JPH087437B2 - Photopolymerizable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention comprises a photopolymerizable compound containing an unsaturated monomer, a photopolymerization initiator, and an organic boron compound, and optionally a linear organic polymer. The present invention relates to a composition, in particular, a highly sensitive photopolymerizable composition that can be used for producing a printing original plate, a resist or photomask for producing a printed circuit board, a black and white or color transfer coloring sheet and a coloring sheet. Is.

[Conventional technology]

A photosensitive composition prepared by mixing a polymerizable ethylenically unsaturated compound, a photopolymerization initiator, a linear organic high molecular polymer having a proper film-forming ability as necessary, a thermal polymerization inhibitor, etc. A method of reproducing an image by a photographic method as an object is widely known at present. That is,
As described in JP-A-35-5093, JP-B-35-8495 and the like, the photosensitive composition undergoes photopolymerization upon irradiation with an actinic ray to become insoluble. Therefore, the photosensitive composition is formed into an appropriate film, the active light is irradiated through the negative image of the desired image, and only the unexposed area is removed with an appropriate solvent (hereinafter simply referred to as development). A superimposed image can be formed. This type of photosensitive composition is extremely useful as a photosensitizer for printing plates, proofs, dry resists, paints, UV inks, transfer recording materials and micro resists.

Conventionally, benzyl, benzoin, benzoin ethyl ether, Michler's ketone, anthraquinone, acridine, phenazine, benzophenone, 2-ethylanthraquinone, etc. are known as typical ones as photopolymerization initiators for polymerizable ethylenically unsaturated compounds. Has been. However, these initiators do not necessarily show sufficient photopolymerization initiation ability in practical use, and it took a lot of time for image formation by light irradiation. In order to improve this drawback, it has been generally proposed to combine a radical generator with a light absorber.
For example, in the trichloromethyl compound of the S-triazine compound represented by the general formula (I) of the present invention, Japanese Patent Publication No. 59-28
Aromatic thiazole compounds disclosed in JP-A No. 328,
Merocyanine dyes disclosed in JP-A-4-151024, JP
Aromatic thiopyrylium salts and aromatic pyrylium salts shown in JP-A-8-40302, other 9-phenylacridine, (In the formula, R is an alkyl group.) And the like, and a light absorbing agent such as
It is known that by combining a hydrogen donor such as -phenylglycine, 2-mercaptobenzothiazole, ethyl N ', N'-dimethylaminobenzoate, etc., excellent photopolymerization initiation ability is exhibited. However, the combination of these radical generators and light absorbers does not always satisfy the sensitivity when used in a practical system, and requires long-time exposure or a strong light source.

[Problems to be Solved by the Invention]

Accordingly, the present invention provides a photopolymerizable composition useful for a printing plate having higher sensitivity, a resist or photomask for producing a printed board, a black and white or color transfer coloring sheet and a photosensitive microcapsule used for a coloring sheet. The purpose is to

[Means for solving the problem]

In view of the current state of the art as described above, the present inventors have earnestly studied, and as a result, in a photopolymerizable composition, a triazine compound as a photopolymerization initiator, an organic boron compound, and light initiate polymerization by themselves. It was found that a more excellent photopolymerization initiation ability can be exhibited by combining the three types of specific sensitizers having the ability, and based on this, the present invention was completed.

 That is, the present invention is a small amount capable of photopolymerization by actinic rays.
If there is at least one ethylenically unsaturated group monomer and light
And a linear organic polymer if necessary.
A photopolymerizable composition containing (a) at least one of the following general formula (I) as a photopolymerization initiator: (X represents a halogen atom. Y represents -CX.₃, -NH₂,-
NHR ', -NR₂Represents 'or -OR'. Where R'is
It represents a kill group or an aryl group. R is an alkyl group,
Aryl group, -CX₃Group or CH = CH_nRepresents R ″.
Here, R ″ is an aryl group or a heterocyclic group, and n is an integer of 1 to 3
Represents a number. ) (B) At least one of the following general formula (II): (R¹, R², R³And R^FourCan be the same or different,
Alkyl group, aryl group, aralkyl group, alkaryl
Group, alkenyl group, alicyclic group, allyl group or
Represents a heterocyclic group, R¹, R², R³And R^FourIs two or more
It may be a cyclic structure in which the groups are bonded. However,
R¹, R², R³And R^FourAt least one of which is alkyl
Group. X Is an alkali metal orRepresents a quaternary ammonium represented by. Where R^Five, R⁶,
R⁷And R⁸May be the same or different, hydrogen, alkyl
Group, aryl group, aralkyl group, alkaryl group, ar group
Kenyl group, alkynyl group, ali cyclic group or ali
Represents a radical. ), And (c) at least one bis (dialkylamino) ben
Zophenone or the following general formula (III): (Z is essential for forming a 5-membered heterocyclic nucleus containing nitrogen.
Represents a group of non-metal atoms, and the heterocycle is S, Se or O
Contain either of them as a hetero atom and become a condensed ring
There is. R⁹Represents an alkyl group. R^TenIs an alkyl group,
Represents a reel group or a cenyl group. R¹¹Is hydrogen orRepresents ) Light weight characterized by using a combination of
It is a compatible composition.

"A monomer having at least one ethylenically unsaturated group capable of being photopolymerized by actinic rays" used in the present invention
Is 1 in at least one molecule with a boiling point of 100 ° C or higher at atmospheric pressure.
It is a monomer or oligomer having a molecular weight of 10,000 or less and having at least one ethylenically unsaturated group capable of addition polymerization. Examples of such monomers or oligomers include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene diester. (Meth) acrylate, trimethylolethane tri (meth)
Acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol di (meth) acrylate, tri (acryloyloxyethyl) ) Isocyanurate, glycerin, trimethylolethane, and other polyhydric alcohols added with ethylene oxide or propylene oxide and then (meth) acrylated, JP-B-48-41708
Urethane acrylates as described in JP-B No. 50-6037, JP-A No. 51-37193 and JP-A No.
-64183, JP-B-49-43191, JP-B-52-30490, and other polyfunctional acrylates such as polyester acrylates, epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid, Methacrylate can be given. Furthermore, the Japan Adhesive Association magazine Vol.
The materials introduced as photocurable monomers and oligomers on pages 20, No. 7, pages 300 to 308 can also be used.

General formula (I) used in the present invention Examples of the compound represented by: 2,4,6-tri (trichloromethyl) -S-triazine, 2- (p-acetylphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2-methyl- 4,6-bis (trichloromethyl)-
S-triazine, And Wakabayashi et al., Bull. Chem. Soc. Japan, 42 , 2924 (1969), for example, 2-phenyl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-chlorophenyl). ) -4,6-Bis (trichloromethyl) -S-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxyphenyl) -4,6 -Bis (trichloromethyl) -S-triazine, 2- (2 ', 4'-dichlorophenyl) -4,6-bis (trichloromethyl) -S-triazine and the like can be mentioned. In addition, compounds described in British Patent No. 1388492,
For example, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methylstyryl)-
4,6-bis (trichloromethyl) -S-triazine, 2
-(P-Methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine and the like, compounds described in JP-A-53-133428, for example, 2- (4-methoxy-naphth-1-yl). -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxy-naphth-1-yl)-
4,6-bis-trichloromethyl-S-triazine, 2-
[4- (2-Ethoxyethyl) -naphth-1-yl]-
4,6-bis-trichloromethyl-S-triazine, 2-
(4,7-dimethoxy-naphth-1-yl) -4,6-bis-
Trichloromethyl-S-triazine, 2- (acenaphtho-5-yl) -4,6-bis-trichloromethyl-S-triazine and the like, compounds described in Japanese Patent Publication No. 59-1281, for example, Compounds described in German Patent No. 3337024, for example, Compounds described in JP-A-62-58241, for example Etc., compounds described in JP-A-63-153542, for example, Etc. can be given.

 General formula (II) used in the present inventionThe compound represented by¹~ R^FourHas 1 carbon
Those of -18 are preferred. Particularly preferred is 1 to 1 carbon atoms.
6 alkyl group, phenyl group, substituted phenyl group and benzene
It is a zircon group. X Is an alkali metal orAnd especially R^Five~ R⁸Is preferably an alkyl group having 1 to 6 carbon atoms.
Good

Specific compounds represented by the general formula (II) include (E) ( _n C ₄ H ₉ ) ₄ B ^- N ⁺ ( _n C ₄ H ₉ ) ₄ Etc. can be given.

Examples of the bis (dialkylamino) benzophenone used in the present invention include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone and 4,4′-bis (dipropylamino) benzophenone. I can give you.

General formula (III) used in the present invention As the compound represented by, R ⁹ is an alkyl group (eg, methyl group, ethyl group, propyl group) or a substituted alkyl group (eg, 2-hydroxyethyl group, 2-methoxyethyl group, carboxymethyl group, 2-carboxyethyl group). Group, 3-carboxypropyl group, 2-sulfoethyl group, 3-sulfopropyl group, 2-carbomethoxyethyl group, benzyl group, phenethyl group, P-sulfophenethyl group, P-carboxyphenethyl group, vinylmethyl group, etc.), R ¹⁰ is an alkyl group (eg, methyl group, ethyl group,
A propyl group) or an aryl group (for example, a phenyl group, a P-hydroxyphenyl group, a P-methoxyphenyl group, a P-chlorophenyl group, a naphthyl group, etc.) or a cenyl group, and Z is a 5-membered nitrogen-containing cyanine dye. Represents a group of non-metal atoms necessary for forming a heterocyclic nucleus of a ring, wherein the heterocycle contains either S, Se or O as a hetero atom and is a condensed ring,
For example, benzothiazoles (benzothiazole, 5-
Chlorobenzothiazole, 6-chlorobenzothiazole, 4-methylbenzothiazole, 6-methylbenzothiazole, 5-phenylbenzothiazole, 6-methoxybenzothiazole, 4-ethoxybenzothiazole,
5-methoxybenzothiazole, 5-hydroxybenzothiazole, 5,6-dimethylbenzothiazole, 5,6-dimethoxybenzothiazole, etc.), naphthothiazoles (α-naphthothiazole, β-naphthothiazole, etc.), benzoselenazoles (Benzoselenazole),
5-chlorobenzoselenazole, 6-methylbenzoselenazole, 6-methoxybenzoselenazole and the like), naphthoselenazoles (α-naphthelenazole, β-naphthelenazole and the like), benzoxazoles (benzoxazole, 5 -Methylbenzoxazole, 5-
Examples thereof include phenylbenzoxazole, 6-methoxybenzoxazole, etc.) and naphthoxazoles (α-naphthoxazole, β-naphthoxazole, etc.).

The concentration of these photopolymerization initiators to be used is usually low, and when the concentration is inappropriately high, unfavorable results such as shielding of effective rays are produced. The total amount of the combination of the photopolymerization initiators in the present invention is in the range of 0.01% by weight to 20% by weight based on the total of the photopolymerizable ethylenically unsaturated compound and the linear organic polymer if necessary. Sufficient, and more preferably 1% to 10% by weight will give good results.
In the compounds of the general formula (I), the compound of the general formula (II) and bis (dialkylamino) benzophenone, the ratio of the compound of the general formula (III) to the total photopolymerization initiator is 60 to 10% by weight, respectively. 10-60% by weight and 30-70% by weight
Is desirable.

Further, the photopolymerization initiator used in the present invention may contain N-
Phenylglycine, 2-mercaptobenzothiazole,
The photopolymerization initiation ability can be further enhanced by providing a hydrogen donating compound such as an N, N-dialkylbenzoic acid alkyl ester.

In the present invention, as the "linear organic high molecular polymer" to be added as necessary, it is of course necessary to select one having compatibility with the photopolymerizable ethylenically unsaturated compound. Any linear organic polymer that is compatible with the photopolymerizable ethylenically unsaturated compound may be used, but it is preferable that it be capable of developing with water or weak alkaline water. A linear organic high molecular polymer should be selected. The linear organic high molecular polymer is used not only as a film-forming agent for the composition but also depending on the developer to be used, such as water, weak alkaline water or an organic solvent. For example, water development becomes possible by using a water-soluble organic high molecular polymer. Examples of such linear organic polymer include addition polymers having carboxylic acid in the side chain, such as methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, and maleic acid. There are acid copolymers, partially esterified maleic acid copolymers and the like, and similarly, there are acidic cellulose derivatives having a carboxylic acid in the side chain. In addition to these, those obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxyl group are useful. In addition, polyvinylpyrrolidone, polyethylene oxide and the like are useful as the water-soluble linear organic polymer. In addition, alcohol-soluble nylon or 2,2-bis- (4-
Polyethers of hydroxyphenyl) -propane and epichlorohydrin are also useful. These linear organic high molecular weight polymers may be contained in any amount in the entire composition, for example, 100 to 100 parts by weight per 100 parts by weight of a monomer having a photopolymerizable ethylenically unsaturated group.
It can be mixed in a proportion of 900 parts by weight, but if it exceeds 90% by weight, favorable results are not obtained in terms of the strength of the image formed.

Further, in the present invention, in addition to the above basic components, a small amount of a thermal polymerization inhibitor is added to prevent unnecessary thermal polymerization of the polymerizable ethylenically unsaturated compound during the production or storage of the photopolymerizable composition. It is desirable to do. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-
Thiobis (3-methyl-6-t-butylphenol),
2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, N-
Examples include cerium nitrosophenylhydroxyamine and the like. In some cases, an inorganic filler may be added for the purpose of improving the physical properties of the cured film.

The photopolymerizable composition of the present invention can be prepared, for example, from a suitable solvent such as 2-methoxyethanol, 2-methoxyethyl acetate, propylene glycol monomethyl ether, 3-methoxypropanol, 3-methoxyproyl acetate, methyl ethyl ketone and ethylene dichloride. They can be applied alone or by dissolving them in a suitable mixed solvent to form a coating on the support. The coating amount in the range of about 0.1 g / m ² ~ about 10 g / m ² in weight after drying are suitable, more preferably from 0.5 to 5 g / m ^2.

Furthermore, the photopolymerizable composition of the present invention may contain other additives known in the art for achieving the intended purpose (for example, a bakeout agent and the like).

As the above support, a dimensionally stable plate-like material is used. Such dimensionally stable plate-like materials include those conventionally used as a support for printing plates, and they can be preferably used. Examples of such a support include paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate such as aluminum (including aluminum alloy), zinc, copper, etc., such as cellulose diacetate, Films of plastics such as cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc., paper on which the above metals are laminated or vapor deposited. Alternatively, a plastic film or the like is included. Among these supports, the aluminum plate is particularly preferable because it is dimensionally remarkably stable and inexpensive. Furthermore, Japanese Examined Japanese Patent Publication 48-18
A composite sheet in which an aluminum sheet is bonded onto a polyethylene terephthalate film as described in Japanese Patent No. 327 is also preferable.

Further, in the case of a support having a surface of metal, particularly aluminum, it is subjected to surface treatment such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like, or anodization treatment. Is preferred. Further, as described in U.S. Pat.No. 2,714,066, an aluminum plate that has been grained and then dipped in an aqueous sodium silicate solution, and an aluminum plate as an anode as described in JP-B-47-5125 are used. A product obtained by immersing it in an aqueous solution of an alkali metal silicate after the oxidation treatment is also suitably used. The anodizing treatment,
For example, an aluminum plate is anodized in an electrolytic solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid or boric acid, or an organic acid such as oxalic acid or sulfamic acid, or an aqueous solution or a non-aqueous solution of these salts, or a combination of two or more thereof. Is carried out by passing an electric current.

Further, silicate electrodeposition as described in US Pat. No. 3,658,662 is also effective.

Further, a support subjected to electrolytic graining as disclosed in JP-B-46-27481, JP-A-52-58602 and JP-A-52-30503, and the anodizing treatment and sodium silicate treatment described above. A surface treatment in which the above is combined is also useful.

Further, as disclosed in JP-A-56-28893, a brush grain, an electrolytic grain, an anodic oxidation treatment, and a sodium silicate treatment which are sequentially performed are also preferable.

Furthermore, after these treatments, a water-soluble resin such as polyvinyl phosphonic acid, a polymer or copolymer having a sulfonic acid group in its side chain, or a polyacrylic acid undercoat is also suitable.

These hydrophilization treatments are performed to make the surface of the support hydrophilic, but to prevent a harmful reaction between the photopolymerizable composition and the support provided thereon, Further, it is also applied to improve the adhesion of the photosensitive layer.

On the layer of the photopolymerizable composition provided on the support,
In order to completely prevent the polymerization inhibition effect due to oxygen in the air, a protective layer made of a polymer having excellent oxygen barrier properties such as polyvinyl alcohol, particularly polyvinyl alcohol having a saponification degree of 99% or more, acidic celluloses, etc. is provided. May be. The coating method of such a protective layer is described in detail, for example, in US Pat. No. 3,458,311 and JP-B-55-49729.

The photosensitive plate provided with the photopolymerizable composition of the present invention on a support is subjected to image exposure using a light source rich in ultraviolet rays such as a metal halide lamp, a high pressure mercury lamp, etc. A printing plate is obtained by removing the exposed portion and finally applying a gum solution. Preferred as the developing solution is an alkaline aqueous solution containing a small amount of an organic solvent such as benzyl alcohol, 2-phenoxyethanol, and 2-butoxyethanol. For example, US Pat.
Mention may be made of those described in 5,171 and 3,615,480.

Further, JP-A-50-26601, JP-B-56-39464, and JP-A-56-39464
The developing solution described in each publication of -42860 is also excellent as a developing solution for the photosensitive plate.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.

Example 1 An aluminum plate having a thickness of 0.30 mm and a nylon brush and 400
The surface was grained using an aqueous suspension of mesh pumice and then thoroughly washed with water. It was immersed in 10% sodium hydroxide at 70 ° C. for 60 seconds for etching, washed with running water, neutralized with 20% HNO ₃ , and then washed with water. This is V _A
= 12.7% using a sinusoidal alternating current under the condition of 12.7V
Electrolytic surface-roughening treatment was performed in an aqueous nitric acid solution at an anode electricity of 160 Coulomb / dm ² , and the surface roughness was measured.
It was 0.6 μ (R _a display). Next, after soaking in 30% H ₂ SO ₄ aqueous solution and desmutting at 50 ° C for 2 minutes, 20% H ₂
Anodizing treatment was carried out for 2 minutes in an SO ₄ aqueous solution at a current density of 2 A / dm ^{2 to} a thickness of 2.7 g / m ² .

On the aluminum plate treated in this manner, a dry coating weight of 1.5 g of a photosensitive solution comprising a photopolymerizable composition having the following composition was applied.
It was coated so as to be / m ² and dried at 100 ° C. for 2 minutes to obtain a photosensitive plate.

Trimethylolpropane tri (acryloyloxypropyl) ether 2.0g Allyl methacrylate / methacrylic acid copolymer (copolymerization molar ratio 80/20) 2.0g Photoinitiator Xg Copper phthalocyanine pigment 0.2g Fluorine nonionic surfactant 0.03g [ Fluorad FC-430 (trade name) manufactured by 3M] Methyl ethyl ketone 20 g Propylene glycol monomethyl ether acetate 20
g Polyvinyl alcohol (saponification degree 86.5
A 3% by weight aqueous solution of ˜89 mol% and a polymerization degree of 1,000) was applied so that the dry coating weight would be 2 g / m ^2, and dried at 100 ° C. for 2 minutes.

On the photosensitive lithographic printing plate thus obtained, Fuji PS Step Guide manufactured by Fuji Photo Film Co., Ltd. (ΔD = 0.
A gray scale whose transmission density changes discontinuously at 15) was adhered, a filter film that cuts light of 380 nm or less was placed thereon, and exposure was performed from above. Light source is 100W
The light intensity on the plate surface after passing through the filter was 0.01 mW / cm ² . As the sensitivity, the exposure amount when the gray scale sixth stage remained after developing the plate was expressed as the practical sensitivity.

The development was carried out by immersing in the following developer at 25 ° C. for 1 minute.

Table 1 shows the results of sensitivity when the combination of photopolymerization initiators was changed. As shown in Table 1, as compared with the case where the photopolymerization initiator is used alone or the combination of the two is used, the sensitivity is tripled or more by using the three combinations of the present invention. It has been found.

Examples 2 to 7 Table 2 shows the results of sensitivity when another initiator was used in place of the initiator of Example 1. Others were the same as in Example 1.

As shown in Table 2, it was found that the combination of the three photopolymerization initiators resulted in high sensitivity.

〔The invention's effect〕

 The photopolymerizable composition of the present invention has extremely high sensitivity.

Claims (2)

[Claims] 1. At least photopolymerizable by actinic rays
Monomer having one ethylenically unsaturated group and photoinitiator
In a photopolymerizable composition containing: and (a) at least one compound of the following general formula (I) as a photopolymerization initiator:(X represents a halogen atom. Y represents -CX.₃, -NH₂, -NH
R ', -NR₂Represents 'or -OR'. Where R'is Archi
Represents an aryl group or an aryl group. R is an alkyl group,
Reel base, -CX₃Group or CH = CH_nRepresents R ".
R ″ is an aryl group or a heterocyclic group, and n is an integer of 1 to 3.
Represents ) (B) at least one compound of the following general formula (II):(R¹, R², R³And R^FourCan be the same or different,
Alkyl group, phenyl group, substituted phenyl group or benzyl group
Represents However, R¹, R², R³And R^FourAt least of
One is an alkyl group. X Is an alkali metal orRepresents a quaternary ammonium represented by. Where R^Five, R⁶,
R⁷And R⁸Can be the same or different, hydrogen,
Kill group, aryl group, aralkyl group, alkaryl group,
Alkenyl group, alkynyl group, alicyclic group or
Represents an allyl group. ), And (c) at least one bis (dialkylamino) ben
Zophenone or a compound of the following general formula (III):(Z is necessary to form a 5-membered heterocyclic nucleus containing nitrogen.
Represents a non-metallic atomic group, wherein the heterocycle is S, Se or O
It contains a gap as a hetero atom and is a condensed ring.
It R⁹Represents an alkyl group. R^TenIs an alkyl group, ant
Group or thienyl group. R¹¹Is hydrogen orRepresents ) Light weight characterized by using a combination of
Compatible composition. 2. The photopolymerizable composition according to claim 1, further comprising a linear organic high molecular polymer.