JPH0415201A - Visible ray-sensitive resin composition and method for image formation using the same - Google Patents

Abstract

PURPOSE:To prepare the title compsn. excellent in sensitivity by compounding a film-forming substance having a polymerizable ethylenically unsatd. bond with a specific photoperoxide-forming radical generator. CONSTITUTION:The title compsn. contains a compd. having at least one polymerizable ethylenically unsatd. bond and a photoperoxide-forming radical generator comprising a triplet photosensitizer which is a 3-ketocoumarine compd. of formula I or a biscoumarine compd. of formula II, a photooxidizable compd., and a redox catalyst. In the formulas, R1 and R2 are each H, chlorine, alkoxy, dialkylamino, or a condensed phenyl ring; R3 is H or cyano; and R4 is lower alkyl or aryl. A photosensitive plate obtd. by molding the compsn. into a film is irradiated with visible rays in the presence of oxygen, heated in an inert gas atmosphere or in vacuum to cause crosslinking and polymn. in irradiated areas, and is developed, thus forming an image.

Description

[Detailed Description of the Invention] [Object of the Invention] (Industrial Application Field) The present invention is applicable to not only photoresist materials using a normal visible light source, plate-making materials marked 11J, etc., but also photoresist materials that are scanned at high speed by a laser light source. A 3-ketocoumarin compound having a specific structure or a biscoumarin compound substituted with carbonyl at the 3-position is used as a triplet photosensitizer as an image forming material using a laser scanning device or as a high-sensitivity photosensitive material in place of silver salt. The present invention relates to a visible light-sensitive resin composition that uses a photoperoxide-forming radical generator in combination with a photooxidizing compound and a redox catalyst and exhibits excellent sensitivity, and an image forming method thereof.

(Prior Art) Various proposals have been made for photosensitive resin compositions that are sensitive to visible light, and among them, photosensitive compositions that use a coumarin compound as a sensitizer in combination with various photopolymerization accelerators. JP-A-52-112681 discloses photosensitive resin compositions using coumarin compounds,
Engineering and Science (Po 1 y
m, Eng, Sci, ) J Volume 23, No. 18, No. 1
022 (1983) describes a photopolymerization initiator consisting of a ketocoumarin compound and various aromatic amines, and JP-A-58-15503 discloses a photosensitive resin composition in which a 3-ketocoumarin compound is combined with an active halogen compound. JP-A-60-88005 discloses a photopolymerization initiator consisting of a combination of a 3-ketocoumarin compound and a diaryliodonium salt, and JP-A-63-23901 discloses a photopolymerization initiator consisting of a combination of a coumarin compound and an organic peroxide. A photosensitive resin composition characterized by a combination of the following has been reported. In addition, a photopolymerization initiator consisting of three components (diphenyliodonium salt and N-phenylglycine) containing a ketocoumarin compound is described in "Journal of Photopolymer Science and Technology (J.

Photopolym, Sci, Technol,)J
Reported in Volume 1, No. 2, Page 222 (1988).

On the other hand, Japanese Patent Publication No. 58-42459 proposes a method for producing a printing plate using a photosensitive composition comprising a photooxidative composition and a photooxidative sensitizer.

(Problem to be solved by the invention) However, in the above-mentioned attempt, the photopolymerizable photosensitive composition using a photopolymerization initiator in which a coumarin compound and various polymerization accelerators are combined cannot be used with a visible laser such as an Ar laser. Although it is possible to form an image by high-speed scanning exposure, it is desired to further improve the sensitivity characteristics. Furthermore, in order to improve the sensitivity characteristics of photosensitive resin compositions using these photopolymerization initiators, it is necessary to block oxygen, which suppresses photopolymerization reactions, during light irradiation, so it is necessary to use a tri-film form,
Alternatively, it is necessary to provide an oxygen inhibiting layer, such as a polyvinyl alcohol film, on the photosensitive layer, which poses difficulties in handling and economy.

In addition, in the latter photosensitive composition consisting of a photooxidative composition and a photooxidative sensitizer, the solubility of the photooxidative sensitizer in various solvents, The ability to generate peroxide and/or wavelength matching with the laser light source are not necessarily satisfactory, and therefore the sensitivity characteristics are insufficient and cannot withstand the high-speed scanning exposure of the laser. In addition, the 3-ketocoumarin compound having a specific structure or the biscoumarin compound substituted with carbonyl at the 3-position, the effects of which have been clarified in the present invention, are very effective compounds as photooxidative sensitizers. Something was completely unknown.

(Means for Solving the Problems) The present inventors took the above points into consideration and achieved the above object (as a result of intensive studies, they found that a 3-ketocoumarin compound having a specific structure or a carbonyl substituted at the 3-position) A photoperoxide-forming radical generator, which is a combination of a biscoumarin compound obtained as a triplet photosensitizer and a photooxidizing compound and a redox catalyst, and at least one polymerizable ethylenically unsaturated bond. A photosensitive plate on which a photosensitive resin composition comprising a film-forming substance and a film-forming substance is irradiated with visible light in the presence of oxygen is exposed to an inert gas (for example, nitrogen gas or argon gas, etc.). ) By heating in an atmosphere or vacuum, causing a crosslinking polymerization reaction in the exposed area, and treating with an appropriate developer, the composition is an unprecedented highly sensitive photosensitive resin composition; They also discovered that the technology exhibits reciprocity-based behavior in response to high-speed laser scanning exposure, and that it is fully applicable to laser direct printing plate materials or resist materials that utilize this technology, leading to the present invention. .

The present invention will be explained in detail below.

The compound (a) having at least one polymerizable ethylenically unsaturated bond constituting the visible light-sensitive resin composition of the present invention may be an oligomer or a high molecular weight compound in addition to a vinyl monomer. Specifically, vinyl monomers include acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, acrylamide, methacrylamide, diacetone acrylamide, 2-hydroxyethyl acrylate, N-vinylcarbazole,
There are high-boiling monomers such as N-vinylpyrrolidone, as well as aliphatic polyhydroxy compounds such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, 1,3-propanediol, 1. 4-butanediol, 1,5-bentanediol, 1,6-hexanediol, 1. di- or poly(meth)acrylic esters of IO-decanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, mannitol, etc., aromatic polyhydroxy compounds such as hydroquinone, resorcinol, catechol, pyrogallol, etc. di or poly (meta)
Polymer reactions between acrylic esters, polymers with reactive functional groups such as hydroxy groups and halogenated methyl groups in their side chains, and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid. Polymers obtained by can also be suitably used. Examples of such polymer compounds include polyvinyl alcohol, copolymers of vinyl alcohol and vinyl acetate, polyepichlorohydrin, phenoxy resins, polychloromethylstyrene, and copolymers of 2-hydroxy(meth)acrylate and various acrylate monomers. , phenolic resin, etc.

Among the photoperoxide-forming radical generators that are another component constituting the visible light-sensitive resin composition of the present invention, the triplet photosensitizer (A) is of the general formula (I ) (In formula (I), R1 and R2 are a hydrogen atom, a chloro atom, an alkoxy group, a dialkylamino group, or a fused benzene ring, R5 is a hydrogen atom or a cyano group, and R4
represents a lower alkyl or aryl group) or a carbonyl compound at the 3-position represented by general formula (II) (R1, R2, and R3 in formula (n) have the same meanings as above) It is a substituted biscoumarin compound.

The 3-ketocoumarin represented by general formula (I) includes 3
-thienoylcoumarin, 3-(4-methoxybenzoyl)coumarin, 3-benzoylcoumarin, 3-(4-cyanobenzoyl)coumarin, 3-thienoyl-7-medoxycoumarin, 7-medoxy-3-(4-methoxybenzoyl) ) Coumarin, 3-benzoyl-7-medoxycoumarin, 3-(4-cyanobenzoyl)-7-medoxycoumarin, 5,7-cymethoxy-3-thienoylcoumarin,
5,7-Simethoxy3-(4-methoxybenzoyl)
Coumarin, 3-benzoyl-5,7-simethoxycoumarin, 3-(4-cyanobenzoyl)-5,7-dimethoxycoumarin, 3-benzoyl-7-ethylaminocoumarin, 7-dinitylamin-3-(4-dimethyl aminobenzoyl)coumarin, 7-diethylamino-3-thienoylcoumarin, 3-(2-benzofuroyl)-7-dinithylaminocoumarin, 3-cinnamoyl-7-dinithylaminocoumarin, 3-(p-diethylaminocinnamoyl) -7-dinithylaminocoumarin. Furthermore, an aromatic ring may be further condensed to the coumarin benzene nucleus. Next, 3 represented by general formula (II)
Examples of biscoumarin compounds substituted with carbonyl at position include 3,3'-carbonylcoumarin, 3,3'-carbonylbis(7-medoxycoumarin L5,7-simethoxy3,3'-carbonylcoumarin, 5.7. 7
° -trimethoxy-3,3'-carbonylbiscoumarin, 3,3'-carbonylbis(5,7-simethoxycoumarin)3,3°-carbonylbis(5,7-diethoxycoumarin), 7-diethylamino- 3,3'-Carbonylbiscoumarin, 7-diethylamino-5', F'-dimethoxy-3,3'-carbonylbiscoumarin, 3,3'-carbonylbis(7-dinithylaminocoumarin), 3,3' -Carbonyl bis (julolithic marine) and the like.

Both of these 3-ketocoumarin compounds or biscoumarin compounds substituted with carbonyl at the 3-position have a quantum efficiency of 0.1 or more for singlet oxygen, which is active oxygen essential for oxidizing the photooxidizable compound (B). In particular, if the coumarin has an alkoxy group or dialkylamino group on the benzene nucleus, or a cyano group on the unsaturated carbon of the coumarin nucleus, it can generate light at the 488 nm or 514 nm oscillation wavelength of the Ar laser. Improves matching performance. The method for synthesizing these 3-ketocoumarin compounds or biscoumarin compounds substituted with carbonyl at the 3-position is based on the ``tetrahedron'' method.
n) Volume 38, No. 9, Page 1203 (1982).

Among the photoperoxide-forming radical generators, the photooxidizing compound (B) has the formula (III) (wherein R3 is a hydrogen atom or a halogen atom such as chlorine or bromine, and R1 is a methyl group). Or it represents a trifluoromethyl group.) Dimethylcyclohexene compound represented by
No. 8-42459), or formula (IV) (in which R8
and R;. have the same meanings as R6 and R7 in formula (I) respectively) and a dimethylfuran compound represented by formula (VI) (
In the formula, R1 and R1 are R3 and R1 in formula (III)
) or a trimethylcyclohexadiene compound represented by formula (V) (wherein R1+ and R12 are R6 in formula (III))
and R6 have the same meanings, respectively).

These compounds have at least one methyl group on the carbon that forms a double bond, and this methyl group reacts with hydrogen or singlet oxygen to produce peroxide.

Among photoperoxide-forming radical generators, redox catalysts (
C) is preferably a metal salt or complex that exists in two or more valence states, such as vanadium oxyacetylacetonate, vanadium oxysulfate, vanadium oxynaphthenate, vanadyl oxytetraphenylporphyrinato, oxyoctaethylporphyrinato. vanadyl, oxytetra-t-butylphthalocyanine vanadyl,
Oxyvanadium salts or complexes such as cobalt cobalt acetylacetonate, cobalt cobalt acetylacetonate, cobalt naphthenate, cobalt naphthenate,
Cobaltous stearate, cobaltous stearate, cobalt acetate, cobalt tetraphenylporphyrinato, cobalt octaethylporphyrinato, Tetra-T
- Salts or complexes of cobalt such as butylphthalocyanine cobalt, manganous stearate, manganous stearate, manganous acetylacetonate, manganous stearate,
Manganese acetylacetonate, manganese acetate, manganese naphthenate, manganese tetraphenylporphyrinato,
Manganese salts or complexes such as octaethylporphyrinatomanganese, tetra-t-butylphthalocyanine manganese, iron(III) acetylacetonate, iron(II[)
Benzoylacetonate, tetraphenylporphyrinato iron (III) chloride, octaethylporphyrinato iron (I) chloride, tetra-T-butylphthalocyanine iron (III) chloride, iron naphthenate (■), ferrocene, cyclopentagenyl- Cumene iron hexafluorophosphate, iron salt or complex with iron (■) 0-phenanthroline, titanyl acetylacetonate, titanocene, dicyclopentadienyl titanium (In)
Examples include dichloride, oxytitanium acetylacetonate, and titanium salts or complexes.

Although there is a wide degree of freedom in the blending ratio of each component forming the visible light-sensitive resin composition of the present invention listed above, in order to use the resin composition more effectively, the following It is desirable to use them at the appropriate blending composition ratio. That is,
The ratio of the photoperoxide-forming radical generator (b) to the compound having at least one polymerizable ethylenically unsaturated bond (a) is 1 to 40 parts by weight per 100 parts by weight of the former. , more preferably from 4 parts by weight to 20 parts by weight. Among photoperoxide-forming radical generators (b), triplet photosensitizers (viii), photooxidizing compounds (
The composition ratio of B) is in the range of 10:1 to 1:10, more preferably in the range of 4:1 to 1=4, but especially for the triplet photosensitizer (A), the visible light sensitizer It is important to take care so that the optical density does not exceed 2.0 in the irradiation wavelength light region when various resin compositions are applied onto the substrate. Further, the content of the redox catalyst (C) is desirably added in a range of 0.01 to 5.0 parts per 100 parts by weight of the compound (a) having at least one polymerizable ethylenically unsaturated bond. .

This is not particularly necessary if the compound (a) having at least one polymerizable ethylenically unsaturated bond has sufficient molecular weight or strength to form a film, but if not. In this case, it is possible to incorporate a polymeric substance as a binder into the above composition as a usual method. Such binders are used to achieve various purposes of improving film-forming properties, developability, adhesiveness, mechanical strength, etc., and an appropriate type may be selected depending on the purpose. Specifically, for example, to improve water-based developability, acrylic acid copolymers, methacrylic acid copolymers, itaconic acid copolymers, partially esterified maleic acid copolymers, and cellulose acetate modified with carboxyl groups in side chains are used. There are materials such as polyethylene oxide and polyvinylpyrrolidone, and to improve film strength or adhesiveness, epoxy resin,
Phenoxy resin, polyether of epichlorohydrin and bisphenol 8, soluble nylon, copolymer of polyalkyl (meth)acrylate (e.g. polymethyl methacrylate, polymethyl acrylate, etc.) and poly(meth)acrylic acid, styrene and (meth)acrylic acid, ) Copolymers with acrylic acid, polyurethane, and polyvinyl butyral. These binders are usually blended in an amount of 1000 parts by weight or less, preferably 50 to 200 parts by weight, per 100 parts by weight of the compound (a) having at least one polymerizable ethylenically unsaturated bond.

A photosensitive solution prepared by dissolving a visible light-sensitive resin parabolite having the above composition ratio in an appropriate solvent is applied directly onto the substrate as a photosensitive film using a spin coater, roll coater or bar coater. Alternatively, it can be used as a dry film in which the photoresist film is coated on a plastic film using a similar box construction method, the solvent is evaporated, and then the photoresist film is covered with another plastic film. In the latter case, when used, one of the inner sides of the plastic film for coating is peeled off and the photoresist film is transferred onto an arbitrary Go board.

A photosensitive plate (or film) formed from the visible light-sensitive resin composition of the present invention obtained as described above can be used in the presence of carbon arc, high-pressure mercury lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, etc. in the presence of oxygen. Either a visible light source such as a lamp is irradiated through a lithium film formed with various patterns, or a visible laser beam such as a helium cadmium laser or an argon laser is used as it is or focused into a minute spot.
It is also possible to scan and expose at high speed using a laser scanner equipped with a beam scanning optical element such as a polygon mirror or a galvano mirror.

Next, the photosensitive plate (or film) is exposed to an inert gas.
For example, by heating in a gas atmosphere such as nitrogen gas or argon gas, or under vacuum, the radical polymerization reaction at the light irradiation site is induced and promoted. The temperature conditions at this time can be selected within the range of 40°C to 120°C, but are preferably between 60°C and 90°C.

Development of a heat-treated photosensitive plate (or film) is
Depending on the composition of the photosensitive resin layer, an appropriate developer capable of dissolving the photosensitive resin layer may be used.

(Function) The visible light-sensitive resin composition of the present invention comprises a compound having at least one polymerizable ethylenically unsaturated bond, a triple photosensitizer, a photooxidizing compound, and a redox catalyst. . When the resin composition is irradiated with visible light, the 3-ketocoumarin compound, which is a triple photosensitizer, or the biscoumarin compound substituted with carbonyl at the 3-position absorbs the light and is excited and activated at the light irradiation site. However, in the triplet photosensitizer, the triplet state quickly transitions to the excited triplet state with a high probability of 0.5 or more. The sensitizer in this excited triplet state is able to impart its energy to oxygen molecules, and as a result, singlet oxygen, which is active oxygen, is generated. At this time, the higher the transition probability (intersystem cross efficiency) of the sensitizer to the excited triplet state, the higher the efficiency of energy donation to oxygen molecules. It is not clear why the 3-ketocoumarin compound or the biscoumarin compound substituted with carbonyl at the 3-position in the present invention is superior in its properties, but it is based on its basic structural skeleton and its transition to an excited triplet state. This may be due to the extremely high probability (intersystem cross efficiency). For the above reasons, the 3-ketocoumarin compound or the biscoumarin compound substituted with carbonyl at the 3-position in the present invention is particularly excellent in the ability to generate active oxygen, and it is possible to convert many oxygen molecules into active oxygen by light irradiation. It is. The active oxygen generated in this manner quickly reacts with the photooxidizing compound of the present invention to generate peroxide. Many compounds are known that react with active oxygen to form peroxides (e.g., H, H, Basserman, R, W, Murray, eds., Singlet Oxygen Academic Press, (1979), p. 287), derivatives of olefin compounds represented by general formulas (III) to (IV) having at least one methyl group on a double bond carbon are particularly effective in the present invention. The reason for this is the reaction rate constant between these olefin compound derivatives and active oxygen in the present invention, or the 10'M-
Because the reaction is faster than 's-' and because the olefin derivative has a dialkyldiphenylmethane skeleton in the molecule as a skeleton, we succeeded in suppressing the volatility of the olefin molecule, which is normally volatile or extremely high. Depends on what you did.

The peroxide formed at the light irradiation site through the above photoreaction process undergoes a redox reaction with a metal salt or complex that can exist in two or more valence states, and the peroxide is Oxides are decomposed and radicals are generated. At this time, by exposing and heating the photosensitive material under vacuum or an inert gas atmosphere such as nitrogen gas or argon gas, the generated radicals are not annihilated by oxygen molecules (increasing efficiency).
This seems to be the result that the crosslinking polymerization reaction of the compound having at least ] or more polymerizable ethylenically unsaturated bonds of the present invention is efficiently promoted.

(Effects of the Invention) The visible light-sensitive resin composition of the present invention can be applied to visible light sources such as carbon arc, high pressure mercury lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, helium cadmium, argon laser, etc. in the presence of oxygen. Even with a visible laser light source such as
It exhibits extremely high sensitivity characteristics ranging from J/cm' to 300 μJ/cm''. Also, it does not show reciprocity failure behavior even in high-speed scanning exposure using laser beam scanning, so it is suitable for image forming materials using laser beam scanning, such as direct printing plates. It can be applied to photoresists for printed wiring boards, non-silver salt image forming materials, etc. It is also applicable to Lippmann holograms, which require high sensitivity to form delicate interference fringes, and which are difficult to make large areas. It can be applied to a wide range of fields, such as as a hologram recording material in relief-type hologram recording in rainbow holograms.

(Example) Next, the present invention will be explained in more detail with reference to Examples.

The molar ratio of tetramethylstyrene and methyl methacrylate is 1.
A copolymer having a ratio of 1:1 and potassium ac-1-norate salt were mixed in 40 ml of dimethylformamide under oxygen gas IJ at 40°C using tetrabutylammonium chloride and potassium carbonate as a phase transfer catalyst. de1
The reaction was carried out for 2 hours to obtain a polymer having an acro-n group in the side chain. The obtained BoIJmer was dissolved in dioxane to prepare a solution with a concentration of 5% by weight, which was subsequently used as a resin for evaluating sensitivity characteristics.

Examples 1 to 10 The present examples are examples in which the following bisphenol derivative (A) of dimethylcyclohexene is used as a photooxidizing compound.

2gt dioxane solution of the above polymer
) to the polymer, 10 parts by weight of the 3-ketocoumarin compound shown in Table 1 or a biscoumarin compound whose 3-position is substituted with carbonyl, 10 parts by weight of dimethylcyclohexene derivative, oxyvanadium acetylaceto A photosensitive solution prepared by adding 0.1 parts by weight of Nato was coated on a glass plate using a spin coater to a thickness of about 2 μm, and an argon laser (488 or 514 nrri light) with a beam diameter of 2 mm or Exposure to helium cadmium laser (441 nm light) by changing the irradiation time at 6o''C under a vacuum of 1 mmHg or more
After heat treatment for 13 minutes, development was performed with toluene, and the exposure dose that gave a cured spot diameter equivalent to the laser beam diameter is shown in Table 1 as the sensitivity.

Examples 11 to 16 In the compositions of Examples 1 to 10, the 3-ketocoumarin shown in Example 3 as the dye and the biscoumarin in which the 3-position was substituted with carbonyl shown in Example 9 were used as the photooxidizing compound ( Table 2 shows the sensitivity characteristics when using the sorefine derivatives B) to (D).

12th

Claims (1)

[Claims] 1. (a) a compound having at least one polymerizable ethylenically unsaturated bond, and (b) a 3-ketocoumarin compound represented by general formula (I) or general formula (II) A triplet photosensitizer (A) which is a biscoumarin compound represented by
A visible light-sensitive resin composition comprising a photooxidizing compound (B) and a photoperoxide-forming radical generator comprising a redox catalyst (C). General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼...(I) (In formula (I), R_1 and R_2 are hydrogen atoms, chlorine atoms, alkoxy groups, dialkylamino groups, or fused benzene rings. , R_3 represents a hydrogen atom or a cyano group, and R_4 represents a lower alkyl or aryl group) General formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼... (II) (In formula (II), R_1, R_2 and R_3 are general formulas (I
) is a biscoumarin compound substituted with carbonyl at the 3-position. 2. A claim in which the photooxidizing compound (B) is an olefin compound having at least one methyl group on a double-bonded carbon that can react with singlet oxygen to form a photoperoxide. 1. The composition according to item 1. 3. The composition according to claim 1, wherein the redox catalyst (C) is a metal salt or complex that can exist in two or more valence states. 4. (a) A compound having at least one polymerizable ethylenically unsaturated bond, and (b) a 3-ketocoumarin compound represented by general formula (I) or a biscoumarin compound represented by general formula (II). A triplet photosensitizer (A),
Oxygen is applied to a photosensitive plate formed into a film of a visible light-sensitive resin composition containing a photoperoxide-forming radical generator consisting of a photooxidizing compound (B) and a redox catalyst (C). An image forming method comprising: irradiating the photosensitive plate with visible light in the presence of light, heating the photosensitive plate under an inert gas atmosphere or under vacuum to cause a crosslinking polymerization reaction in the exposed area, and then developing the photosensitive plate. .