JPH0254268A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To obtain the high-sensitivity photopolymerizable compsn. useful for photosensitive microcapsules used for master plates for printing, resist for forming printed circuit boards, etc., by combining specific three sensitizers. CONSTITUTION:The compds. expressed by the formulas I, II and III are combined as a photopolymn. initiator. In the formula, X denotes a halogen atom; Y denotes -CH3, -NH2, etc.; R denotes an alkyl group, aryl group, etc.; n denotes 1 to 3 integer. In the formula II, R<1> to R<4> denote an alkyl group, aryl group, etc.; X<+> denotes an alkaline metal or quaternary ammonium; R<5> to R<8> denote hydrogen, alkyl group, etc. In the formula III, Z denotes a nonmetallic atom group necessary for forming a heterocyclic nucleus of a 5-membered ring contg. nitrogen; R<9> denotes an alkyl group; R<10> denotes an alkyl group, aryl group, etc.; R<11> denotes hydrogen, etc. The high-sensitivity photopolymerizable compsn. usable for applications such as the master plates for printing and the resist for forming the printed circuit boards in particular is obtd. in this way.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention provides a photopolymerizable material containing an unsaturated monomer, a photopolymerization initiator, an organoboron compound, and, if necessary, a linear organic polymer. Regarding compositions, in particular, highly sensitive photopolymerizable compositions that can be used for purposes such as the production of printing original plates, resists or photomasks for producing printed circuit boards, and the production of monochrome or color transfer coloring sheets and coloring sheets. It is.

[Conventional technology]

A photosensitive composition is a mixture of a polymerizable ethylenically unsaturated compound, a photopolymerization initiator, and, if necessary, a linear organic polymer having an appropriate film-forming ability, a thermal polymerization inhibitor, etc. 2. Description of the Related Art Methods of copying images using photographic methods are now widely known. In other words, Tokko Sho 3
As described in Japanese Patent Publication No. 5-5093 and Japanese Patent Publication No. 35-8495, the photosensitive composition undergoes photopolymerization and becomes insolubilized by irradiation with actinic rays. Therefore, by forming a photosensitive composition into a suitable film, irradiating active light through the negative of the desired image, and removing only the unexposed areas with an appropriate solvent (hereinafter simply referred to as development), the desired light can be produced. A polymerized image can be formed. This type of photosensitive composition is extremely useful as a photosensitive agent for printing plates, proofs, dry resists, paints, UV inks, transfer recording materials, microresists, and the like.

Conventionally, representative photopolymerization initiators for polymerizable ethylenically unsaturated compounds include benzyl, benzoin, benzoin ethylethenobemichler ketone, anthraquinone, acridine, phenazine, benzophenone, and 2-ethyl anthraquinone. known as. However, these initiators do not necessarily exhibit sufficient photopolymerization initiation ability for practical use, and it takes a long time to form an image by light irradiation. In order to improve this drawback, it has been proposed to combine a radical generator with a light absorber. For example, in the trichloromethyl compound of the S-) riazine compound represented by the general formula (I) of the present invention,
Aromatic thiazole compounds shown in JP-A No. 8328, merocyanine dyes shown in JP-A-54-151024, aromatic thiopyrylium salts and aromatic pyrylium salts shown in JP-A-58-40302, and other 9-phenyl Acridine, (in the formula, R is an alkyl group) and other light absorbers are combined, and these combinations are further combined with N.
-Phenylglycine, 2-mercaptobenzothiazole N/, N/-It is known that excellent photopolymerization initiation ability is exhibited by combining hydrogen donors such as ethyl dimethylaminobenzoate. However, when these combinations of radical generators and light absorbers are used in practical systems, they are not necessarily satisfactory in terms of sensitivity, requiring long-time exposure or a powerful light source.

[Problem to be solved by the invention]

Therefore, the present invention provides a photopolymerizable composition useful for highly sensitive printing original plates, resists or photomasks for producing printed circuit boards, and photosensitive microcapsules used in monochrome or color transfer coloring sheets and coloring sheets. The purpose is to

[Means to solve the problem]

In view of the current state of the technology as described above, the present inventors have conducted intensive research and found that in a photopolymerizable composition, a triazine compound and an organic boron compound are used as a photopolymerization initiator, and the polymerization itself is initiated by light. We have obtained the knowledge that a combination of three specific sensitizers having this ability can exhibit superior photopolymerization initiation ability, and based on this, we have accomplished the present invention.

That is, the present invention provides a photopolymer containing a monomer having at least one ethylenically unsaturated group that can be photopolymerized by actinic light, a photopolymerization initiator, and, if necessary, a linear organic polymer. In the polymerizable composition, as a photopolymerization initiator (a) at least one type of the following general formula (1): (X represents a halogen atom, Y represents -Cx3, -Nl2, -N
HR' represents -NR2' or -OR'. Here R
' represents an alkyl group or an aryl group. R is an alkyl group, an aryl group, a -CL group, or a thousand CH=CH+r
Represents R'. Here, R' represents an aryl group or a heterocyclic group, and n represents an integer of 1 to 3. ), etc.) At least one of the following general formula (■): (RISR2, R3 and R4 may be the same or different, and are an alkyl group, an aryl group, an aralkyl group, an alkaryl group, an alkenyl group, an alicyclic group) , represents an allyl group or a heterocyclic group, R1, R
2, R3 and R4 may be a cyclic structure in which two or more groups thereof are bonded. However, at least one of R1, R2, R3 and R4 is an alkyl group. X
○ indicates alkali metal or S. R5, R6, R' and R8 may be the same or different and may be hydrogen, an alkyl group, an aryl group, an aralkyl group, an alkaryl group, an alkenyl group, an alkynyl group, an alicyclic group or an allyl group. represents. ),
and (C) at least one bis(dialkylamino)
Benzophenone or the following general formula (■): (2 represents a nonmetallic atomic group necessary to form a nitrogen-containing 5-membered heterocyclic nucleus, and the heterocyclic ring has either S, Se, or 0. (R9 represents an alkyl group. RIO represents an alkyl group, an aryl group, or a thienoyl group. R11 represents hydrogen or -〇-R10.) This is a photopolymerizable composition characterized by using.

The "monomer having at least one ethylenically unsaturated group that can be photopolymerized by actinic rays" used in the present invention has a boiling point of 100:00 or more at normal pressure, and at least one per molecule, or more. Preferably, it is a monomer or oligomer having two or more addition-polymerizable ethylenically unsaturated groups and having a molecular weight of less than io or ooo. 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; polyprolene glycol di(meth)acrylate, polypropylene Di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate
(meth)acrylate, pentaerythritol tetra
Ethylene oxide and (meth)acrylate after adding propylene oxide,
Special Publication No. 4111-41708, Special Publication No. 50-6037
Urethane acrylates as described in JP-A-51-371/93, JP-A-48-641
No. 83, Special Publication No. 49-43191, Special Publication No. 52-30
Examples include polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates prepared by reacting an epoxy resin with (meth)acrylic acid, which are described in each publication of No. 490.

Furthermore, Japan Adhesive Association Journal Vat, 20, No. 7.30
Those introduced as photocurable monomers and oligomers on pages 0 to 308 can also be used.

The compounds represented by the general formula (1) used in the present invention include 2.4.6-)U(trichloromethyl)-3-)riazine, 2(p-acetylphenyl)-4,6-bis(trichloromethyl) )-3-)
Riazine, 2-methyl-4,6-bis(trichloromethyl)-3-) riazine, Ya Wakabayashi et al., Bull, Chem, Sac, Jap
Compounds described in An, Satue, 2924 (1969), such as 2-phenyl-4,6-bis(trichloromethyl)-8-triazine, 2-(p-chlorophenyl)-
4,6-bis(trichloromethyl)-3-triazine,
2-(p-)lyl)-4,6-bis(trichloromethyl)-3-)riazine, 2-(p-methoxyphenyl)-
4,6-bis(trichloromethyl)-3-)riazine,
Examples include 2-(2',4'dichlorophenyl)-4,6-bis(trichloromethyl)-3-)riazine. Other compounds described in British Patent No. 1388492, such as 2-styryl-4,6-bis(trichloromethyl)-3-)riazine, 2-(p-methylstyryl)-4,6-bis(trichloromethyl) )-3-) riazine, 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-3-) riazine, etc., JP-A-1973
-133428, for example, 2-
(4-methoxy-naphth-1-yl)-4,6-bis-
Trichloromethyl-S-)riazine, 2-(4-ethoxy-naphth-1-yl)-4,6-bis-trichloromethyl-S-triazine, 2-[:4-(2-ditoxyethyl)-naphtho- 1-yl: l-4,6-bis-trichloromethyl-S-) liazine, 2-(4゜7-dimethoxy-naphthol-1-yl)-4,6-bis-trichloromethyl-S-) riazine, 2 -(acenaphth-5-yl)-4,6- and sootrichloromethyl-S-)riazine, etc. Compounds described in Japanese Patent Publication No. 59-1281, e.g. Compounds described in JP-A No. 62-58241, e.g. Compounds described in Japanese Patent No. 3337024, such as, and compounds described in JP-A-63-153542, such as, can be mentioned.

The compound represented by the general formula used in the present invention is preferably one in which R1 to R4 have 1 to 18 carbon atoms. Particularly preferred are alkyl groups having 1 to 6 carbon atoms, phenyl groups, substituted phenyl groups, and benzyl groups. XO is a(e) (,C-H5)-8-N'' (,,C,H,).

R' As such, an alkyl group having 1 to 6 carbon atoms is preferable.

Specific examples of the compound represented by the general formula (II) include the following.

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 it to you.

In the compound represented by the general formula ([[) used in the present invention, R9 is an alkyl group (e.g., methyl group, ethyl group, propyl group, etc.) or a substituted alkyl group (e.g., 2-hydroxyethyl group, 2-methoxyethyl group, etc.). group, carboxymethyl group, 2-carboxyethyl 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'' is an alkyl group (e.g. methyl group, ethyl group, propyl group, etc.) or an aryl group (e.g. phenyl group,
P-hydroxyphenyl group, P-methoxyphenyl group,
P-chlorophenyl group, naphthyl group, etc.) or thienyl group, Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing 5-membered heterocyclic nucleus usually used in cyanine dyes, and the heterocycle is 5SSe. or 0 as a foreign atom and a fused ring, such as benzothiazoles (benzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole,
4-Methylbenzothiazole 6-methylbenzothiazole, 5-phenylbenzothiazole, 6-medoxybenzothiazole 4-ethoxybenzothiazole, 5-methoxybenzothiazole, 5-hydroxybenzothiazole, 5.6-dimethyl benzothiazole, 5,6-simethoxybenzothiazole, etc.), naphthothiazoles (α-naphthothiazole, β-naphthothiazole, etc.)
, benzoselenazole @ (benzoselenazole, 5-chlorobenzoselenazole, 6-methylbenzoselenazole, 6-methylbenzoselenazole, etc.), naphthoselenazole (α-naphthoselenazole, β-naphthoselenazole, etc.) ), benzoxazole (benzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-methoxybenzothiazole, etc.), and naphthoxazole (α-naphthoxazole, β-naphthoxazole, etc.). I can do it.

The concentration of these photopolymerization initiators used is usually small, and if the concentration is inappropriately high, undesirable effects such as blocking of effective light rays will occur. The total amount of the photopolymerization initiator combination in the present invention is 0.01% to 20% by weight based on the total of the photopolymerizable ethylenically unsaturated compound and, if necessary, the linear organic polymer. A range of 1% to 10% by weight is more preferable, and good results are obtained. Also, the compound of the general formula (I), the general formula (II)
) and bis(dialkylamino)benzophenone, the proportions of the compound of general formula (III) to the total photopolymerization initiator are 60 to 10% by weight and 10 to 60% by weight, respectively.
and 30 to 70% by weight.

Furthermore, N-phenylglycine, 2-mercaptobenzothiazole, N
The ability to initiate photopolymerization can be further enhanced by providing a hydrogen-donating compound such as N-dialkylbenzoic acid alkyl ester.

In the present invention, as the "linear organic polymer" added as necessary, it is necessary to select one that is compatible with the photopolymerizable ethylenically unsaturated compound. Any linear organic polymer can be used as long as it is compatible with the photopolymerizable ethylenically unsaturated compound, but it is preferable to use a linear organic polymer that can be developed with water or weakly alkaline water. A linear organic high molecular weight polymer should be selected. The linear organic polymer is used not only as a film-forming agent in the composition, but also depending on the developer used, such as water, weak alkaline water, or an organic solvent. For example, water development becomes possible when a water-soluble organic polymer is used. Examples of such linear organic polymers include addition polymers having carboxylic acid in the side chain, such as methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers,
These include crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and the like, as well as acidic cellulose derivatives having carboxylic acid in their side chains. An addition polymer having a hydroxyl group to which a cyclic acid anhydride is added is useful. Other useful water-soluble linear organic polymers include polyvinylpyrrolidone and polyethylene oxide. In order to increase the strength of the cured film, alcohol-soluble nylon and polyether of 2,2-bis-(4-hydroxyphenyl)-propane and shrimp chlorohydrin are also useful. These linear organic high-molecular polymers can be used in any amount in the total composition, for example, 10 parts by weight per 100 parts by weight of monomers having a photopolymerizable ethylenically unsaturated group.
It can be mixed in a proportion of 0 to 900 parts by weight,
If it exceeds 90% by weight, it will not give favorable results in terms of the strength of the image formed.

Furthermore, 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 polymerizable ethylenically unsaturated compounds during the production or storage of the photopolymerizable composition. It is desirable to do so. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-phthyl-p-cresol, pyrogallol, t-butylcatechol, benzenequinone, 4,4'thiobis(3-methyl-6-t-butylphenol), 2
．． 2'-methylenebis(4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, N
- Nitrosophenylhydroxyamine cerous salt, etc. In some cases, an inorganic brightening agent 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 using a suitable solvent such as, for example, 2-methoxyethanol, 2-methoxyethyl acetate, propylene glycol monomethyl ether, 3-methoxypropanol, 3-methoxypropyl acetate, methyl ethyl ketone, or ethylene dichloride. Alternatively, they can be coated on a support by dissolving them in an appropriate mixed solvent. The coating amount is about 0.1 g/m' to about 10.0 g/m' after drying. A suitable range is g/m', more preferably 0.5 to 5 g/m'.

Furthermore, the photopolymerizable composition of the present invention may contain other known additives (eg, printing out agents, etc.) to achieve the intended purpose.

As the support, a dimensionally stable plate-like material is used. Such dimensionally stable plate-like materials include those conventionally used as supports for printing plates, and these can be suitably used. Such supports include:
Paper, paper laminated with plastics (e.g. polyethylene, polypropylene, polystyrene, etc.), plates of metals such as aluminum (including aluminum alloys), zinc, copper, etc., e.g. cellulose diacetate, cellulose triacetate, propionic acid Includes plastic films such as cellulose, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc., paper or plastic films laminated or vapor-deposited with the above metals, etc. It will be done. Among these supports, aluminum plates are particularly preferred because they are extremely dimensionally stable and inexpensive. In addition, the special public official 1832-1832
Also preferred is a composite sheet in which an aluminum sheet is bonded onto a polyethylene terephthalate film as described in Japanese Patent No. 7.

In addition, in the case of a support having a metal surface, especially aluminum, surface treatments such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, etc., or anodization treatment are performed. Preferably. In addition, as described in U.S. Pat.
As described in Japanese Patent No. 5125, an aluminum plate which is anodized and then immersed in an aqueous solution of an alkali metal silicate is also preferably used.

The above anodic oxidation treatment can be performed using, for example, phosphoric acid, chromic acid, sulfuric acid,
It is carried out by passing an electric current through an aluminum plate as an anode in an electrolytic solution consisting of an aqueous or non-aqueous solution of an inorganic acid such as boric acid, an organic acid such as oxalic acid or sulfamic acid, or a salt thereof, or a combination of two or more thereof. .

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

Furthermore, Japanese Patent Publication No. 46-27481, Japanese Patent Publication No. 52-58
Also useful is a surface treatment that combines a support subjected to electrolytic duplexing and the above-mentioned anodic oxidation treatment and sodium silicate treatment as disclosed in JP-A-602 and JP-A-52-30503.

Furthermore, those which have been subjected to brush darein, electrolytic darein, anodic oxidation treatment, and sodium silicate treatment as disclosed in JP-A-56-28893 are also suitable.

Furthermore, after these treatments, it is also suitable to apply an undercoat with a water-soluble resin such as polyvinylphosphonic acid, a polymer or copolymer having a sulfonic acid group in the side chain, polyacrylic acid, or the like.

These hydrophilic treatments are performed to make the surface of the support hydrophilic, but in order to prevent harmful reactions between the photopolymerizable composition provided thereon and the support, Furthermore, it is 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 caused by oxygen in the air,
For example, a protective layer made of a polymer with excellent oxygen barrier properties such as polyvinyl alcohol, especially polyvinyl alcohol with a degree of saponification of 99% or more, acidic cellulose, etc., may be provided. A method for applying such a protective layer is described, for example, in U.S. Pat.
It is described in detail in Publication No. 29.

A photosensitive plate provided with the photopolymerizable composition of the present invention on a support is imagewise exposed using a light source rich in ultraviolet rays such as a metal halide lamp or a high-pressure mercury lamp, and then treated with a developer to remove the photosensitive layer. A printing plate is obtained by removing the exposed areas and finally applying a gum solution. Preferably, the developer is an alkaline aqueous solution containing a small amount of an organic solvent such as benzyl alcohol, 2-phenoxyethanol, or 2-butoxyethanol, such as U.S. Pat.
Examples include those described in No. 75.171 and No. 3.615.480.

Furthermore, Japanese Patent Publication No. 50-26601, Japanese Patent Publication No. 56-394
64 and No. 56-42860 are also excellent as developers for the photosensitive plate.

The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 The surface of an aluminum plate with a thickness of 0.30111 (O) was grained using a nylon brush and a water suspension of 400 mesh pumice stone, and then thoroughly washed with water.
After etching by immersing in sodium hydroxide at 70°C for 60 seconds, washing with running water and neutralizing with 20% HNO3,
Then, it was washed with water. This was heated to 1% in a 1% nitric acid aqueous solution using a sinusoidal alternating current waveform under the condition of VA = 12.7 V.
Electrolytic surface roughening treatment was carried out using an anode special electricity amount of 60 corons/dm'. When the surface roughness was measured, it was found to be 0.6 μ(
R, indicated). 82S mouth continues to be 30%.

After immersing in an aqueous solution and desmutting at 50°C for 2 minutes,
It was anodized for 2 minutes in a 0% H=SO4 aqueous solution at a current density of 2 A/dm2 to a thickness of 2.7 g/m''.

A photosensitive solution consisting of a photopolymerizable composition having the following composition was applied onto the aluminum plate treated in this way to a dry coating weight of 1.5.
g/m' and dried at 100°C for 2 minutes to obtain a photosensitive plate.

Photopolymerization initiator copper phthalocyanine pigment g O 12 g 1 potassium silicate potassium hydroxide methyl ethyl ketone 0 g Polyvinyl alcohol (saponification degree 86.
Apply a 3% by weight aqueous solution of 5 to 89 mol%, degree of polymerization 1.000) so that the dry coating weight is 2 g/rn'',
It was dried at 100°C for 2 minutes.

A Fuji PS step guide (ΔD=0.1 manufactured by Fuji Photo Film ■) was placed on the photosensitive lithographic printing plate thus obtained.
5) (a gray scale in which the transmission density changes discontinuously) was placed in close contact with the film, a filter film that cuts light of 380 nm or less was placed on top of the film, and the film was exposed to light from above. The light source was a 100 W high-pressure mercury lamp, and the light intensity at the plate surface after passing through the filter was 0.01 mW/cm'. As for the sensitivity, the exposure amount when the sixth level of the gray scale remained after the plate was developed was expressed as the practical sensitivity.

Development was performed by immersing the film in the following developer at 25° C. for 1 minute.

Table 1 shows the sensitivity results when the combination of photopolymerization initiators was changed.

It has been found that high sensitivity can be achieved by combining three types of photopolymerization initiators as shown in Table 2.

〔Effect of the invention〕

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

Claims (1)

[Claims] Contains a monomer having at least one ethylenically unsaturated group that can be photopolymerized by actinic rays, a photopolymerization initiator, and, if necessary, a linear organic polymer. In the photopolymerizable composition, as a photopolymerization initiator (a) at least one of the following general formula (I): ▲ mathematical formula,
There are chemical formulas, tables, etc. ▼ (X represents a halogen atom. Y is -CX_3, -NH
_2, -NHR', -NR_2' or -OR'. R' here represents an alkyl group or an aryl group. In addition, R represents an alkyl group, an aryl group, a -CX_3 group, or ▲a numerical formula, a chemical formula, a table, etc.▼R''.Here, R
'' represents an aryl group or a heterocyclic group, and n represents an integer of 1 to 3.) (b) At least one type of the following general formula (II): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R^1, R^2, R^3 and R^4 may be the same or different and represent an alkyl group, an aryl group, an aralkyl group, an alkaryl group, an alkenyl group, an alicyclic group, an allyl group or a heterocyclic group; , R^1, R^2, R
^3 and R^4 may be a cyclic structure in which two or more groups thereof are bonded. However, R^1, R^2, R^3
and R^4, at least one of which is an alkyl group. X^■ represents an alkali metal or quaternary ammonium shown by ▲Formula, chemical formula, table, etc. are available. Here, R^5, R^6, R^7 and R^8 may be the same or different and represent hydrogen, an alkyl group, an aryl group, an aralkyl group, an alkaryl group, an alkenyl group,
Represents an alkynyl group, an alicyclic group or an allyl group. ), and (c) at least one type of bis(dialkylamino)benzophenone or the following general formula (III): ▲ Numerical formula, chemical formula, table, etc. ▼ (III) (Z is a 5-membered heterocyclic nucleus containing nitrogen represents a group of nonmetallic atoms necessary to form a heterocyclic ring containing S, Se, or O as a foreign atom, and is a condensed ring. R^9 represents an alkyl group. .R^1^0 represents an alkyl group, an aryl group or a chenyl group.R^1
^1 represents hydrogen or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. ) A photopolymerizable composition characterized by using a combination of the following.