JPS589936B2 - Photopolymerizable composition - Google Patents

Description

[Detailed description of the invention] The present invention relates to photopolymerizable compositions.

Traditional polymeric imaging systems are for negative polymeric images.

That is, a photopolymerizable coating is exposed to radiation through a process transparency and a negative polymeric image is produced.

[Negative polymeric image] means a polymeric image that corresponds to the transparent portion of a process transparency.

In recent years, methods have been developed that provide positive polymeric images.

One such system is described in Belgian patent no. 818,37.
It is stated in No. 1.

This method is (a) Substrate (1) to (3) below, i.e. (1)
a non-gaseous, ethylenically unsaturated polymerizable compound; (2) an organic radiation-sensitive free radical generating system in an amount of 0.001 to 1.0 parts by weight per part of the polymerizable compound; and (3) a photopolymerizable composition. 0.1-10% by weight based on the product
(b) exposing the photopolymerizable coating through a process transparency to radiation having a wavelength of less than 3400 Å, at least some of which is thereby exposed to the irradiated portions; dissociating the nitrosodimer into polymerization-inhibiting nitrosomonomers, and (C) exposing the majority of the photopolymerizable coating to radiation substantially limited to wavelengths greater than 3400 Å, such that the initial imagewise radiation is The second irradiation, which was not received, consisted of forming a positive polymeric image in the area that was received.

Although this approach can produce excellent positive polymeric images, it involves time constraints.

That is, the second exposure must be performed immediately after the first imagewise exposure, since the nitrosomonomers formed during the first exposure can recombine to form inactive nitrosodimers.

It would also be desirable to develop a system that does not rely on exposure to such short wavelength radiation.

Another method for producing positive polymeric images is disclosed in U.S. Pat.
, 5 5 6, 7 9 4.

In this system, in combination with the above components, namely (1) an ethylenically unsaturated monomer, (2) a photoinitiator system consisting of a photooxidant dye and a reducing agent for this dye, and (3) a carboxylate group, A photopolymerizable material consisting of an ionizable desensitizer having benzyl moieties is imagewise exposed to radiation in the wavelength range of 2000-4000 Å, thereby inhibiting polymerization by desensitization of the initiator system, and then this Photopolymerizable material 3800-7
Exposure to radiation in the 200 Å wavelength range forms a polymeric image in areas not exposed to imagewise radiation.

This approach has the disadvantage that the desensitizing effect of the desensitizer is only temporary.

The US patent states that the desensitization effect lasts "up to about 15 minutes or more" and in Example 1
The second exposure was performed 30 seconds after the imagewise exposure.

According to the invention, the following components are present: (a) a normally non-gaseous ethylenically unsaturated compound capable of addition polymerization by a free radical-initiated chain-head growth reaction; (b) 1 part by weight of component (a); Approximately 0.004 per hit
0.7 parts of the general formula (wherein Rl, R2, R3 and R4 are the same or different, H, OH, halogen, NO2, CN, carbon number 1 -
18 alkyl, alkoxy with 1-18 carbon atoms in the alkyl moiety, aryl with 6-18 carbon atoms, benzyl, halogen-substituted phenyl, polyether with 2-18 carbon atoms and 1-6 oxygen atoms , the number of carbon atoms in each alkyl is 1
-18 dialkylamino, thioalkyl having 1 to 18 carbon atoms in the alkyl portion, or thioaryl having 6 to 18 carbon atoms in the aryl portion, or Rl
, R2, R3 and R4 together form the residue of another benzene ring fused to the benzene nucleus, except that more than one of R1, R2, R3 and R4 R5 is H, alkyl having 1-18 carbon atoms, halogen, phenyl, or alkoxy having 1-18 carbon atoms in the alkyl moiety, and R6 is H10H, alkyl having 1-18 carbon atoms. alkyl, phenyl, or alkoxy having 1 to 18 carbon atoms in the alkyl moiety, provided that only one of R5 and R6 is H, or R5 and R6 together =0, =CH2, −0
-C H2-, 2N C6H,, =NC6H4N-(alkyl)2 (where each alkyl has 1-18 carbon atoms), -0-C2H4-0-, =N (wherein the hydrocarbylene group has 1 to 18 carbon atoms {herein, R8 and R9 are the same or different and are H or alkyl having 1 to 4 carbon atoms, and R7 and RIO are the same or different and are -CN, -COR11 (R11 is -5 alkyl) or -COOR12 (R12 is alkyl having 1 to 6 carbon atoms, which may contain an oxygen atom in the middle, alkenyl having 2 to 5 carbon atoms, or alkenyl having 2 to 5 carbon atoms)
or R7 and R8 or R9 and R10 may be taken together to complete a 6-membered carbocyclic ring containing a keto group]. and (c) an organic radiation-sensitive free radical-generating system that can be activated by actinic radiation in an amount of from about 0.001 to 10 parts by weight per part of component (a), including the nitroaromatic compounds described above. shall not significantly rearrange into free radical polymerization inhibitors)
A photopolymerizable composition containing the following is provided.

A positive polymeric image is prepared by: (1) coating a base layer with the photopolymerizable composition described above; (2) passing a portion of the photopolymerizable coating through an image-bearing transparency so that at least about 20% imagewise exposure to radiation having a wavelength of 200 to 380 nm, thereby rearranging at least some of the nitroaromatic compounds to nitrosoaromatics having polymerization-inhibiting properties; (3) the portions exposed during this imagewise exposure; A second exposure is performed on the coating in which the majority of the coating, including, is exposed to substantially controlled radiation at wavelengths greater than about 380 nm, thereby exposing the majority of the coating, including the It is produced on a substrate by a process consisting of forming a positive polymeric image in the areas not exposed during imagewise exposure.

The image formed in step (3) is formed by removing the non-polymerized portions of the photopolymerizable coating corresponding to the portions exposed to the imagewise radiation or by exposing the photopolymerizable coating to the imagewise radiation. The pigment toner is developed by differential adhesion of pigmented toner to the non-polymerized areas corresponding to the exposed areas.

Negative polymeric images can be produced by: (1) coating a base layer with the photopolymerizable composition described above;
) imagewise exposing a portion of this photopolymerizable coating through an image-bearing transparency to radiation limited to wavelengths substantially greater than about 380 nm, thereby depositing a negative polymer in the portions exposed to the radiation; on the base layer by a method comprising forming a shaped image.

In a preferred embodiment of the photopolymerizable coating composition, component (a) is an unsaturated ester of a polyol and an alpha-methylene carboxylic acid selected from the group consisting of acrylic acid and methacrylic acid; All groups have 1-6 carbon atoms, and component (C) has 38
0 nm or more up to 800 nm, more preferably 400-
= 600 nm and has an active radiation absorption band with a molecular extinction coefficient of at least about 50 and is selected from the group consisting of phenanthrenequinone and 2,4,5-IJ arylimidazole dimers.

Preferably, component (b) is about 0.04-0.0% of component (a).
．． present in an amount of 15 parts by weight, and component (C) is present in an amount of 15 parts by weight;
It is present in a proportion of about 0.01-2 parts by weight per part of a).

In a preferred embodiment of the method for producing positive polymeric images, at least about 30% of the radiation in the imagewise exposure is at a wavelength of about 200-380 nm, and the radiation in the second exposure is substantially less than about 380 nm. Approximately 8
00 nm, more preferably wavelengths of about 400-600 nm.

The present invention provides that certain nitroaromatic compounds in which the nitro group is ortho to the hydrogen-containing alpha-carbon substituent do not significantly retard or inhibit free radical polymerization in certain photopolymerizable systems, but about It is based on the discovery that it photochemically rearranges into nitrosoaromatic free radical polymerization inhibitors when exposed to radiation at wavelengths of 200-380 nm.

These nitroaromatic compounds are relatively unaffected by long wavelength radiation.

On the other hand, some radiation-sensitive free-radical initiators absorb longer wavelength radiation, especially in the presence of added sensitizers, and are present at concentrations greater than those at which inhibitory nitrosoaromatic compounds can be observed. If not, sufficient groups are supplied for polymerization of the polymerizable monomer.

Nitroso compounds, which are formed by irradiating the nitroaromatic compounds described above with short wavelength radiation, interfere with common free radical-induced polymerization reactions.

That is, when using the short wavelength region of the spectrum in the presence of nitrosoaromatic compounds, polymerization does not occur because an insufficient number of initiating and propagating free radicals are available.

Exposure of the compositions of the present invention to radiation at wavelengths greater than about 380 nm leaves the nitroaromatic compounds relatively unaffected;
The photoinitiator system acts to generate polymerization initiating groups.

These groups can undergo chain growth as usual,
Then polymerization occurs.

Polymerizable compounds suitable for use as component (a) of the photopolymerizable coating compositions of the present invention include U.S. Pat.
0 2 2 and Belgian Patent No. 769,694, which are normally non-gaseous ethylenically unsaturated compounds.

"Non-gaseous" refers to a compound that is not gaseous under atmospheric conditions.

The compound is preferably monomeric and has a boiling point at normal pressure of about 9
It has a temperature of 0°C or higher and contains at least one terminal ethylene group, and in some cases 2 to 5 terminal ethylene groups.

Monomers containing two or more terminal ethylene groups are particularly preferred.

Suitable polymerizable compounds include unsaturated esters of polyols, especially esters of polyols with α-methylenecarboxylic acid, such as ethylene glycol diacrylate, diethylene glycol cyacrylate, glycerin diacrylate, glycerin triacrylate, mannitol polyacrylate, sorbitol Acrylate, ethylene glycol dimethacrylate, ■,3-propanediol dimethacrylate, 1,2,4-butanetriol trimethacrylate, 1,1,1-trimethylolpropane triacrylate, triethylene glycol diacrylate, ■,4-cyclohexane diol diacrylate, ■,4-benzenediol dimethacrylate, pentaerythritol di, tri and tetra methacrylate, dipentaerythritol polyacrylate, pentaerythritol di, tri and tetra acrylate,
1,3-propylene diol diacrylate, ■,5-
Pentanediol dimethacrylate, molecular weight 200-4
000 polyethylene glycol bis-acrylates and methacrylates, unsaturated amides, especially amides of α-methylenecarboxylic acids, and amides of α,ω-diamines and oxygen-intervening ω-diamines, such as methylene bis-acrylamide, methylene bis-methacrylamide,
Ethylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, bis(γ-methacrylamidoproboxy)ethane and β-methacrylamidoethyl methacrylate, vinyl esters such as divinyl succinate, divinyl adipate, divinyl phthalate, terephthalic acid divinyl, sivinyl benzene-1,3-disulfonate and divinyl butane-1,4-disulfonate,
These include styrene and its derivatives, unsaturated aldehydes such as hexadienal, etc. and mixtures thereof.

Preferred polymerizable compounds (because of the good physical properties of compositions containing them) include the following:

N-phenyl-N-methylacrylamide, N-vinylphthalimide, diacetone acrylamide, N-vinylsuccinimide, p-xylylene diacrylate, 1,4-bis(2-acryloxyethyl)benzene, pentaerythritol triacrylate, 4 -acryloxybenzophenone, 4-methacryloxybenzophenone, N-(2-acryloxyethyl)succinimide, 1,
1,1-trimethylolpropane triacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,1.1-trimethylolpropane trimethacrylate, 4-acryloxydiphenylmethane, N- (2-acryloxypropyl)succinimide, 2,4-diacryloxybenzophenone, 4-(α,α
-Simethylbenzyl) phenyl acrylate, 3-acryloxybenzophenone, 2-acryloxybenzophenone, 2-acryloxy-4-octyloxybenzophenone, and mixtures thereof.

The most preferred polymerizable compound is an ester of alpha-methylene carboxylic acid selected from the group consisting of acrylic acid and methacrylic acid.

Many of the above polymerizable compounds undergo thermal polymerization, especially when stored for long periods of time or at elevated temperatures.

When such compounds are supplied commercially, they usually contain a small but effective amount of a thermal polymerization inhibitor.

This inhibitor may remain in the heptanomer when preparing the photopolymerizable coating composition of the present invention, as in the examples below.

In this case, the compositions obtained usually have satisfactory thermal stability.

Hydroquinone, methylhydroquinone, P
- Incorporation of thermal polymerization inhibitors, such as methoxyphenol, etc. in amounts up to 5% by weight of the monomers results in compositions with sufficient shelf life.

The photopolymerizable coating composition also contains a nitroaromatic compound of the general formula above.

In this formula, preferred alkyl groups are lower alkyl groups having 1 to 6 carbon atoms.

"Hydrocarbylene" in bis compounds has 1 carbon number
- Represents any divalent group consisting of only 18 carbons and hydrogen.

Representative groups include 0-, m- and P-phenylene, vinylene, 2-butynylene, 1,3-butadienylene, hexamethylene, octamethylene, octadecamethylene, naphthylene (1,2; 2,3; 1, 4; and 1, 5), etc.

It has been found that the nature of the R5 and R6 substituents of the nitroaromatic compound is of great importance.

Unsubstituted compounds in which R5 and R6 are H do not rearrange into photoinhibitors and are therefore ineffective.

Additionally, some R5 and R6 substituents render the CH moiety inactive against rearrangement.

For example, substituents commonly thought to destabilize positive charges such as nitro, cyano, carboxy and 2-pyridyl.

For example, it has been found that the method does not work according to the present invention.

Suitable di-aromatic compounds include:

0-nitrobenzyl alcohol, 0-nitrobenzaldehyde, α-phenyl 10-nitrobenzyl alcohol, 0-(
Diphenylmethyl)nitrobenzene, α-phenylimino O-nitrotoluene, α,α-diethoxy O-nitrotoluene, α,α-1ethylenecyoxy10-nitrotoluene, 3-methoxy-2-nitrobe/dualdehyde, 4-methoxy-2-nitrobenzaldehyde , 3,4-dimethoxy-2-nitrobenzaldehyde, 3,4-dimethoxy-2-nitrobenzyl alcohol,
4-cyano-2-nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 4-hydroxy-
3-methoxy-2-nitrobenzaldehyde, 1-nito-2-naphthaldehyde, 2,3,4,5-tetramethyl-6-nitrobenzyl alcohol, 3,4.5-1-lichloro-2-nitrobenzaldehyde, 3,5-dibromo-4,6-dichloro-2-nitrobenzaldehyde, 4 5-dimethoxy-2-nitrobenzyl alcohol, 4,5-dimethoxy-2-nitrobenzaldehyde, 2.4-)nitrobenzaldehyde, 5-tolyl-2- Nitrobenzaldehyde, 5-benzyl-2-nitrobenzaldehyde, 5-(m-'7-ruphenyl)-2-nitrobenzaldehyde, 4-(2-methoxyethoxy)-2-nitrobenzaldehyde, 4-ethoxyethyl-2- Nitrobenzaldehyde, 3-diethylamino-2-nitrobenzaldehyde, 4-butylthio-2-nitrobenzaldehyde, 4
-Phenylthio 2-nitrobenzaldehyde, 2-nitrostyrene, 4,5-dimethoxy-2-nitrostyrene, α-(p-
Dimethylamine phenyl) imino 2-nitrotoluene, 4,5-dimethoxy 2-nitro α-7 enyliminotoluene, 2-nitrostyrene oxide 2-nitrocumene, 4,5-dimethoxy 2-nitropenzyl chloride, α
, α-ethylenedioxy-2-ditrotoluene, N,N'-bis(4,5-dimethoxy-2-nitrophenylmethylene)1,6-hexanediamine, N,N'-bis(2,4-dinitro phenylmethylene)
-2,5-dimethyl-2,5-hexanediamine, N,N-bis(4,5-dimethoxy-2-ditrophenylmethylene)-1m-phenylenediamine N,N'-
Bis(4,5-dimethoxy-2-nitrophenylmethylene)-1P-phenylenediamine, N,N'-bis(4,
5-dimethoxy-2-nitrophenylmethylene)α,α
'-bee p-t'luisine,
IN,N bis(4,5-dimethoxy-2
-nitrophenylmethylene)4-4'-stilbendiamine, 2,6-dimethyl-4-(2'-ditrophenyl)-1
, 4-dihydropyridine-3,5-dicarboxylic acid dimethyl ester, 2,6-dimethyl-4-(2'-nitrophenyl)-1
．． 4-Sihydropyridine-3,5-dicarboxylic acid diethyl ester 2,6-dimethy/I/-4-(2'-ditro-4',5'-dimethoxyphenyl)1,4-dihydropyridine-3 , 5-dicarboxylic acid diethyl ester,
2,6-dimethy/L/-4-(2'-ditrophenyl)-1,4-dihydropyridine-3,5-dicarboxylic acid di-m-probyl ester, 2,6-dimethy/L/-4 - (Diisopropyl ester of 2'-nitrophenyl-1,4-dihydropyridine-3,5-dicarboxylic acid, 2,6-dimethy/L/-4-(2'-nitrophenyl)
-1,4-dihydropyridine-3,5-dicarphonic acid di(β-ethoxyethyl) ester, 2,6-dimethy/
I/-4-(2'-nitrophenyl)-1,4-dihydropyridine-3,5-dicarboxylic acid diallyl ester, 2,6-dimethyl-4-(2'-nitrophenyl)-1
, 4-dihydropyridine-3,5-dicarboxylic acid dipropargyl ester, 2,6-dimethyl-4-(2'-nitrophenyl)-1
, 3- of 4-dihydropyridine-3,5-dicarboxylic acid
Methyl-5-ethyl ester, 2,6-dimethyl-4-
3-isopropyl-5-methyl ester of (2'-nitrophenyl)-1,4-dihydropyridine-3,5-dicarboxylic acid, 4-(2'-nitrophenyl)2,6-dimethyl-3-aceto 1, 4-dihydropyridine-5-
Ethyl ester of carboxylic acid, 2,6-dimethy/I/-4-(2'-1 ditrophenyl)-3,5-diaceto-1,4-dihydropyridine, 2-methyl-4-(2'-nitrophenyl)- 1
, ethyl ester of 4,5,6,7,8-hexahido-5-oxoquinoline-3-carboxylic acid, 2-methyl-
4-(2-nitrophenyl)-1,4,5,6,7,8
-Hexahydride-5-oxoquinoline-3-carboxylic acid methyl ester, 2-methyl-4-(2'-nitrophenyl)-1,4,5,6,7,8-hexahydride-5
-Isoprobyl ester of oxoquinoline-3-carboxylic acid, 1,2,3,4,5,6,7,8,9,10-tecahyde-9-(2'-nitrophenyl)-1,8-di Oxoacridine, and 1,2,3,4,5,6,7,8,9,10-decahyde-3,3,6.6-tetramethyl-9-(2'-nitrophenyl)1,8-dioxo Acridine.

The nitroaromatic compound is normally used in a proportion of about 0.004 to 0.7 parts by weight per part of polymerizable compound.

The preferred amount in a particular case will depend on the type of monomer/radical generating system used.

Generally, the preferred amount of nitroaromatic compound used is from about 0.04 to 0.15 parts by weight per part of polymerizable compound.

The third component that the photopolymerizable coating composition must contain is an organic radiation-sensitive free radical generating system that initiates and then does not terminate the polymerization of the monomers.

The term "organic" refers to compounds containing carbon and one or more atoms of oxygen, hydrogen, nitrogen, sulfur and halogen, but no metals.

This free radical-generating system has an approximately 200-80
Absorbs activating radiation at wavelengths in the 0 nm range.

"Activating radiation" means radiation that is active toward the generation of free radicals necessary to initiate polymerization of monomeric materials.

A free radical generating system consists of one or more compounds that directly supply free radicals when activated by radiation.

It may also consist of a plurality of compounds, one of which forms free radicals after being acted upon to provide free radicals by a sensitizer activated by radiation.

Preferably, the free radical generating system has a molecular extinction coefficient of at least about 5 in the range of greater than about 3 8 O nm to about 800 nm, more preferably in the range of about 400 to 600 nm.
It contains at least one component having a zero radiation absorption band.

A large number of free radical-generating compounds can be used in the practice of this invention, including aromatic ketones such as penzophenone, Michler ketone (4
, 4'-bis(dimethylamino)penzophenone),
4,4'-bis(diethylamino)penzophenone, 4
-Acryloxy-47-dimethylaminobenzophenone, 4-acryloxy-4'-dimethylaminobenzophenone, 4-methoxy4'-dimethylaminepenzophenone, phenanthrenoquinone, 2,7-ditertiary butylphenanthrenequinone, and other aromatic ketones,
Benzoin ethers such as benzoin methyl ether, benzoin ethyl ether and penzoin phenyl ether, methylbenzoin, ethylbenzoin and other benzoin compounds, 2,4,5-triarylimidazole dimers such as 2-(0-chlorophenyl)-4 ．． 5-diphenylimitasol dimer,
2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2,2'-bis(2
-chlorphenyl) -4, 4', 5, 5
'-Tetrakis(3-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4.5-diphenylimitasol Amount L 2-(o-methoxyphenyl)-4.5-diphenyl Enylimidazole dimer, 2
(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4-di(p-methoxyphenyl)
-5-phenylimidazole dimer, 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazole dimer, 2(p-methylcabutophenyl)-4,5-diphenylimidazole U.S. Patent No. 3,47 for Dimer etc.
No. 9,185 and British Patent No. 997,396
No. 1,047,569.

The imidazole dimer is Michler's ketone, 2,5-bis(4'-diethylamino-2'-methylbenzylidene)
It can also be used with hydrogen donors such as 2-mercaptobenzoxazole or 2-mercaptobenzothiazole, with or without the presence of sensitizers such as cyclopentanone and various dyes.

Another example of a suitable initiator is U.S. Pat. No. 2,760,8
6 Described in Specification No. 3.

Redox systems, especially those containing dyes, can also be used.

This includes Rose Bengal.
/2-dibutylaminoethanol, 2-o-chlorophenyl-4. 5-cy(m-methoxyphenyl) imidazole dimer/2-mercaptohensuoxazole, 2-o-chlorphenyl-4,5-di(m-methoxyphenyl) imitasol dimer/2-mercaptobenzothiazole, etc. There is a combination of

Preferred free radical generating systems characterized by high efficiency include phenanthrenequinone and 2,4.5-}ryarylimidazole dimers, particularly in the presence of sensitizers, 2-mercaptobenzoxazole and 2-mercaptobenzoxazole. −
Preferably, it is used with or without a hydrogen donor such as mercaptobenzothiazole.

The concentration of the free radical generating system is from about 0.001 to 10.0 parts, preferably about 0.01-10.0 parts by weight, per part of polymerized compound.
It is 2.0 parts.

The coating composition of the present invention may further contain other components as desired.

For example, coatings contain thermoplastic macromolecules (macromol).
ecul ar) may be of the monomer/binder type further containing an organic polymeric binder.

The coating may also be of the substantially dry, predominantly crystalline type described in Belgian Patent No. 769,694.

In this case, the coating, in addition to a suitable nitroaromatic compound,
It contains a solid ethylenically unsaturated polymerizable compound, an organic radiation-sensitive free radical generating system, and a non-polymeric normally liquid or solid organic substance that does not inhibit polymerization.

Thermoplastic macromolecular organic polymer binders suitable for use in monomer/binder systems are described in U.S. Patent No. 3.661.
5 8 8, which comprises (a) copolyesters based on terephthalic acid, isophthalic acid, sebacic acid, adipic acid and hexahydroterephthalic acid, (b) nylon or polyamide, (c) Vinylidene chloride copolymer, (d) ethylene/vinyl acetate copolymer, (e) cellulose ether, (f) polyethylene, (g) cold rubber, (ht senolose ester, (i) polyvinyl acetate/acrylate and polyvinyl acetate/ Polyvinyl esters including methacrylate copolymers, (j) polyacrylates and polyα
- alkyl acrylate esters such as polymethyl methacrylate and polyethyl methacrylate, (k) high molecular weight ethylene oxide polymers (polyethylene glycol) with an average molecular weight of 4000-4,000,000, (1) polyvinyl chloride and copolymers, (m )
polyvinyl acetal, (n) polyformaldehyde,
Includes such types of polymers as (o) polyurethane, (p) polycarbonate, and (q) polystyrene.

In particularly preferred embodiments of the invention, the polymeric binder is selected such that the unexposed photopolymerizable coating is soluble in primarily aqueous solutions (e.g., dilute aqueous alkaline solutions), but when exposed to activating radiation. This is done so that it is relatively insoluble in this.

Typically, polymers that meet this requirement are carboxylated polymers, such as vinyl addition polymers containing free carboxylic acid groups.

Other preferred binders include polyacrylate esters and polyalpha-alkyl acrylate esters, especially polymethyl methacrylate.

If a monomer/binder is used, the amount of polymeric binder is about 10-80% by weight, preferably about 25-75% by weight, based on total solids content.

Polymerizable compounds containing ethylenically unsaturated bonds at only one site are generally unsuitable for use in monomer/binder systems.

When the substantially dry, predominantly crystalline system described in Belgian Patent No. 769,694 is used as an embodiment of the present invention, the system inhibits polymerization of polymerizable materials in addition to polymerizable compounds. a normally liquid non-polymeric organic compound that does not absorb incident radiation in sufficient quantities to prevent initiation of polymerization by free radical-generating systems, per part by weight of polymerizable compound. It can be contained in a proportion of .25 parts.

In another aspect of the invention, the system comprises a non-polymerizable crystalline organic solid by weight that does not inhibit polymerization of the polymerizable compound and does not absorb incident radiation to an extent that prevents initiation of polymerization by the free radical generating system. It may be present in a proportion of about 0.01-250 parts per part of polymeric compound.

Representative examples of suitable organic compounds that may be added include octadecanol, triethanolamine, stearic acid, cyclododecane, 1,10-decanediol, dimethylaminobenzonitrile, acetone oxime, desoxybenzoin, naphthalene, N , N'-dimethylhexamethylenediamine, p-diethoxybenzene, ■,2-diphenylethane, biphenyl, dotriaconcune, tetramethylurea, tributylamine, 2-dimethylaminoethanol, pentamethylbenzene, 1,12-dodecanediol, l,2-diphenoxyethane, octacosane,
Examples include trichlorooxylene and cyclododecanol.

Preferred examples of solid compounds include hbenzyl, biphenyl, l,2-diphenoxyethane, p-diethoxybenzene, octacosane, l-octadecanol and cyclododecanol.

The photopolymerizable compositions of the present invention can be coated onto a wide variety of substrates.

By "base layer" is meant any natural or synthetic support, preferably flexible or rigid, which can be present in the form of a film or sheet.

For example, the base layer may be a metal sheet or foil, a synthetic organic resin sheet or film, cellulose paper,
It is a fiber board or the like or a composite made of two or more of these materials.

Specific base layers include alumina-blasted aluminum, alumina-blasted polyethylene terephthalate film, polyethylene terephthalate film, polyvinyl alcohol-coated paper, cross-linked polyester-coated paper, nylon, glass, acetyl cellulose film, and heavy-duty materials such as lithographic printing paper. There are quality papers etc.

The particular substrate will generally be determined by its intended use.

For example, the compositions and methods of the present invention are particularly useful in the manufacture of printed circuits using copper-clad plates on fiberboard as the base layer.

When the photopolymerizable composition is applied onto a metal surface, it is useful in making presensitized lithographic printing plates.

For example, such printing plates can be made from a combination of a grained aluminum substrate and a photopolymerizable coating.

After the image has been developed, the printing plate is first applied with water and then brought into contact with a roller that wets only the photopolymer image with ink.

The inked plate can be used for lithographic printing in the conventional manner.

Preferably the base layer is impermeable to oxygen.

The applied composition is useful as a photoresist in the fabrication of eroded or plated circuits or in chemical milling applications.

This composition also has color blueing (co l
It can also be used to prepare color images from color separation negatives suitable for color separation.

Images formed using these elements can also be used to make copies by thermal transfer to a substrate; specific applications will be apparent to those skilled in the art, and there are numerous applications for positive images on a substrate. is U.S. Patent No. 2,76
No. 0,863, No. 3.06 0,023, and No. 3,060,026.

Methods for coating the base layer are described in the three US patents mentioned above.

Methods using substantially dry, primarily crystalline type coating compositions can be categorized into five general methods:

(1) the components of the coating composition are melted together to form a generally homogeneous melt which is applied onto the substrate; (2) the components of the coating composition are preferably melted together to form a generally homogeneous melt; (3) dissolving each component of the coating composition in a volatile solvent and dissolving the resulting solution together in a solvent in which it is completely soluble and casting or coating the resulting solution onto the substrate; (4) melting the components of the coating composition together and spraying the melt as a fine mist onto the substrate; (5) cooling each component of the coating composition; A method in which the components are mixed together in a heated vessel (where the distance from the mixture to the cooling surface can be varied) with an inner surface of

Details of these methods can be found in Belgian Patent No. 769,6 mentioned above.
It is described in the 94th Moebisho.

A preferred coating method is a solution coating method as described in item 2) above.

One of the features of the photopolymerizable coating composition of the present invention is that
It can be used to prepare both positive and negative polymeric images.

Positive polymeric images are prepared by a two exposure process, whereas negative polymeric images are prepared by a single exposure process.

The compositions of the invention are exposed to radiation at wavelengths in the range 200-800 nm.

Suitable radiation sources include, in addition to sunlight, carbon arcs, mercury vapor arcs, fluorescent lamps containing ultraviolet-producing fluorescers, argon and xenon glow lamps, electronic flash devices, and photographic light bulbs.

Other sources of fluorescent radiation can also be used, such as tracing on the surface of a cathode ray tube.

Electron accelerators and electron beam sources through appropriate masks can also be used.

When using an artificial radiation source, the distance between the photosensitive layer and the radiation source can be varied depending on the radiation sensitivity of the composition and the nature of the photopolymerizable polymer.

Typically, a mercury vapor arc is used at a distance of 1.5-20 inches (3.8-50.8 cm) from the photopolymerizable layer.

It is generally appropriate to use a dose of 10-10,000 μw/CrrL2.

For the first exposure when preparing a positive polymer image,
Although radiation with a wavelength of approximately 200-380 nm is used, there is no need to limit the wavelength to this range.

The wavelength of the radiation may span the entire range of about 200-800 nm.

To generate an effective amount of inhibitor during the first exposure, at least about 20% of the radiation is in the range of about 200-380 nm, and preferably about 30% or more of the radiation is within this range. It is.

The radiation used during the second exposure is substantially around 380 nm.
should be limited to longer wavelengths.

By "substantially limiting" is meant exposing or otherwise limiting the radiation to wavelengths longer than about 380 nm so as to exclude about 95% or more of the radiation below about 380 nm.

Preferably, the wavelength of the second exposure radiation is greater than about 380 nm and up to about 800 nm, more preferably about 400 nm.
Practically limited to 600 nm.

All of the photopolymerizable compositions of the present invention have a minimum wavelength of about 38
Although it can be imaged with a second exposure of 0 nm, many nitroaromatic compounds absorb radiation far into the visible range, so filtering out wavelengths up to about 420 nm shortens the exposure time. It is commonly experienced that this is the case.

During the second exposure, a large portion of the coating, generally the entire surface of the coating, is irradiated.

As a result, free radicals are generated and polymerization occurs in areas that were irradiated during the second exposure but not during the first exposure.

The time the composition is exposed to radiation ranges from as low as a fraction of a second to a wide range.

Exposure times will also vary depending on the nature and concentration of the polymerizable composition and initiator, as well as the type of irradiation.

Exposure can be carried out over a wide range of temperatures, for example from about -80°C to about 1150°C for certain compositions.

Preferred exposure temperatures range from about -30°C to about +35°C.

It is clearly economically advantageous to carry out the treatment at room temperature.

For example, when preparing a printing plate, the first imagewise exposure is conveniently carried out by exposing a layer of photoactive composition to radiation through a process transparency.

That is, a process transparency may include an image-bearing transparency that consists of only substantially opaque and substantially transparent portions to the irradiation, the optical density of the opaque portions being substantially the same, e.g. Using so-called line or halftone negatives or positives.

Process transparencies may be constructed from any suitable material including acetyl cellulose film and polyethylene terephthalate film.

One example is the production of lithographic plates that act as positives using the novel method of the present invention.

In positive imaging systems, the polymer ultimately forms under the opaque portions of the process transparency, ie, in those areas that were not exposed to radiation passing through the process transparency.

When a plate coated with a photoactive composition containing nitroaromatics is exposed through the negative of an acetylcellulose or polyethylene terephthalate film to the full spectrum of a mercury vapor lamp, the irradiated area changes from nitroaromatics to nitrosoaromatics. A transition to occurs.

Polymerization cannot be initiated in the area that was irradiated during the first exposure, so this area becomes a non-image area.

After removal of the process transparency, a second exposure to radiation substantially limited to wavelengths longer than about 380 nm causes polymerization to occur in areas not exposed to radiation during the first exposure.

Irradiation at this wavelength is not absorbed by nitroaromatics to the extent that rearrangement to nitrosoaromatics occurs.

The coating on the areas thus exposed becomes a polymeric image area.

The double-exposed plate is developed to produce a solid printing plate suitable for use in lithography.

Development of the exposed photosensitive layer can be accomplished by removing unpolymerized ethylenically unsaturated compounds from the coating, leaving behind a polymeric replica of the original.

This can be accomplished by heating the coating under conditions such that all or part of the volatile components evaporate, leaving behind the photopolymer.

The thermal development conditions are selected depending on the nature of the base layer, the volatility of the components to be removed and the thermal stability of the components.

Alternatively, development can be performed by solvent washing, thermal transfer, pressure transfer, or a difference in adhesion between exposed and non-exposed areas.

Preferably, development of the polymeric image is accomplished by solvent washing.

Alternatively, development can be performed without washing by utilizing the differential adhesion of pigmented toner to sticky unpolymerized areas.

The photopolymerizable compositions of the present invention have the advantage that the same compositions used in the above-described two-exposure positive applications can also be used to form negative polymer images in a single exposure operation. .

For this application, a layer of the photopolymerizable composition containing the nitroaromatic compound described above is passed through the image-bearing transparency for about 30 minutes.
Exposure to radiation substantially limited to wavelengths longer than 80 nm until polymer formation occurs in the exposed areas.

The unpolymerized portions of the photopolymerizable layer are then removed by solvent washing or any other removal method described above, leaving a negative polymeric image of the pattern of the transparency used.

The photopolymerizable composition of the present invention can be used in the first step in a positive forming process.
It has the very distinct advantage that multiple imagewise exposures can be carried out using polyethylene terephthalate process transparencies.

This is possible because nitroaromatic compounds are sensitive to radiation at a wavelength of about 366 nm, which is easily transmitted through polyethylene terephthalate films.

Previously known sources of nitrone inhibitors in positive-acting photopolymerizable compositions require activation with radiation at wavelengths below about 330 nm, which wavelengths are blocked by polyethylene terephthalate films.

Therefore, the present invention can be used in the latest and most preferred image-bearing transparencies.

As used herein, the term "image" refers to an image representing a certain shape, and does not necessarily mean a visible image, as will be clear from the context of the specification to a person skilled in the art.
Please note that this does not mean

The method and composition of the present invention will be explained in more detail below using Examples.

Parts and percentages are by weight unless otherwise specified.

Example l (A) 3.5 ml of 1,1,1-trimethylolpropane triacrylate containing about 200 ppm of hydroquinone and/or methylhydroquinone inhibitor;
0.1532 F of 0-nitrobenzyl alcohol and 0.021 F of phenanthrenequinone were added.

A layer of the resulting clear solution was applied with a doctor knife to each of two glass microscope slides, and the coated slides were covered with polyethylene terephthalate film and another microscope slide.

The following exposures were performed at room temperature. (B) Slide one of the above slide assemblies through an image-bearing transparency at 275 watts. E. Exposure was made to total radiation from a sunlamp for 1 minute at a distance of 6 inches (15.2 cm).

This lamp produces radiation with wavelengths in the range 280-600 nm, approximately 40% of which is in the range 280-380 nm.

Upon exposure, o-nitrosobenzaldehyde was generated in the irradiated portions of the photopolymerizable layer.

The image-bearing transparency is then filtered with a filter (Dow Corning, 3
-73 filter) and the assembly was again exposed to the same lamp for 1 minute.

Thereafter, the polyethylene terephthalate film immediately above the photopolymerizable layer was peeled off.

The presence of a positive polymer image in areas that were not exposed during the first exposure (i.e., the areas underlying the opaque image on the transparency) was determined by gently sprinkling carbon black on this layer. did it.

The Rikibon Black adhered to the sticky, unpolymerized areas containing the 0-nitrobenzaldehyde inhibitor, and the dry areas that had polymerized during the second exposure remained clear.

(C) A second slide assembly was passed through the image-bearing transparency used in B and through the filter described in B to block and eliminate all radiation at wavelengths shorter than about 400 nm. A single exposure for 1 minute at a distance of 6 inches (15.2 crrL) was applied to radiation from a solar lamp.

Since phenanthrenequinone acts as an effective photoinitiator when irradiated with a wavelength of about 410 nm, the irradiated portion that passed through the door was polymerized.

Thereafter, the polyethylene terephthalate film immediately above the photopolymerizable layer was peeled off.

The presence of a negative polymer image in areas that were hit by radiation that passed through the transparency (e.g., areas that were not obscured by the opaque image of the transparency) was demonstrated by gently sprinkling this layer with carbon black. .

The carbon black adhered to the sticky unexposed areas, leaving the remaining dry polymerized areas transparent.

Examples 2-18 These examples demonstrate the utility of the compositions of the present invention in methods of forming images by photocuring and application of colorants.

A raw material solution containing the following components was prepared.

In all of the Examples except the Reference Example, an O-nitroaromatic compound (photoinhibitor) was used to prepare the coating solution.

The amounts of photoinitiator and photoinhibitor added, calculated as % based on the total solids in the coating solution, are shown in Table 1 below.

U.S. Patent No. 2,779,684 (Example 4)
O. which was coated with resin by the method of Each coating solution was applied to the resin surface of an I mm polyethylene terephthalate film at room temperature, and two coated samples were prepared.

When the coating film is dried at 55°C, the thickness of the dried coating film is 0.
It was 0076 mm.

A 0.025 mm polyethylene terephthalate cover sheet was laminated by pressure onto the coating at room temperature.

A set of films is subjected to conventional photopolymerization by exposure in a vacuum frame to radiation at wavelengths greater than about 380 nm through a step-wedge process transparency in which the radiation transmission between steps increases by a factor of -J2. determined the speed.

The irradiation source is 8. 1. A 1000 watt quartz monoiodide lamp placed at a distance of 2 cm and exposure times are shown in Table 1.

After exposure, the polyethylene terephthalate cover sheet was removed and a fine blue pigment toner was sprinkled onto the photopolymer surface.

When excess toner was removed with a cotton pad, a duplicate image of the stair wedge remained.

That is, the toner did not adhere to the polymerized portion, but only to the sticky unpolymerized portion.

In this way, the number of uncolored (ie, polymerized) steps found in the replicated image provides a relative comparison of the rate of photopolymerization in the presence of the 0-nitroaromatic compound.

The results are shown in Table 1 below.

Another set of films is first placed in a vacuum frame through the above steps (rust process transparency), with wavelengths ranging from 310 to 430 nm and approximately 88% being 310-380 nm.
exposed to radiation.

The illumination source for this first exposure was Sylvania Blacklight.
The device included 8 (model F15T8-BLB) lamps (model F15T8-BLB).

This was placed at a distance of 5.08 crfL from the sample film.

This exposure (see Table 1 for exposure times) is effective to generate aromatic nitroso inhibitors from the 0-nitroaromatics in the film in an amount inversely proportional to the optical density of the steps of the step wedge. be.

Therefore, if the process transparency is removed and the sample is exposed to activating radiation at wavelengths longer than 380 nm using the quartz monoiodide lamp described above, photopolymerization will occur only in areas where the concentration of nitroso inhibitor is negligible or low. It was.

Once the cover sheet is removed and the toner is applied as described above, a tacky blank will appear that corresponds to the steps (i.e., the lower numbered steps) that came to contain higher concentrations of nitroso inhibitor on the first exposure. Pigment adhered to the polymerized part.

The data obtained from this two exposure process is also shown in Table 1.

Examples 19-20 The following two examples demonstrate the applicability of the compositions of the present invention for the preparation of lithographic films.

In these Examples, the unpolymerized portion was completely removed by washing with an alkaline aqueous solution until it reached the underlying base layer.

The polymerized portion insoluble in this solvent was opaque due to the high concentration of colloidal carbon.

The film obtained could therefore be used as a photomask, such as a lithographic film, for the preparation of further copies.

A coating solution was prepared containing the following ingredients (%
is based on total solids《).

0 as in Example 2-18. Two coatings were prepared using a polyethylene terephthalate cover sheet with a thickness of 3 mm.

The thickness of the dried coating film was 0.005117171 mm.

The negative image forming method of these Examples is 1 of Example 2-18.
It was conducted in the same manner as the repeated exposure test.

Specifically, a set of films was exposed through an I'E step wedge to radiation at wavelengths longer than 380 nm for 90 seconds to determine the rate of conventional negative imaging photopolymerization.

The exposure device is a commercially available Nuerkyu vacuum frame (model FT26).
L), which contains 43.2 cIr from the polymerizable layer.
A 2000 watt pulsed xenon radiation source is located at a distance L.

Irradiation with wavelengths shorter than 380 nm was excluded by inserting a suitable filter between the irradiation source and the sample.

This used either Eastman Kodak Wratten Light filters IA or 2C.

After exposure, the cover sheet is removed and the unpolymerized steps are treated with Na 2 CO 3 and Na H
44.4 with a dilute aqueous solution of C O a (pH 9.3)
Washed at ℃.

The polymerized stages were easily visible to the naked eye due to the colloidal carbon dispersed within the photopolymer.

The positive image forming method of the composition was as follows in Example 2-18.
Irradiation from a black light blue lamp of the form described above (<380 nm) through a rust process transparency
), followed by a 90 second exposure to activating radiation (<380 nm) from the above-mentioned derusted pulsed xenon source, followed by a further 90 seconds of alkaline exposure as above. The measurement was carried out by development by washing with an aqueous solution.

The data obtained are shown in Table 2 below.

Table 2 Positive/Negative Image Formation Photopolymerization Speed Example Number Photo Inhibitor Positive Method 3 Negative Method 5 Control
8 19 2-2-5-methoxy 47 cy”b dinon-anole-co-no-re 20 α-phenynoreimino-2 3
5-nitrotonoleene a = total washed away (i.e. not polymerized), /7 number of steps in the step wedge.

b=Number of steps in all Jl step wedges that were not washed away (i.e. remained polymerized and black).

The above or similar composition was applied to the drafting film base layer described in U.S. Pat. No. 2,964,423 at 65°C.
Equally satisfactory results were obtained even when laminated with

In this way, clear black industrial reproduction films with positive or negative images, washed and developed, were produced.

Example 2l This example demonstrates the applicability of the composition of the present invention for the fabrication of photoresists.

A coating composition containing the following ingredients was prepared (
% based on total solids).

These ingredients were added to methibine chloride in an amount to give a 10% solids solution.

This solution was applied to polyethylene terephthalate with a thickness of 0.025 mm using a doctor knife and air-dried.

The dry coating thickness was approximately 0.038 mm.

This layer is described in U.S. Patent No. 3.469,982 (
It was laminated to a copper coated epoxy fiberglass board substantially as described in Example I (lines 46-55).

Positive and negative photocopies or laminates were evaluated by exposing the polyester film side through a J7 step Rust Process transparency as described in Examples 2-18.

Single exposure was 2 minutes to a quartz monoiodide lamp.

The dual exposures were 1 minute of radiation with a wavelength <380 nm, followed by 2 minutes of activation radiation with a wavelength >380 nm.

After exposure, the polyester film is removed and the replica (
The unpolymerized portions of the duplicate image) were dissolved away with a 15 second spray of t,i,i-trichloroethane, leaving a protective resist of the polymer on the copper surface.

In the single-exposure negative imaging system, the portion corresponding to the 1-6 step was polymerized (resist), and the portions below the subsequent steps were not polymerized.

In the double-exposure positive production method, the parts of the replica corresponding to the 1st to 4th steps of the staircase (rust) were clean copper surfaces, whereas polymerization occurred in the higher steps (resist).

As taught in US Pat. No. 3,469,982, both unprotected coppers could be corroded with ferric chloride.

The resist was then removed (eg, with CH2Ct2) to produce a printed circuit board where one side of the step wedge target was positive and the other side was negative.

Examples 22-24 These examples demonstrate the applicability of compositions of the invention containing various photoinhibitors to the preparation of lithographic films.

A raw material solution (solid content IO%) containing the following components was prepared.

The above raw material solution, 2,2'-bis(2-chlorophenyl)-4. 4', 5, 5'-tetraphenylbiimidazole (photoinitiator), 2,5-bis(4'-diethylamino-2'-methylbenzylidene)cyclopentanone (sensitizer) and as specified in Table 3 A coating solution was prepared using the photoinhibitor mixture prepared.

The amounts of photoinitiator and sensitizer are stated relative to the total solids content.

Two coatings were prepared using a method similar to that used in Examples 19-20.

The coating was air-dried for 30 minutes at room temperature, and a polyethylene terephthalate Hersheet film was applied to the coating at 65.6°C by 0.91 m/min.
I put them together at the speed of minutes.

The thickness of the coated film after drying was approximately 0.005 mm.

The negative imaging system was tested as described in Examples 19-20 using a Numark 2000 Watt xenon source and a Wratten 2C filter to exclude radiation shorter than 380 nm.

Exposure times are shown in Table 3.

After exposure, remove the cover sheet and remove the unpolymerized column by 25.
Dilute solution of Na2CO3 (pH = 9.3) at 5 °C
After that, it was washed with water at 32° C. while being rubbed lightly with a sponge.

Table 3 shows the number of stages polymerized. Positive imaging of the composition was performed first through the step-wedge process transparencies of Examples 2-18 with unfiltered radiation from a Nuark 2000 Watt xenon source containing approximately 25% radiation below 380 nm. exposure, and then the radiation from the pulsed xenon source described above was filtered through an ultraviolet filter at 38°C.
The test was carried out by total exposure to activating radiation limited to wavelengths shorter than 0 nm, followed by washing away using an aqueous alkaline solution which completely removes the unpolymerized parts down to the base layer.

The polymerized portion that was insoluble in the solvent was opaque because it contained a high concentration of colloidal carbon.

Table 3 shows the first exposure time.

The exposure time for the single exposure negative imaging method and the second exposure time for the two exposure positive imaging method were the same times specified in Table 3.

a=Number of unwashed (i.e., not polymerized) steps of all J7 step wedges/Number of steps that were not completely polymerized; /Incompletely Polymerized Plate Number Example 25 This example demonstrates the use of compositions of the present invention for the preparation of positive image lithographic printing plates similar to those described in U.S. Pat. No. 3,458,311. Demonstrate applicability.

A photosensitive composition containing the following components was prepared.

Each component was added in such amounts as to yield a solution with a solids content of 18.6%.
- A coating solution was prepared by dissolving in ethoxyethanol.

This solution was spin coated onto an anodized aluminum plate and dried at 38° C. The weight of the dry photopolymerizable coating was 20.4 mii'/am2.

After cooling to room temperature, the coated aluminum plate was coated with polyvinyl alcohol (medium viscosity, degree of hydrolysis 87-89
%) aqueous solution (10% solids) was used to overcoat the oxygen barrier polymer.

Also, when dried at 38℃, this overcoat (top coat)
The weight of is 1 8. ,9mv2.

Example 22 shows the negative and positive production method of this plate.
- Jl from the overcoat layer side as described in 24.
The step wedge process was evaluated by exposure through a transparency.

Exposure times are shown in Table 4.

After exposure, the overcoat layer and the unpolymerized stage were washed away at 22° C. with a solution of sodium carbonate (1.8%) and diethylene glycol monobutyl ether (8%) in distilled water (development).

Development was completed in 60 seconds at 25°C.

The plates were then rinsed with water while being gently rubbed with cotton, and blotted dry.

The results obtained are shown in Table 4. The overlapping areas of the magnified plate accepted conventional grease-like lithographic inks, and the underlying areas of the aluminum support from which unpolymerized material had been removed were easily wetted by water, resulting in a high quality lithographic plate.

Example 26 Example 25 was repeated, but the photosensitive composition was the same as Example 25.
In addition to the components present in It further contained N,I'(-dioxide.

The resulting printing plate containing a lower amount of a better thermal polymerization inhibitor had an increased shelf life and improved thermal stability compared to the plate of Example 25.

The photopolymerization rates obtained are shown in Table 4.

Example 27 This example demonstrates the applicability of the compositions of the present invention for the preparation of positive image printing relief plates similar to those described in US Pat. No. 2,923,673.

After mixing the above ingredients, the composition was placed in a rubber mill preheated to 100°C and milled for about 5 minutes into a homogeneous mass.

This mass was placed on an anodized aluminum plate using a lamination press at 118°C and 40,00°C.
2 at 0 ps i (2800 kVcrIl2)
The mixture was pressed for a minute to form a photopolymerizable layer or film having a thickness of 0.040 inches.

During this lamination, a thickness of 0.004 inch (o.o.ic.
A flame-treated polyethylene terephthalate film (r/L) was laminated as a cover sheet.

The resulting element was then placed in a vacuum frame and the polymer side was brought into contact with the line negative original.

The elements were then exposed in a positive exposure mode as described in Examples 19-20, except that the imagewise exposure to <380 nm O radiation from a Black Lyle Blue lamp was 4.
．． It was 5 minutes.

After that, the transparent original image was removed and the element was replaced with Example 19-
Total exposure was for 4 minutes to >380 nmO active radiation from a pulsed xenon source, which was passed as described in [20].

After exposure, remove the cover sheet and heat the element to 41℃.
Developed for 3 minutes by spraying with NaOH:water solution (0.04N).

A positive ridge was obtained with raised photopolymer areas corresponding to the opaque areas of the negative original.

The depth of this letterpress is 0.025 inch (0.06 inch).
crrL), and the depression corresponded to the transparent part of the negative original.

Example 28 This example demonstrates the applicability of the compositions of the present invention for the preparation of positive image thin film resists particularly useful for microelectronic semiconductor wafers.

A photosensitive composition containing the following components was prepared.

A coating solution of the above components was prepared by dissolving them in an amount of 1.1.2-}lichloroethane to give a 15 part solids solution.

This solution was mixed with 0.0012mm thick silica (
S t 02 ) coated on a silicon wafer with a surface layer.

The coating film was prepared using a spin coater at room temperature.

Operating the coater at approximately 250 rpm for 45 seconds results in a thickness of approximately 0.0001 inch (0.0025 mm).
A dry photopolymerizable layer or film was obtained.

The coated wafer was exposed to a 200 watt, 4 inch (10 crfL) high pressure mercury arc lamp (Qriel Model 8) from a distance of approximately 13 inches (33 crfL) in a vacuum frame.
010) through the resolution test target (1951 U.S. Air Force standard), the irradiation of <380■
-6 second imagewise exposure.

The test target was then filtered through an ultraviolet filter (Example I).
9-20) and the photopolymerizable layer was exposed to >380 nm radiation from an Oriel source for 4 minutes.

The unpolymerized portion of the layer corresponding to the transparent portion of the test target was
A mixture of l,1.1-}lichloroethane and ingropanol (volume ratio 90/I
It was removed by spray development for 30 seconds using O ), then sprayed with the above mixture and naphtha for 5 seconds, and finally with naphtha alone for 10 seconds.

The resulting resist exhibited a resolution of 228 pairs/h, an exact replica of the highest resolution obtained by the test target.

After baking the resist at 120° C. for 1 hour, the resist-protected silica-coated silicon wafers were etched at room temperature for 12 minutes.

The corrosive liquid is ammonium fluoride aqueous solution (40%) 210ml
, 3 oy of concentrated hydrofluoric acid (49.z%) and 0.0 oz of fluorocarbon surfactant FC-95 (product of 3M Company).
It consisted of 5rnl of 2nd section aqueous solution processing.

The corroded wafer was washed with water and dried.

Protective resist with caroic acid at 140-150℃ for 30
After peeling for a minute, a pattern of silica was formed on the silicon wafer.

Claims (1)

[Scope of Claims] 1. The following components: (a) a normally non-gaseous ethylenically unsaturated compound capable of undergoing addition polymerization by a chain growth reaction initiated by free radicals; (b) component (a) by weight; ) 0.004 to 0 per part
．． 7 parts of the general formulas R1, R2, R3 and R4 are the same or different,
H, OH, halogen, N02, CN, alkyl having 1 to 18 carbon atoms, alkoxy having 1 to 18 carbon atoms in the alkyl moiety, noaryl having 6 to 18 carbon atoms, benzyl, halogen-substituted phenyl, 2 to 18 carbon atoms Polyether with 18 carbon atoms and 1 to 6 oxygen atoms, dialkylamino in which each alkyl has 1 to 18 carbon atoms, thioalkyl in which the alkyl moiety has 1 to 18 carbon atoms, or aryl moiety has 6 to 1 carbon atoms
8 thioaryl, or R1, R2, R3
and R4 together form the residue of another benzene ring fused to the benzene nucleus, provided that OH is N02 for R1, R2, R3 and R4. R5 is H, alkyl having 1 to 18 carbon atoms, halogen, phenyl, or alkoxy having 1 to 18 carbon atoms in the alkyl moiety, R6 is H, OH, or alkoxy having 1 to 18 carbon atoms; ~18 alkyl, phenyl, or alkoxy having 1 to 18 carbon atoms in the alkyl moiety, provided that only one of R5 and R6 is H, or R5 and R together =0, =CH2,
-0-CH2-, = N C6H5, = NC6H4N(
alkyl) 2 (wherein each alkyl has 1 to 18 carbon atoms), (wherein the hydrocarbylene group has 1 to 18 carbon atoms)
Here, R8 and R9 are the same or different and are H or alkyl having 1 to 4 carbon atoms, and R7 and RIO are the same or different and are -CN, -COR11 (R11 is alkyl having 1 to 5 carbon atoms) Or - COOR12 (
R12 has 1 to 6 carbon atoms in which an oxygen atom may be present;
alkyl, alkenyl having 2 to 5 carbon atoms, or alkynyl having 2 to 5 carbon atoms,
7 and R8 or R9 and RIO may be taken together to complete a 6-membered carbocyclic ring containing a keto group] and produce a polymerization inhibitor upon exposure to radiation. a nitroaromatic compound, and (C) activating irradiation without significantly converting the nitroaromatic compound into an inhibitor of free radical polymerization in an amount of from 0.001 to 10 parts by weight per part of component (a). 1. An imaging photochromic coating composition characterized in that it contains an organic radiation-sensitive free radical generating system that can be activated by. 2. The composition according to claim 1, wherein component (c) contains at least one component having an active radiation absorption band with a molecular extinction coefficient of at least 50 within a range of greater than 380 nm to 800 nm. 3. The composition of claim 2 further comprising 10 to 80% by weight, based on total solids content, of a polymeric binder. 4. The composition according to claim 3, wherein component (a) is an ester of a polyol and an ethylenically unsaturated carboxylic acid having an α-methylene group. 5. The composition according to claim 4, wherein the ethylenically unsaturated carboxylic acid having an α-methylene group is selected from the group consisting of acrylic acid and methacrylic acid. 6 Component (C) is 0.01 per part of component (a) by weight
6. A composition according to claim 5, wherein the composition is present in an amount of ~2 parts. 7 Component (C) is phenanthrenequinone and 2,4,
7. The composition of claim 6, comprising a compound selected from the group consisting of 5-triarylimidazole dipolymers. 8 Component (b) is 0.04 per part of component (a) by weight
7. A composition according to claim 6, wherein the composition is present in an amount of ˜0.15 parts. 9. The composition according to claim 8, wherein the alkyl group in component (b) has 1 to 6 carbon atoms. 10. The composition of claim 9, wherein the polymeric binder is selected from the group consisting of vinyl addition polymers containing free carboxylic acid groups, polyacrylate esters, and poly(alpha-alkyl acrylate esters). 11. The composition according to claim 10, wherein component (c) contains at least one component having an active radiation absorption band with a molecular extinction coefficient of at least 50 within the range of 400 to 600 nm. 12 Component (a) is trimethylolpropane triacrylate, component (b) is 2-ditro-4,5-dimethoxybenzaldehyde, and component (C) is 2,2
-bis(2-chlorophenyl)-4. 4', 5
, 5'-tetraphenylbiimidazole. 13 component (b) is capable of being rearranged to a nitroso aromatic compound having polymerization inhibiting action upon imagewise exposure to radiation with a wavelength of 200 to 380 nm;
c) is the wavelength of the radiation used for the second exposure 38
At least one component having an active radiation absorption band with a molecular extinction coefficient of at least 50 within the range of 0 to 800 nm.
A composition according to claim 1 for forming a positive image, containing seeds.