JPS60184518A - Curable composition and use - 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 [Industrial Application Field] The present invention relates to a) a substance polymerizable by cationic polymerization or free radical monomerization, b) iron (■)-η6-benzene-η5-cyclopentadienyl complex salt, c) a curable composition consisting of a sensitizer for the compound b) and d) an electron acceptor as an oxidizing agent for said substance polymerizable by free radical polymerization, polymerizing this substance by the action of radiation. The present invention relates to methods and materials coated with said compositions and uses thereof.

[Conventional technology]

Patent document EP-A-0.094,915 describes curable compositions consisting of substances polymerizable by cationic polymerization, which contain (π-arene)-metal complexes as initiators. The composition can be cured directly by the action of heat, or it can be first irradiated to activate the initiator and then cured by the action of heat. However, for complete curing, the exposure time must be relatively long, which is not economical. Therefore, it is desirable to increase the photosensitivity. It is also desirable to avoid thermal curing after irradiation and to cure only by radiation. It has further been found that thermal curing can be largely avoided by the concomitant use of sensitizers.

[Disclosure of the invention]

The present invention relates to a) a substance polymerizable by free radical polymerization or cationic polymerization, b) at least one iron compound consisting of the following formula I [(R1)(R2FeII)a]+a-(LQm)-q
(■) (However, a is 1 or 2, q is 1.2 or 3, L is a divalent to heptavalent metal or nonmetal, Q is)・Rogge/atom, m
is an integer corresponding to the sum of the valence of L and the value of q, R1 is η6-henzene with or without a substituent, and R2 is a cyclopentanoenyl anion with or without a substituent), and C) Comprising at least one sensitizer for the compound of the formula (1) and, in the case of substances polymerizable by free radical polymerization, furthermore d) Compositions containing an electron acceptor as oxidizing agent.

[Best mode for carrying out the invention]

Said compositions comprising substances curable by cationic polymerization also advantageously contain electron acceptors as oxidizing agents, especially when used for curing by radiation.

The iron compound of the formula I or the iron compound of the formula 1 and the oxidizing agent d) are comprised between 01% and 15% by weight, in particular between 01% and 10% by weight.
, more specifically in an amount of 0.1% to 5% by weight. The weight ratio of iron compound of formula I to oxidizing agent d) is preferably from 1:1O to 5:1, in particular from 1:1 to 5:1.

Said sensitizer C) is 0.1% to 10% by weight, in particular 0.1% to 10% by weight.
Preferably, it is incorporated in an amount of from 0.1% to 5% by weight, especially from 0.1% to 25% by weight.

As a monocyclic π-arene derived from benzene, R1 in formula I is the same or different;
-Nyl group, C2-C engineering. It may be mono- or polysubstituted by an alkynyl group, a C□-C8 alkoxy group, a cyano group, a C1-C□2 alkylthienyl group, a C2-C5 alkanoyl group or a benzoyl group.

Cyclobencdienyl anion R2 is the same or different, C1-C8 alkyl group, C2-C8 alkenyl group,
It may be mono- or polysubstituted by a C2-C8 alkynyl group, a C2-C6 monocarboxylic acid ester group, a cyano group, a C2-C5 alkanoyl group or a benzoyl group.

Each of the alkyl, alkoxy, alkylthio, monocarboxylic acid alkyl ester, and alkanoyl substituents may be linear or branched.

Typical alkyl, alkoxy, monocarboxylic acid 7 esters and alkanoyl substituents are methyl, ethyl, n-propyl, 'I 7 7', respectively.
cyle, n-butyl, sec-butyl, ter
t-butyl, n-pentyl, n-hexyl and n-octyl; methoxy, ethoxy, n-propoxy, impropoxy, n-methoxy, 11-hexyloxy and l]
-Octyloxy; methylthio, ethylthio, l]-propylthio, inopropylthio, n-butylthio, n-
Pentylthio and n-hexylthio; CalS? methyl, ethyl, n-propyl, isopropyl, l]-butyl and n-pentyl esters; and acetyl, propionyl, butyryl and valeroyl. Preferably each of the pre-Ne alkyl, alkoxy, alkylthio and monocarboxylic acid alkyl ester groups has 1 to 4, especially 1 or 2, carbon atoms in its alkyl portion, said alkanoyl group having 2 or 3 carbon atoms. Preferably, it has atoms. π in which R1 has a substituent derived from benzene
- in the case of arenes, R1 contains one or two of the above-mentioned substituents, in particular chlorine or bromine atoms, methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, cyanogen, methyl carmate or ethyl ester and acetyl groups. is preferable.

Examples of compounds having a benzene ring that are good or bad π-arenes include benzene, toluene, xylenes, ethylbenzene, methoxybenzene, ethoxybenzene, dimethoxybenzene, p-10 lotluene, chlorobenzene, fromobenzene, dichlorobenzene, and acetylbenzene. , trimethylbenzene, trimethoxybenzene, 1
．． 2-) Hydronatsutaleno, ], 2,3゜4-tetrahydronaphthalene, mesitylene, cumene, biphenyl,
They are anisole and stardecylbenzene. Preferred are benzene, toluene, xylene, cumene, mesitylene, chlorobenzene, chlorotoluene, anisole, dimethoxybenzene, biphenyl, dodecylbenzene or tetralin.

Preferably R2 is a cyclopentanoenyl anion or a C1-C4 alkylated cyclopentadienyl anion, especially a methylcyclopentadienyl anion.

In formula (2), a is preferably l.

Suitable examples of metals or non-metals include Sb, Fe.

S n + B + + A I + G a + I
n + T l + Z r + S c + V +
Cr + Mn and Cu; lanthanides such as Ce, Pr and Nd; and actinides such as Th, Pa, U and Np. Suitable non-metals are in particular B, P and AS.

L is preferably P, As, B or sb, particularly preferably P. Preferably, the halogen atom Q is CI and especially F.

In formula I, it is preferred that q is 1, ITI is 6, Q is F and L is B 2 , P 2 , As or sb.

be. A particularly preferred complex anion is SbF6. BF, -.

AsF6- and PF6-.

Compounds of formula (1) are known or can be prepared by analogous methods.

The electron acceptor d) as oxidizing agent is preferably an organic hydroperoxide, an organic peracid or a quinone. Specific examples include tert-butylhydroperoxide, cumene hydroperoxide, triphenylmethyl hydroperoxide, tetralin hydroperoxide, α-methyltetralin hydroperoxide, decalin hydroperoxy P, perbenzoic acid, m-chloroperbenzoic acid, or There is benzoquinone.

Suitable examples of sensitizers C) include at least 3 per mole
0, preferably at least 35 kilocalories.

They are, for example, monocyclic or polycyclic, aromatic or heteroaromatic hydrocarbons, phenones, in particular acetophenones and benzophenones, benzyls, stilbenes, polyacetylenes, xanthones and thioxanthones, It can be chosen from the group consisting of anthracenes, phthalimides, especially phthalimide thioethers, and diones with vicinal Ce groups. Other suitable sensitizers and examples thereof are varnishes.

murOv [Photochemistry Handbook;
M, Terrakar Inc.; New E-li; pages 27 onwards, (19
1973)].

Preferred sensitizers are thioxanthones, phthalimides,
In particular, phthalimidothioethers, coumarins and anthracenes. Suitable phthalimidothioethers are described in patent documents DB-A-3117589 and EP-A
-0,062,615. Suitable thioxanthones are described, for example, in patent document DE-A-3018
No. 891 and EPO, No. 033,720.

Particularly preferred sensitizers are anthracenes with or without substituents or mixtures of these anthracenes.

Anthracenes correspond to the following formula H 4 [However, R3-R8 are each independently a hydrogen atom, rogene, a cyano group, a straight or branched C1-C18 alkyl group, a 01-C□8 alkoxy group Or 01~C18 or C5
~C1゜cycloalkyl group, straight chain or branched chain C3~C1
8 alkenyl group, C7-CI6 aralkyl group, -CnH
2n-OZ, -C,H2n-CN, -C,,H2
n-COOR or (where n is a number from 1 to 18, R9 is a linear or branched 01-C18 alkyl group, a C5-C1 substituted or unsubstituted with a 01-C6 alkyl group)
2cycloalkyl group, C6~C1□aryl group, C7~
C16 alkaryl group, 07-016 aralkyl group, 0
8-C alkalkyl group or metal cation/, and R10 and R11 are each independently a hydrogen atom, a 01-C18 alkyl group or a C5-C
12 cycloalkyl group, or R10 and R11 together are a tetramethylene group, pentamethyleneno group or 3-oxapentele group, and 2 is a hydrogen atom or a C1-C18 alkyl group].

In a preferred embodiment, at least one of the groups R3 to R8 is one of the substituents defined above.

In other embodiments, R3, R5, R6 and R8 are hydrogen atoms, and R4 and/or R7 are C1-C18 alkyl groups or C1-C18 alkoxy groups. In another preferred embodiment, R4 and R6-R8 are hydrogen atoms, R3 and R5 are one of the substituents defined above, R3 is bonded especially in the 6- or 7-position, and R5 is 2
connected to the position.

When R3-R8 is a halogen, it is preferably chlorine; when R3-R8 is an alkyl group, an alkoxy group and an alkylthio group, R3-R8 has 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms. It is preferable to have R3-R
When 8 is a cycloalkyl group, R3-R8 preferably has 5 or 6 ring-forming carbon atoms. When R3-R8 is an alkenyl group, it is preferred that R3-R8 have 3 to 8 carbon atoms. When R3-R8 is an aralkyl group, it is particularly preferred that R3-R8 is a phenylalkyl group having 7 to 12 carbon atoms.

Numerical value 1] is preferably 1-12, particularly 1-6.

When R9 is an alkyl group, R9 is 1 to 12, especially 1 to
Preferably it has 6 carbon atoms, and in the case of cycloalkyl groups preferably 5 or 6 ring-forming carbon atoms. When R9 is an aryl group, R9 is preferably a phenyl group, and when it is an alkaryl group, a C7-C1□ alkylphenyl group is preferable. If R9 is an aralkyl group,
R9 is preferably a 07-C1□ phenyl alkyl group, and in the case of an alkalkyl group, a 08-C1□ alkylphenyl alkyl group is preferable. When R9 is a metal cation, the cation is preferably selected from alkali metals and alkaline earth metals, such as Mg, Ca, K and especially Na.

When RIO and R11 are alkyl groups, R10 and R
Preferably, 11 has 1 to 12, especially 1 to 6 carbon atoms. When R10 and R11 are cycloalkyl groups, they preferably have 5 to 6 ring carbon atoms.

When 2 is an alkyl group, it preferably has 1 to 12, especially 1 to 6 carbon atoms.

Examples of alkyl groups, alkoxy groups and alkylthio groups include methyl group, ethyl group, n-propyl group, l-propyl group, l]-butyl group, 1-butyl group, t-butyl group,
1-22- or 3-pentyl group, ■-12- or 3-hexyl group, hebutyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl group or octadecyl group and corresponding alkoxy and alkylthio groups.

Examples of cycloalkyl groups include cyclopentyl, methylcyclopentyl, cyclohexyl and methylcyclohexyl.

Examples of alkenyl groups are allyl and l-zorobenyl.

Examples of aryl, aralkyl, aralkyl and alkalkyl groups include phenyl, benzyl, 2-phenylethyl, methylphenyl, ethylphenyl and methylbenzyl.

Some of the compounds of formula (1) above are known.

New compounds of formula (1) can be obtained by known methods, for example by subjecting anthracene or anthracenes having substituents to a Friedel-Crafus alkylation reaction.

Examples of sensitizers include perylene, 3,4-benzopyrene,
1,12-benzoperylene, pyrene, pentaphene, 1
, 2-benzopyrene, fluoroanthrene, 1,2-benzochrysene, l-aminonaphthalene, coronene, 1-
Nitronaphthalene, 3,4-benzofluorene, 2.2
'-Binaphthyl, ■-Nandaldehyde, 5.6-benzochrysene, ■-Acetylnaphthalene, 3゜4.5.6
-dibensyphenanthrene, chrysene, 1.2 and 2.
3-benzofluorene, 1-benzoylnaphthalene, ■
-naphthonitrile, naphthalene-1-force/L/zenic acid,
1,2,6.7-dibencypyrene, 9-acetylphenanthrene, 1-naphthol, 1-iodonaphthalene, 2
-Phenylnaphthalene, 3.4-benzophenanthrene, 3-acetylphenanthrene, 1-bromonaphthalene, ■-chloronaphthalene, 2-naphthonitrile, acenaphthene, 2-nandaldehyde, naphthalene-2-carboxylic acid, 2-acetylnaphthalene, 2-benzonaphthalene, l-methylnaphthalene, l-methoxynaphthalene,
1-fluoronaphthalene, 2-iodonaphthalene, 2-
Bromonaphthalene, 2-chloronaphthalene, 2-naphthol, 2-methylnaphthalene, naphthalene, phenanthrene, anthraquinone, triphenylene, 4-benzoylpyridine, 2-benzoylpyridine, fluorene, 3
-benzoylpyridine, carbazole, 4-acetylpyridine, 4-methoxybenzaldehyde, 4-methylbenzaldehyde, benzaldehyde, anthrone, l-
Tetralone, 4-phenylacetophenone, 3,4-methylenedioxyacetophenone, 4-cyanoacetophenone, α-chloroacetophenone, 3,4゜5-trimethylacetophenone, 3,5-dimethylacetophenone/
, 4-bromoacetophenone, 4-methoxyacetophenone, 3,4-)methylacetophenone, trinoenylmethylacetophenone, 4-chloroacetophenone, 4
-Trifluoromethylacetophenone, 2,4゜6-trimethylacetophenone, 3-methoxyacetophenone, 3-methylacetophenone, 3-bromoacetophenone, 4-methylacetophenone, 3-cyanoacetophenone, 3-trifluoromethylacetophenone, acetophenone, allyl Acetophenone, benzophenone, 4
-phenylbenzphenone, 4,4'-hisdimethylaminobenzophenone, 4-cyanobenzophenone, 4
, 4'-dichlorobenzophenone, 4-trifluoromethylbenzophenone, 3-methoxybenzophenone, 4
-chlorobenzophenone, 3-chlorobenzophenone,
4,4'-dibromobenzophenone, 4-methoxybenzophenone, 3,4-dimethylbenzophenone, 4-nor-11-rubenzophenone, 2-methylbenzophenone, 4,4'-tsumethylbenzophenone, 2,S-dimethylbenzophenone, 2. 4-dimethylbenzophenone,
4-Fluorobenzophenone, orthobenzylbenzophenone, 4゜4'-dimethoxybenzophenone, 2-phenylbutyrophenone, β-phenylpriophenone, propiophenone, parellophenone, fuy-lofuenone, benzyl, trans-stilbene, cis- Stilbene, diphenyltetraacetylene, tetraacetylene, glycol, diethyltetraacetylene, diphenylacetylene, xanthone, thioxanthone, 2-inopropylthioxanthone, 2-chlorothioxanthone, 2
-dodecylthioxanthone, ■-methoxy/tridinylthioxanthone, 2-ethoxycal 7j? Nylthioxanthone, 3-(n-methoxyethoxycarbonyl)thioxanthone, 4-butoxyruzenylthioxanthone, 1-cyano-3-chlorothioxanthone, 2-ethoxycarbonyl-3-ditrothioxanthone, anthracene, 1-chloroanthracene, 2 -Methylanthracene, 9-methylanthracene, 2-tert-butylanthracene, 9-methoxyanthracene, 9,10-dimethoxyanthracene, 2°6- or 2,7-trimethylanthracene, 2°6- or 2,7- tert-butylanthracene, 2-(methoxycarbonylmethyl)
Anthracene, 2-(5-methoxy-2-methylbent-2-yl)anthracene, 2.6- or 2
．． 7-di(5-methoxycarbonyl-2-methylbent-2-yl)anthracene, 1゜2-benzanthracene, l, 2,3.4-nobenzanthracene, 1,2,
5.6-) Benzanthracene, 1,2,7. s-)benzoanthracene, 3-thiophenyl phthalimide, N
-Methyl-4-thiophenyl phthalimide and 2,3-butanone.

Examples of organic substances suitable for the curable compositions according to the invention which can be polymerized by cationic polymerization are of the following types, which can be used on their own or as a mixture of at least two components: It is also possible.

■ Ethylenically unsaturated compounds that can be polymerized by a cationic mechanism. These compounds include: ■) Modiolefins and diolefins, such as inzotylene, butanoene, isoprene, styrene, α-
methylstyrene, divinylbenzenes, N-vinylpyrrolidine, N-vinylpyrrolidine) L//ζ sol and hyacrolein.

2) Vinyl ethers, such as methyl vinyl ether, inobutyl vinyl ether, trinotyrolpropane trihinyl ether and hyethylene glycol novinyl ether; and cyclic vinyl ethers, such as 3.4-
Sibaidro 2-formyl-2H-pyran (acrolein dimer) and 2-hydroxymethyl-3,4-dihyF
Rho 2 If-pyran 3,4-dihydro-2H-pyran-2-carzenic acid ester 3) Vinyl esters,
For example, vinyl acetate and vinyl stearate.

■ Heterocyclic compounds that can be polymerized by cationic polymerization:
For example, ethylene oxide F, propylene oxide,
Shrimp chlorohydrin, -hydric alcohols or phenolics IJ nodyl ethers, such as n-butyl glycidyl ether, l]-octyl glycidyl ether, phenyl glycidyl ether and cresyl) V glycidyl ether; grindyl acrylate, glycidyl methacrylate , styrene oxide and cyclohexene oxide;
Oxetanes such as 3,3-trimethyloxetane and 3,3-di(chloromethyl)oxetane; tetrahydronerane; dioxolanes, trioxane and 1,3.
6-Dryoxacyclooctane; lactones such as β-gloviolactone, γ-valerolactone and ε-caprolactone; thiiranes such as ethylene sulfide and propylene sulfide; N-acylazetidines; e.g. N-penzoylazetidine, as well as diisocyanate adducts of azetidine, such as toluylene-2,4-twincyanate, toluylene-2,6-twincyanate or 4,4/-noaminophenylmethane diisocyanate. azetidines; epoxy resins; and linear or branched polymers with glycidylation in the side chain, such as glycidyl 7 of acrylic or methacrylic acid.
Homopolymers or copolymers of diester.

Of particular importance among these above-mentioned polymerizable compounds are Fj':oxy resins, especially diepoxides and polyepoxides, and epoxy resin prepolymers of the type used to make crosslinked epoxy resins. Geboxides and polyepoxides can be aliphatic, cycloaliphatic and aromatic. Examples of such compounds include glycidyl ethers and β-methylglycidyl ethers of aliphatic or cycloaliphatic falls or polyols, such as ethylene glycol, zo0/ξ7-1.2-')ol, noronoξ-1 ,3-nol, butane-1,4-
diol, noethylene glycol, polyethylene glycol, polypropylene glycol, glycerol, trimethylolpronone or 1,4-/1'methylolonechlorohexane or 2,2-his(4-hydroxycyclohexyl)pronone and N.

The above ethers of N-bis(2-hydroxyethyl)aniline; and diphenols and polyphenols, such as resolzonol, 4,4'-dihydroxydiphenyl meta7.4,4'-dihydroxydinophenyl-2
, 2-f lonoξn, nozeranokids and 1,1,2.2-
There is a glycidyl ether of tetrakis(4-hydroxyphenyl)ethane. Further examples of these include N-glycidyl compounds such as ethyleneurea, 1,3-zolopyleneurea, 5-dimethylhydantoin or 4,4
These include diglycidyl compounds of '-methylene-5,5'-tetramethylnohydantoin or incyanuric triglycidyl compounds.

Other glycidyl compounds of industrial importance are carboxylic acids,
In particular, glycidyl esters of nocarboxylic and polycarboxylic acids. Examples of these are succinic acid, adipic acid, azelaic acid, sepacic acid, phthalic acid, terephthalic acid, tetrahydro and hexahydrophthalic acid, isophthalic acid or trimellidic acid, or glycidyl esters of fatty acid dimers.

Examples of polyepoxides other than glycitur compounds include noepoxides of vinylcyclohexene and nonclopenotanoene, 3-(3/,4/-epoxychlorohexyl)-8,9-epoxy-2,4-dioxaspiro(5,S ) undecane, 3/, 4/-epoxycyclohexyl methyl ester of 3,4-epoxychlorohexanecarboxylic acid, butanoene diepoxide or isoprene diepoxide, epoxidized linoleic acid derivatives or epoxidized polybutanoene.

Preferred epoxy resins are dihydric phenols or 2-4
diglycidyl ethers of dihydric aliphatic alcohols (with or without pre-long chains) having 5 carbon atoms.

Particularly preferred are 2,2-bis(2-hydroxyphenyl)pronoξ and bis(4-hydroxyphenyl)
It is a diglycidyl ether of methane (which may or may not have long chains beforehand).

The following compounds are also suitable as compounds that can be polymerized by cationic polymerization.

■ Methylol compounds: ■) Amides or related compounds, such as ethylene urea (imidazolidin-2-one), hydantoin, uron (tetrahydroxacyanon-4-one), 1,2-propylene urea (4-methyl imidazolidin-2-one), danolidin-2-one),
1.3-zolopylene urea (hexahydro-2H-pyrimidin-2-one), hydroxypropylene urea (5-hydroxyhexahydro-2H-pyrimidin-2-one)
, N-hydroxymethyl of cyclic ureas such as 1,3,5-melamine and other polytriazines such as acetoguanamine, benzoguanamine and adipolyamines,
N-methoxymethyl, N-n-butoxymethyl and N
-Aminoplasos such as acetoxymethyl derivatives.

If desired, both N-hydroxymethyl and N-alkoxymethyl groups or both N-hydroxymethyl and N-acetoxymethyl groups (e.g. hexamethylolmelamine in which 1 to 3 hydroxyl groups are etherified with methyl groups) It is also possible to use aminoplasts with

Preferred aminopurasos are condensates of urea, uron, hydantoin or melamine with formaldehyde and the products of partial or complete etherification of these condensates with aliphatic alcohols having 1 to 4 carbon atoms. .

2) Phenoplasts Preferred phenosols are resols made from phenol and aldehydes. Suitable phenols include phenol itself, resorcinol, 2,2-bis(p-hydroxyphenyl)propane, p-chlorophenol, each having from 1 to 9 carbon atoms, such as ortho-, meta- and q-lacresols. Phenols substituted with 1 to 2 alkyl groups, xylenols, tert-butylphenol and hihalanoylphenol, and phenyl-substituted phenols,
In particular, it contains ξ phenylphenol. Formaldehyde is preferred as the aldehyde condensed with phenol, but other aldehydes such as acetaldehyde and furfuror are also possible. Mixtures of these types of curable phenolic/aldehyde resins can be used if desired.

Preferred resols are phenol, ξ-chlorophenol, resorcinol or condensates of ortho-, meta- or para-cresol with formaldehyde.

Suitable organic substances which can be polymerized by free-radical polymerization are in particular monoethylenically or polyethylenically unsaturated compounds. Examples of these are styrene, vinylpyridine, vinyl acetate, divinylbenzene, vinyl ether,
There are acrylamides, methacrylamides, bisacrylamides, bismethacrylamides or unsaturated polyesters, especially those based on maleic acid. Preferred substances are esters or amides of acrylic acid and/or methacrylic acid with linear or branched-chain alcohols or polyols or monoamines or polyamines, respectively. Partial esters and amides can also be used in conjunction with polyols and amines.

Examples of polyamines include ethylenenoamine, propylene diamine, butylene diamine, pequinediamine,
These include phenylene diamine, benzylene diamine, naphthylene diamine, diethylene triamine, triethylene tetramine and diaminoethyl ether. Examples of polyols include ethyleneol, propylene diol,
Linear or branched alkylene diols such as butylene diol, pentylene diol, hexylene diol and octylene diol, diethylene glycol and hydryethylene glycol, and polyoxas such as polyethylene glycol with a molecular weight of 200 to 500. Alkylene diols, 1,4-nohydroxycyclohexane, 1,4-no(hydroxymethyl)cyclohexane, dihydroxybenzenes, hydroxymethylphenols, 1,2,3-trihydroxypropane, 1,2,4-
These include triols such as trioxybutane and trimethylolpropane, pentaerythritol, dipene chloride, and low molecular weight polyesters having multiple terminal hydroxyl groups.

Suitable examples of alcohols and monoamines are methanol, ethanol, pro-ξol, butanol, pentanol, hexanol, heptatool, octatool, 2-ethylhexanol, cyclohexanol, phenol, glycidol, methylamine, These are trimethylamine and ethylamine.

Preferred organic substances polymerizable by free radical polymerization are partial esters of epoxy resins with acrylic acid, methacrylic acid or mixtures of these acids and acrylic and/or methacrylic esters of polyols.

The curable compositions according to the invention can be obtained, for example, in a homogeneous mixture or in homogeneous or heterogeneous glass form. Homogeneous glassy product 1, in a manner known per se,
For example, a solid polymerizable organic material may be liquefied by adding a suitable solvent if necessary, in the dark or under a red light.
d 11g1]t) and heated to a temperature above their glass transition temperature, components b) and if necessary d)
and cooling the resulting mixture. If desired, the glassy product can then be ground. Heterogeneous glass products can be obtained, for example, by mixing components b) and C) and, if necessary, d) with pulverulent, glassy polymerizable substances.

Since the composition according to the invention is stable, it is possible to store it at room temperature and under yellow light conditions. These compositions advantageously contain component b
) and C) and optionally added component d) can be directly cured by heating at a temperature close to the melting point or decomposition point. In the case of sensitizers that absorb light in the wavelength range below 400 nm, the compositions are stable to yellow light despite having high photosensitivity.

The main advantage of the compositions according to the invention containing component d) is that they can be cured by the action of radiation, complete curing being substantially achieved by the heat of reaction, and no external heating is necessary.

For example, if you want a shorter reaction time,
It is sometimes advantageous to apply external heat after exposure.

The invention therefore also relates to a process for the polymerization of polymerizable organic substances under the action of radiation, in the presence of a photoinitiator and, if necessary, by heating to form free radicals or cations, in which said photoinitiator is a) at least one iron compound consisting of the following formula (where a is 1 or 2, q is 1, 2 or 3, and L is 2il);
lI11-7 valent metal or nonmetal, Q is a halogen atom,
m is an integer corresponding to the sum of the valence of L and the value of q, R1 is η6-benzene with or without a substituent, and R2
is a cyclopentanoenyl anion with or without substituents; b) at least one sensitizer for the compound of formula 1; and C) at least one electron acceptor as an oxidizing agent. and, if necessary, the polymerization reaction is further completed by heating.

These curable mixtures preferably have a
It is advantageous to irradiate with an electron beam or electromagnetic radiation having a wavelength of 150 nm and an intensity of 150 to 5000 watts. Examples of suitable light sources include metal arc lamps such as xenon lamps, argon lamps, tungsten lamps, carbon arc lamps, metal halide lamps and low-pressure, medium-pressure and high-pressure mercury discharge lamps. Irradiation is preferably carried out with a metal halide lamp or a high pressure mercury discharge lamp. The irradiation time depends on various factors including, for example, the polymerizable organic material, the type of light source, and the distance of the light source from the material being irradiated. The irradiation time is preferably 10 to 60 seconds.

The exposed composition can be heated in a conventional convection oven. If short heating or reaction times are required, the heating can be carried out, for example, by exposure to infrared radiation, an infrared laser or a microwave device. Polymerization temperatures range from room temperature to about 80'C.

The compositions according to the invention may also contain other known additives commonly used in the art regarding photopolymerizable materials.

Examples of these additives include pigments, dyes, fillers and reinforcements, glass fibers and other fibers, flame retardants, antistatic agents,
There are flow control agents, antioxidants and light stabilizers as well as customary photoinitiators such as acetophenones, acylphosphine oxytes or aromatic ketones.

In order to improve the final properties of the epoxy resin, polyfunctional hydroxyl compounds, such as DE 26
It is possible to incorporate those described in No. 39395.

In order to increase the storage stability in the dark, the curable composition may contain organic weak bases such as nitrides, amyl-Ss, lactones or urea derivatives. I can do it. Small amounts of UV absorbers and/or organic dyes can be added to prevent pre-reactions due to accidental exposure.

The compositions according to the invention can be applied to substrates (or surfaces) by conventional methods. Coated substrates also form the subject matter of the invention. Examples of suitable substrates include steel, aluminum, copper. , metals and semimetals such as cadmium, zinc, silicon, and ceramics, glass, plastics, paper, and wood.The coated substrates can be used to form protective and inert layers by exposure to light; constitutes a further subject of the invention.

If during exposure only part of the coating is irradiated through a photomask, the unexposed parts can be subsequently removed with a suitable solvent. The coated substrates are therefore suitable both as photographic recording materials for the production of printing plates, in particular printed circuits, and as solder resists. The use as a photographic recording material also constitutes a subject of the invention.

Compositions according to the invention containing substances polymerizable by cationic polymerization and without any oxidizing agent d) are disclosed in US Pat.
It can be cured by the method described in P-A-0-094,915. These compositions are directly curable by the action of heat.

The iron complex of formula I is first activated by irradiation and the resulting activated precursor is then heated, e.g.
Preference is given to a two-stage polymerization process in which the polymer is cured by the action of a temperature of 20'C. If the irradiation is carried out via a photomask, photographic images can be obtained. The irradiation time is between about 5 and 60 seconds and the heat curing time is between about 30 seconds and 5 minutes.

These compositions according to the invention are characterized by high sensitivity.

The compositions according to the invention can also be used for the production of adhesives or adhesives, fillers or fiber-reinforced composites and laminates.

The high sensitivity of the compositions according to the invention also means that exposure times during the curing process are short. Initiators with cationic and free-radical action are generated simultaneously during exposure, thereby widening the range of polymerizable substances that can be used.

It is further surprising that the oxidizing agent becomes active only after exposure, allowing curing by irradiation. It is very advantageous that curing takes place by the action of radiation, generally without external heating.

〔Example〕

The following examples illustrate the invention in further detail.

Example a.

(η6-toluene)(η5-cyclopentadienyl)iron([)hexafluorophosphate 'Bull・Soc
, Ch im, Fra 7s, 2572 pages (1975)
Manufactured according to Pa.

Example.

(η6-Aninyl) (η5-Cyclopentanoenyl)
Iron (nl hexafluoromonoate)'Dokl.

Akad, Nauk 5SSR, I 75, p. 609 (1967).

Example C1 (η"C'j') l-quinbenzene O (η5-cyclopentadienyl) iron tetrafluoroborate" J
, Chem, Soc, C, p. 116 (19'69).

Example d.

(η”-1)-chlorotoluene)(η5-cyclopentadienyl)iron U hexafluorophosphate” J, Or
ganomet, Chem, 20, p. 169 (19
69)''.

Example e.

(η6-itsuprobylbenzene)(η5-cyclopentanoenyl)iron(U)hexafluorophosphate
R,Acad,Sc,/”ri,Ser,C,27
2, 1337 (1971) 9''.

Example f.

(η6-itzolobylbenzene)(η5-cyclobentanoenyl)iron([)hexafluoroantimonate,
Prepared according to Example e except that potassium hexafluoroantimonate was used.

Example g.

(η6-Itzolobylbenzene)(η5-encrohentacyenyl)irontll)hexafluorophosphate was prepared according to Example e except that potassium hexafluoroarsenate was used.

Example.

(η6-biphenyl) (η5-cyclopentadienyl)
Iron (U) hexafluoroline salt” J, Chem.

Soc, Chem, Comm, p. 907 (1972
Manufactured in accordance with the year)''.

Example 1゜(η6-titraline) (η5-cyclopentagenyl)
Iron (river hexafluorophosphate ■.

Organomet, chem, 101, p. 221 (
1975).

USE EXAMPLES Example 1 10.9 industrial epoxy cresol novolank (epoxy content 45 equivalents/kg), 0.25 jj (7Xl
025 g (1,3X10"
A solution also consisting of 9-methylanthracene (mol) and 4 g of 1-acetoquino-2-ethoxyethaneka) was applied to a copper coated epoxy board with a 25 micron wire doctor.

The initially wet film was dried at 80'C (the thickness of the dry film was approximately 15 microns).

The photopolymerizable plate produced in this way was placed on the sample stand 0.50c.
Exposure was with a 5000 watt high pressure mercury discharge lamp at a distance of rfL. 21 stage Stouffer
Sensitivity guide, 6ter 7 (VV, S, DeForest, Photoresist, McGraw-Hill Publishers, New York, 10
(see pages 9 onwards). The exposure time was 30 seconds and the exposed plates were then cured for 2 minutes at 0°C. It was developed with 1-acetoxy-2-X-ethoxyethane to dissolve the unexposed areas. As a result, a relief image was obtained.

The final step in forming the image was the fifth step.

Examples 2-1 = 1 The procedure of Example 1 was continued using different initiators and sensitizers.

The results are not summarized in [cloth]. The initiator (arene-ferrocenium complex) was always 25% by weight based on epoxy cresol novolanoque and the corresponding sensitizer concentration was always 13 mmol based on epoxy cresol novolanoque. Exposure is 10.20 on each side
and for 30 seconds.

Claims (1)

[Scope of Claims] (11a) a substance polymerizable by free radical polymerization or cationic polymerization; b) at least one iron compound consisting of the following formula (wherein a is 1 or 2 and q is 1.2 or 3); , Lba bivalent ~
Heptavalent metal or nonmetal, Q is a halogen atom, m is an integer corresponding to the sum of the valence of L and the value of q, R1 is η6-benzene with or without a substituent, and R2 has a substituent C) a cyclopentagenyl anion with or without a cyclopentagenyl anion; , further comprising d) an electron acceptor as an oxidizing agent. (2) A composition according to claim 1, wherein an electron acceptor is also present as an oxidizing agent for the substance polymerizable by cationic polymerization. A composition according to claim 1 or claim 2, wherein the composition is present in an amount of %. (4) The composition according to claim 3, wherein the weight ratio of the iron compound b) and the oxidizing agent d) is 1:10 to 5:1. (5) The sensitizer C) is 0% of the amount of the polymerizable substance.
A composition according to claim 1, wherein the composition is present in an amount of 1% to 10% by weight. (61R' is the same or different halogen atom or 01
~C□2 alkyl group, C2~C□2 alkenyl group, C-
C alkynyl group, C, ~ C8 alkoxy 2 12 group, cyano group, C1 ~ C8 alkylthio group, 02 ~ C6
Claim 1, which is η6-benzene mono- or polysubstituted with a monocarboxylic acid ester group, phenyl group, C2-C5 alkanoyl group or benzoyl group
Compositions as described in Section. +7) C1-C8 alkyl group, C2-C8 alkenyl group, C2-C8 alkynyl group, where R2 is the same or different;
C2-C6 monocarzenate group, cyan group, C2
The composition according to claim 1, which is a cyclopentagenyl anion mono- or polysubstituted by a ~C5 alkanoyl group or benzoyl group. (8) Claim 1 in which a is 1 in formula I
Compositions as described in Section. (9) In formula ■, m is 6 and L is B, P, As or Sb
, Q is F and q is 1. 00) In formula (■), R1 is benzene, toluene, xylene, cumene, mesitylene, chlorobenzene, chlorotoluene, anisole, dimethoxybenzene, biphenyl,
The composition according to claim 1, which is 1-decylbenzene or tetralin. The composition according to claim 1, wherein UD in formula 1 is R2 cafuclopentagenyl or methylcyclopentagenyl anion. A composition according to claim '1, wherein R2 said oxidizing agent d) is an organic hydroperoxide, an organic peracid or a quinone. α9 The oxidizing agent d) is tert-butyl hydroperoxide, cumene hydroperoxide, trinoenylmethyl hydroperoxide, tetralin hydroperoxide, α-methyltetralin hydroperoxy P, decalin hydroperoxide, perbenzoic acid, m- The composition according to claim 12, which is chloroperbenzoic acid or benzoquinone. I @ Nun Sensitizer C) monocyclic or polycyclic aromatic or heteroaromatic hydrocarbons, phenones, especially acetophenone and benzophenone, benzyls, stilbenes, polyacetylenes, xanthones and thioxanthones 2. A composition according to claim 1, selected from the group consisting of anthracenes, phthalimides, especially phthalimi P-thioethers and diones having adjacent CO groups. 15. A composition according to claim 14, wherein said sensitizer C) is a thioxanthone, a phthalimide, a coumarin and, in particular, anthracene. uQ The composition according to claim 1, wherein the organic substance polymerizable by cationic polymerization is an epoxy resin. (17) The composition according to claim 1, wherein the substance polymerizable by free radical polymerization is a monoethylenically or polyethylenically unsaturated compound. R81 according to claim 17, wherein the substance polymerizable by free radical polymerization is a partial ester of an epoxy resin with acrylic acid, methacrylic acid or a mixture of these acids, or an acrylic ester or methacrylic ester of a polyol. Composition. a) a substance polymerizable by free radical polymerization or cationic polymerization; b) at least one iron compound consisting of the following formula I (where a is 1 or 2, q is 1, 2 or 3, and L is Bivalent~
Heptavalent metal or nonmetal, Q is a halogen atom, m is an integer corresponding to the sum of the valence of L and the value of q, R1 has a substituent or has a substituent η6-benzene, and R2 has a substituent or C) at least one sensitizer for the compound of formula (1) and which is polymerizable by free radical polymerization, further d) Applying the composition containing the electron acceptor as an oxidizing agent as a layer, irradiating it with radiation through a photomask, heating if necessary 1 and then removing the unexposed areas with a developer solution. Characteristic method for forming photographic relief images.