JPS6343133A - High-sensitivity photopolymerizable composition - Google Patents

Abstract

PURPOSE:To improve sensitivity to visible laser light by using a photopolymn. initiator combined with a specific (thio)xanthene dye, diaryl iodonium salt and compd. having a methylene group in the alpha position of an N atom. CONSTITUTION:The titled compsn. contains the addition polymerizable compd. having ethylenic unsatd. double bonds (e.g.: methyl methacrylate/methacrylic acid copolymer) and the photopolymn. initiator. The photopolymn. initiator is constituted by the combination of the (thio)xanthene dye expressed by formula I, the diaryl iodonium salt expressed by formula II and the compd. having the methylene group in the alpha position of the N atom (more preferably N-phenyl glycine, etc.). In formulas, A denotes O, S; X denotes H, halogen; Y denotes C, N; Z denotes O, lower alkoxy, etc.; R<1> denotes (hydroxy) lower alkyl, etc.; R<2> denotes H, lower alkoxy, etc.; R<3>-R<6> denote H, halogen, etc.; X<-> denotes, a halogen ion, BF4<->, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a photopolymerizable composition that exhibits high sensitivity to light in a wide wavelength range including ultraviolet rays and visible light.

In particular, the present invention relates to a photopolymerizable composition that exhibits excellent photosensitivity to visible laser light such as argon ion laser light.

[Prior Art] When reproducing images by photographic techniques, compositions containing photosensitive compounds such as diazonium salts, ANDs, and quinonediazides, or photopolymerizable compositions containing photopolymerization initiators that act with ultraviolet light are used. composition is used.

The above-mentioned compounds or compositions all have a problem in that they exhibit photosensitivity to ultraviolet rays but almost no photosensitivity to visible rays. Visible light (wavelength 400
Photopolymerizable compositions having photosensitivity to wavelengths of up to 700 nm) include dyes and photosensitizers as disclosed in, for example, JP-A-57-114139 and JP-A-59-142205. Compositions are known.

In recent years, with advances in scanning exposure technology using laser light sources, and in particular the practical application of scanning exposure equipment using visible laser tips, there has been a desire to develop photosensitive materials that are highly sensitive to visible laser light such as argon ion laser light. Ta. However,
Conventional photosensitive materials are not only sensitive to ultraviolet rays, but even those that are sensitive to visible light are not necessarily sufficiently sensitive to visible laser light. Even if recording by laser beam scanning exposure is possible, it requires considerably high output and is not economical.

[Object of the Invention] An object of the present invention is to provide a photopolymerizable composition that exhibits high sensitivity to wavelengths in a wide range of wavelengths including ultraviolet rays and visible light. In particular, it is an object of the present invention to provide a photopolymerizable composition that exhibits excellent photosensitivity to visible laser light such as argon ion laser light.

[Structure of the Invention] According to research conducted by the present inventors, in a system of a photopolymerizable composition containing an addition polymerizable compound having an ethylenically unsaturated double bond and a photopolymerization initiator, By using a combination of a certain xanthine or thioxanthin dye, a diaryliodonium salt, and a compound having a methylene group at the alpha position of the nitrogen atom such as N-phenylgrine, the desired result can be obtained. I found out the fact that I can achieve my goal.

That is, according to the present invention, in a photopolymerizable composition containing an addition polymerizable compound having an ethylenically unsaturated double bond and a photopolymerization initiator, the photopolymerization initiator has (a) the following general formula: [1] [In the formula, A is an oxygen atom or a sulfur atom, X is a hydrogen atom or a halogen atom, and Y is a carbon atom or a nitrogen atom (however, when Y is a carbon atom, there ) is a double bond, and if Y is a nitrogen atom, it is a single bond with the adjacent carbon atom.), Z is an oxygen atom (in this case, with the adjacent carbon atom) ), lower alkoxy group or lower alkanoyloxy W, R' is lower alkyl shield,
Hydroquine lower alkyl group, lower alkoxyl lower alkyl group, lower alkylamino lower alkyl group or aryl group, R2 is a hydrogen atom, lower alkoxy group or di-lower alkylamino group.

Note that Z and R1 may be expressed together as -Z-4'-. ] A compound represented by (b) a diaryliodonium salt, and (C)
Provided is a photopolymerizable composition comprising a combination of compounds having a methylene group at the alpha position of a nitrogen atom.

A compound represented by the above general formula [+] (hereinafter referred to as component (a)
It is also sometimes called. ), specific examples of the halogen atom represented by X include chlorine and bromine. In addition, examples of the lower alkoxy group represented by Z include methoxyno, ethoxy, propoquino, etc. (Examples of the alkanoyl oxine group include acetyloquino, propionyl oxine, butyryloxy, etc.). Specific examples of lower alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and denyl; specific examples of hydroxy lower alkyl groups include hydroxymethyl, hydroxyethyl, hydroxypropyl, and hydroxyl. Specific examples of butyl, lower alkoxy, lower alkyl groups include methoxymethyl, methoxyethyl, methquinpropyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, proboquinedyl, propoquinpropyl, and di-lower alkylamino lower alkyl groups. Specific examples include dimethylaminomethyl, diethylaminoedyl, dimethylaminopropyl, dimethylaminomethyl, dimethylaminopropyl,
Examples of the aryl group include phenyl, xoryl, tolyl, naphthyl, etc., and examples of the lower alkoxy group represented by R2 include methoxy, ethquine, propoxy, di-lower alkylamino, etc. Specific examples include trimethylamine and diethylamino. The compound represented by the general formula [+] is a substance generally known in the literature as a xanthine or dioxanothene pigment.

The diaryliodonium salt (hereinafter sometimes referred to as component (b)) is a compound represented by the following general formula [■].

[In the formula, R3 to R0 are the same or different, hydrogen atoms,
Halogen atoms (e.g. chlorine, bromine), lower alkyl groups (
(e.g. methyl, ethyl, propyl, t-butyl), lower alkoxy group (e.g. methoxy, ethoxy, propokine) or nitro group, and X- represents a halogen ion (e.g. CQ-1Br-1I-), r3F, diPFa −
1AsP, - or 5bFa-.

] The compound represented by the general formula [II] is described, for example, in "Journal of Polymer Science
ym, Symp, ) vol. 56, pp. 383-395 (10
For example, diphenyliodonium, bis(p-chlorophenyl)iodonium, notryliodonium, bis(p-
Examples include chlorides, bromides, borofluoride salts, hexafluorophosphate salts, hexafluoroarsenate salts, and hexafluorophosphate salts of iodonium such as t-butylphenyl)iodonium and bis(m-nitrophenyl)iodonium. .

Examples of the compound having a methylene group at the alpha position of the nitrogen atom (hereinafter sometimes referred to as component (C)) include triethylamine, N-methyljetanolamine, triethanolamine, N-ethyl-N-benzyl Aniline, N, N-diethyl-p-phenylenediamine, N-
Examples include phenylgrin, and N-phenylgrin is particularly preferred.

The addition-polymerizable compound having an ethylenically unsaturated double bond (hereinafter sometimes referred to as a double-bond-containing compound) is addition-polymerized and cured by the action of a photopolymerization initiator, and substantially Any monomer or polymer can be used as long as it has a stable double unsaturated bond that causes insolubilization. Specific examples include unsaturated carboxylic acids, esters of unsaturated carboxylic acids and aliphatic polyhydroxy compounds, esters of unsaturated carboxylic acids and aromatic polyhydroxy compounds,
Addition products of unsaturated carboxylic acids and epoxides, esters obtained by esterification reactions of unsaturated carboxylic acids and polycarboxylic acids with polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroquino compounds. Can you name it?

Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, and maleinoic acid. Aliphatic polyhydroquino compounds include ethylene glycol, diethlene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, propylene glycol, dihydric alcohols such as 1,2-butanol, trimethylolethane, trimethylolpropane, and glycerol. Examples include trihydric alcohols such as, tetrahydric or dihydric alcohols such as pentaerythritol and tripentaerythritol, and polyhydric hydroquinocarboxylic acids. Examples of aromatic polyhydroxy compounds include hydroquinone, resorcinol, catechol, and pyrogallol. Epoxides include trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, propylene glycol diglycidyl ether, diglyndyl phthalic acid ester, epichlorohydrin and 2.2-
Examples include reactants with bis(4-hydroxyphenyl)-propane. Examples of polycarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, trimellitic acid, piC1mellitic acid, benzophenone dicarboxylic acid, maleic acid, fumaric acid, malonic acid, geltaric acid, anopic acid, and sebacic acid. , tetrahydrophthalic acid, etc.

Typical examples of esters of unsaturated carboxylic acids and aliphatic polyhydroxy compounds, or esters of unsaturated carboxylic acids and aromatic polyhydroquine compounds include acrylic acids of the above aliphatic polyhydroxy compounds or aromatic polyhydroxy compounds. Or ester of methacrylic acid. Typical examples of esters obtained by the esterification reaction of unsaturated carboxylic acids and polyhydric carboxylic acids with polyhydroquino compounds include those shown below. (However, Z″ is an acryloyl group or a methacryloyl group.)
-C1l = Cll -Cooi C211,0 juice Z'
Z' -QC, IL-00C- (C112), -CO
O-Cll2Z'-0Ct11. -00C-(C!
l,)4-COO-C11Z'-0C2+1. -00
C-(Cll2), -COO-Cll, -
Examples of double bond-containing compounds that can be used in the pond water invention include acrylamide, acrylamides such as ethylenebisacrylamide and hexamethylenebisacrylamide, methacrylamides such as ethylenebismethacrylamide and hexamethylenebismethacrylamide, and phthalates. Examples include double bond-containing compounds such as allyl esters such as noallyl acid, diallyl malonate, noallyl fumarate, and triallylisocyanurate-1.

Among double bond-containing compounds as polymers, examples of compounds with double bonds in the main chain include unsaturated dihydric carboxylic acids (e.g., maleic acid, fumaric acid) and nohydroquino compounds (e.g., the dihydric alcohols mentioned above). Examples include polyesters obtained by a polycondensation reaction between the above-mentioned unsaturated dihydric carboxylic acids and diamines (eg, ethylenediamine, hexamethylenediamine), and the like. Examples of compounds with a double bond in the side chain include dicarboxylic acids with a double bond in the side chain (e.g. itaconic acid, α-methylitafunic acid, γ-methylitaconic acid, propylidenesuccinic acid, α-edithic acid). redenedigtaric acid,
Examples include polyesters obtained by a polycondensation reaction of ethylidenemalonic acid or p[Jpylidenemalonic acid) with the above-mentioned divitroxy compounds, and polyamides obtained by a polycondensation reaction with the above-mentioned diamines. In addition, polymers obtained by polymer reaction between polymers with functional groups such as hydroquino groups or methyl halide in their side chains and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid are also used. can. In addition, as a polymer having a functional group in the side chain,
Polyvinyl alcohol, partially saponified polyvinyl acetate, copolymer of acrylonitrile with styrene, vinyl chloride, hnylidene chloride, completely saponified copolymer of acrylonitrile and vinyl acetate, 2-hydroquinethyl methacrylate and acrylonitrile , methyl methacrylate, butyl methacrylate-1, copolymers with styrene, vinylidene chloride, vinyl acetate, poly(4-hydroxystyrene), poly(N-methylolacrylamide), and the like.

Among the double bond-containing compounds mentioned above, it is particularly preferable to use monomers of acrylic esters or methacrylic esters.

In the composition of the present invention, component (a) is added in an amount of 0.01 to 0.2 weight flL per 1 part by weight of the double bond cargo compound.
&T4 Niji<iio, 02 to 0.1 parts by weight, component (b)
and (C), preferably 0.0005 to 0.02 parts by weight. It is used at a ratio of 1 to 0.08 parts by weight.

If the proportion of any of these three components used is less than the respective lower limit, the photosensitivity will decrease and it will take a long time to insolubilize the composition. Moreover, if the amount exceeds the upper limit, the strength and solvent solubility resistance of the filter film formed from the composition will deteriorate, making it unsuitable for practical use.

The composition of the present invention comprises the above-mentioned double bond naturally occurring compound and the component (a
In addition to the photopolymerization initiator consisting of the combination of (bXc), a polymeric binder, a thermal polymerization inhibitor, a plasticizer, a coloring agent, etc. may be used in combination as necessary. Polymer binders often meet various objectives, such as compatibility, film-forming properties, developability, and stability, and if an appropriate type is selected according to the purpose, good. For example, to improve developability with an aqueous solvent, copolymers of acrylic acid (or methacrylic acid) and acrylic acid (or methacrylic acid) alkyl esters (such as methyl ester, ethyl ester, butyl ester), itaconic acid copolymers, Partially esterified maleic acid copolymer, carboxyl j in the side chain,
Acidic cellulose modified products having ξ, polyethylene oxide, polyvinylpyrrolidone, etc. are used for one coat, and to improve film strength and adhesion, corohydrin and 2.2-
Polyethers, polyamides, etc. with bis(4-hydroxyphenyl)bu[1] are suitable for use.As thermal polymerization inhibitors, examples include hyde[1, p-methoxyphenol, pyrogallol, catechol, 2.6 - p-cresol, β-naphthol, etc. are useful. Examples of suitable IH agents include noocdylphthalate, nododenulphthalate, dibutyl phthalate, sitalic acid noester, and dioctyl adipate. ,
Useful examples include esters of 11 aliphatic dibasic acids such as butyl anovate and dibutyl sebacate. Useful colorants include, for example, phthalocyanine pigments, azo pigments, carbon black, titanium oxide pigments, triphenylmethane dyes, azo dyes, anthraquinone dyes, and the like.

The composition of the invention may be prepared in a conventional manner.

For example, if the above-mentioned essential components and optional components are used as they are, a solvent such as a ketone solvent such as methyl ethyl ketone, acetone, or cyclohexanone, an ester solvent such as ethyl acetate or butyl acetate, or an aromatic solvent such as toluene or quinolne is added as necessary. Solvents, cellosolve solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve,
Alcohol solvents such as methanol, ethanol and propatool, and ether solvents such as tetrahydrofuran and dioxane) are blended and mixed in a cool, dark place using, for example, a niegu or a mixer to prepare the product for 1 hour.

1. Effects of the Invention] A photosensitive layer based on the composition of the present invention can be formed by applying the composition onto a support according to a conventional method, for example, using a bar coater or a spinner, and drying it. Note that known techniques may be applied to the formed photosensitive layer to protect its surface and prevent adverse effects such as a decrease in sensitivity due to oxygen. For example, a removable transparent cover note may be provided on the photosensitive layer, or a coating layer made of a waxy material with low oxygen permeability, a water-soluble or alkali-soluble polymer, etc. may be provided.

The photosensitive layer can be used for lasers such as argon ion laser, helium cadmium laser, krypton laser, high pressure mercury lamp, low pressure mercury lamp, metal halide lamp, etc.
Insolubilization can be achieved using a general-purpose light source that generates ultraviolet or visible light, such as a xenon lamp or tungsten lamp.

Note that the phenomenon after light irradiation may be carried out using an appropriate developer capable of dissolving the unexposed photosensitive layer depending on the composition of the photosensitive layer.

As described above, the composition of the present invention exhibits high sensitivity to light in the wide wavelength range from ultraviolet rays to visible light, more specifically, from ultraviolet rays to 600 nm, which further expands the applicability of the composition. be able to. However, it exhibits excellent photosensitivity to visible laser light in the above wavelength range, such as argon ion laser light, so it can be used to print image signals using a scanning exposure device without using conventional negative film. a ray body directly provided with the composition of the present invention,
For example, lithographic printing plates, resists for producing printed wiring boards,
It can be written on a master plate for making a porogram matrix, and its practical effects are very large.

"Examples" The present invention will be specifically explained below using Examples and Comparative Examples, but the present invention is not limited to these Examples.

Practical Examples 1 to 8 and Comparative Examples 1 to B Preparation of Polymerizable Ingredient Methyl methacrylate/methacrylic acid copolymer (r13R-77j manufactured by Mitsubishi Rayon Fu, heavy industry average molecular weight '1't?
J70000) I00fW< (parts by weight, the same applies hereinafter) was dissolved in methyl ethyl ketone, and then 100 parts of pentaerythritol triacrylate was dissolved therein to obtain a first liquid.

Next, photopolymerization initiators (components (a) to
(C)) was dissolved in 300 parts of methyl cellosolve and a second
The total amount of each liquid was added to the first liquid and thoroughly stirred to obtain a molten tgL (photosensitive liquid) of the photopolymerizable composition.

Preparation of photosensitive layer (test plate) The above photosensitive solution was coated on an aluminum support using a bar coater so that the coating amount was 2 g/m2 when dry.
It was dried for 3 minutes in a dryer at 60°C.

A photosensitive layer with a thickness of 2.0 μm was obtained. This photosensitive layer was coated with 5% polyvinyl alcohol (
saponification degree 88%, polymerization degree 500) aqueous solution to a thickness of 2.0μ
It was coated in a uniform manner to form an overcoat layer.

Measurement of Sensitivity The Kodak Step Tablet No. 2 (21 steps) and the above test plate were superimposed, and Toshiba KL-/19 was exposed to light from a xenon lamp (manufactured by Ushio Inc., 150'#).
Light with a wavelength of around 490 parts m (light intensity 4, 0 mW/cm') extracted through a filter was irradiated from above for 10 seconds. Developed with a developer (10 parts by weight of anhydrous sodium carbonate, 50 parts of butyl cellosolve and 3 parts of anionic activator dissolved in 1000 parts of water),
The exposure energy required for curing was calculated based on the number of photocured stages, and the value was defined as "sensitivity". The results are shown in Table 1.

Argon ion laser - image formation output by light 0.2W
A laser beam (488 parts m) focused from an argon ion laser light source through an optical system to a beam diameter of 20μ is changed:
Cylindrical scanning on the test plate while modulating with A device (1000 rpm
m, 600 lines/inch).

Next, this was developed using the developer described above to obtain an ``argon ion laser image''. The results are shown in Table 1.

(Note) Component a-1: The above general formula [where A=S, X=1-
1. Y=C, Z=OC, I-(5, R'=C.

H5 (phenyl), a compound where R''=H.

Component a-2: In general formula [l] m, A=O1X-C
l, Y = N, Z = O1R'=C, ll5
0(CH2)3, R2-N(C,R5).

Component bl: Borofluoride salt of diphnyliodonium.

Component b-2 Borofluoride salt of p-tolyliodonium.

Ingredient c-1 N-phenylglycine.

Component c-2: t-liethanolamine.

As is clear from the results in Table 1, when a combination of components (a) to (C) is used as a photo-synthesis initiator, compared to a case where the combination of components (a) to (C) is used as a photo-synthesis initiator, the 5
It is recognized that the sensitivity is about twice as high, indicating its high practicality, and that it also exhibits high photosensitivity to visible laser light.

Example 9 All tests were conducted in the same manner as in Example I, except that 100 parts of a compound obtained by adding 2 moles of acrylic acid to 1 mole of propylene glycol diglycidyl ether was used instead of 100 parts of pentaerythritol triacrylate in Example 1. A plate was prepared, sensitivity was measured, and an image was formed using argon ion laser light. As a result, the sensitivity is 0.6
mJ7cz', and the image obtained by the argon ion laser was as clear as that obtained in Example 1.

Claims (1)

[Claims] 1. A photopolymerizable composition containing an addition polymerizable compound having an ethylenically unsaturated double bond and a photopolymerization initiator,
The photopolymerization initiator has the following general formula [I] ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, A is an oxygen atom or a sulfur atom, X is a hydrogen atom or a halogen atom, and Y is a carbon atom. or a nitrogen atom (however, if Y is a carbon atom, there is a double bond between the adjacent carbon atoms (indicated by a dotted line), and if Y is a nitrogen atom, the adjacent carbon atom ), Z is an oxygen atom (in this case, there is a double bond between adjacent carbon atoms), a lower alkoxy group or a lower alkanoyloxy group, R^1 is a lower alkyl group , a hydroxy lower alkyl group, a lower alkoxy lower alkyl group, a di-lower alkylamino lower alkyl group or an aryl group, and R^2 is a hydrogen atom, a lower alkoxy group or a di-lower alkylamino group. In addition, Z and R^1 are both combined as -Z-R^1-,
▲There are mathematical formulas, chemical formulas, tables, etc.▼ It can also be expressed. ] A photopolymerizable composition comprising a combination of a compound represented by (b) a diaryliodonium salt, and (c) a compound having a methylene group at the α-position of a nitrogen atom. 2. The composition of item 1 above, wherein component (c) is selected from the group consisting of N-phenylglycine, triethylamine and triethanolamine.