was obtained by gentle rubbing and development with a 15% aqueous sodium hydroxide solution.

Example 13 Wood MV (5 parts), 2-hydroxyethyl methacrylate (7 parts) and bis(π-methylcyclopentadienyl)bis(sigmahexaneoxytetrafluorophenyl)titanium (0.2 parts) were uniformly mixed. Mixed until .

This mixture was coated onto a gold copper coated laminate to a thickness of 12 microns. The coated laminate was then irradiated for 71/2 minutes under nitrogen using a 500 W tungsten-halogen lamp similar to Example 1. Thereafter, the hardened coating was irradiated for 2 minutes at a distance of 75 cm using a s kW metal halide lamp through the transparency. A positive image corresponding to a transparent image was obtained by immersing the film in an aqueous solution of IJ (0.5% hydroxide) and developing it.

Example 14 mtiVl (3 parts), 2-hydroxoethyl methacrylate (7 parts) and bis(π-methyl7chlorobentadienyl)bis(sigmahexaneoxytetrafluorophenyl)titanium (0.2 parts) were uniformly mixed. Mixed with a sieve.

This mixture was coated onto a copper coated laminate to a thickness of 12 microns. The coated laminate was then irradiated for 5 minutes under nitrogen using a 500 W (1.5 cm) tungsten-halogen lamp similar to that used in Example 1. Thereafter, the solidified coating film was irradiated for 2 minutes at a distance of 75 cm using a 5 kW metal halide lamp through the transparency. By rubbing with a 0.5% aqueous sodium hydroxide solution and developing, a positive image corresponding to a transparent image was obtained.

Claims (14)

[Claims] (1) (i) a support comprising: (A) a cationically polymerizable or free radically polymerizable component; (B) a radiation-activated polymerization initiator for (A); and (C) applying a layer of a liquid composition containing a radiation-solubilized component; (ii) radiation having a wavelength that activates said (B) but does not substantially activate said (C); (A) is applied to said composition and then, optionally heated, polymerizes said (A) so as to solidify the layer of liquid composition; (iii) said solidified layer is developed in exposed areas more than in unexposed areas; Radiation having a wavelength which activates said component (C), unlike the radiation used in step (ii), in a predetermined pattern to make said solidified layer more soluble. and (iv) treating and removing the exposed area with a developer. (2) the liquid composition comprises (B) a radiation-activated polymerization initiator and [1] a substance having at least one polymerizable component (A); or [2] at least one polymerizable component (C) in the same molecule, which is activated by radiation of a different wavelength than
A) and a component (C) which is activated by radiation of a different wavelength than that which activates (B) and is solubilized by radiation; or [3] at least one kind. at least one radiation-solubilized component (C) with a material having a polymerizable component (A) and/or a material having at least one radiation-solubilized component (C). 2. A method according to claim 1, comprising at least one of said difunctional substances with a substance having the following properties: (3) The method according to claim 1 or 2, wherein (A) is an ethylenically unsaturated group or a mixture of an ethylenically unsaturated group and a thiol group. (4) (A) has the following formula CH_2=C(R^1)COO-I (wherein R^1 represents hydrogen, chlorine, a bromine atom, or an alkyl group having 1 to 4 carbon atoms) 4. A method according to claim 3, which is an ester having the group represented. (5) The method according to claim 4, wherein (A) is a monoacrylate or a monomethacrylate. (6) The method according to claim 3, wherein (A) is a mixture of a phenol and a polythiol substituted with two or more allyl groups. (7) The initiator (B) is a benzoin ether, an acyloin ether, a halogenated alkyl or aryl derivative, an aromatic carbonyl derivative, a metallocene, a mixture of a Group IVA organometallic compound and a photoreductive dye, a quinone, an aliphatic dicarbonyl 7. The method according to any one of claims 1 to 6, which is a mixture of a compound, a 3-ketocoumarin, an acylphosphine oxide, a metal carbonyl, or a photoreducing dye and a reducing agent. (8) The method according to claim 1 or 2, wherein (A) is 1,2-epoxide, vinyl ether or a mixture thereof. (9) The initiator (B) has the following formula (VII) [R^1^0]^+^a^n (an/q) [LT_m]
^-^q (VII) [In the formula, L represents a divalent to heptavalent metal or nonmetal, T represents a halogen atom, or one of the T represents a hydroxyl group, and q represents 1 to 3. represents an integer, m represents an integer corresponding to the valence of L + q, a represents 1 or 2, n represents an integer from 1 to 3, and R^1^0 is (i) aromatic iodonium ion (ii) The following formula: [G-Z-(CO)_x]^+ (wherein, G represents an arene or dienylium group, and Z represents titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, niobium , represents an atom of a d-block transition element selected from molybdenum, ruthenium, rhodium, palladium, silver, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold;
and X represents a positive integer such that Z is a closed shell electron configuration. ); (iii) aromatic diazonium ion; (iv) [(R^1^1)(R^1^2M)_a]^+
^a^n (wherein a represents 1 or 2, n represents an integer of 1 to 3, M is a monovalent or represents a trivalent cation, R^1^1 represents π-arene,
Further, R^1^2 represents π-arene or an anion of π-arene. ) represents an ion selected from (v) aromatic sulfonium ion; or (vi) aromatic sulfoxonium ion (vii) iodosyl ion. ] The method according to claim 8, wherein the compound is a compound represented by: (10) (C) is O-quinonediazide, nitrophenyl acetal or its polyester derivative or end-capped derivative, resin containing a benzoin group in the chain, aromatic containing a carbonyl group at the α- or β-position of the sulfonate ester group sulfonic acid esters of group alcohols,
The method according to any one of claims 1 to 9, which is an aromatic N-sulfonyloxyimide or an aromatic oxime sulfonate. (11) Claims 1 to 5, 7, and 10, wherein the liquid composition contains a bifunctional substance having an acrylic group and an O-quinonediazide sulfonyl ester group.
The method described in any one of the following paragraphs. (12) The method according to claim 10 or 11, wherein the liquid composition comprises an aqueous base-soluble film-forming polymer. (13) A method according to any one of claims 1 to 12, wherein step (iv) is carried out by treatment with an aqueous base. (14) a radiant-edge activated polymerization initiator for (A) consisting of (A) a free radically polymerizable component; (B) a metallocene or Group IVA organometallic compound and a photoreducible dye;
and (C) a component that is solubilized by radiation;
) is activated by radiation having a wavelength different from that at which (B) is activated.