JPH09227547A - Visible light photosensitive resin composition and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a visible light photosensitive resin composition high in sensitivity to a second harmonic such as argon laser or YAG laser as a stable laser light source having high output and excellent in compatibility to resin and shelf stability. SOLUTION: This composition comprises a 3-keto-substituted coumarin compound of formula I [R1 and R2 are each H, an alkyl, an alkenyl, an aralkyl, an aryl, etc.; R3 is H, a halogen, an alkyl, etc.; R4 is H, a halogen, OH, etc.; R5 is a group of formula II (A is an aromatic ring), etc.] and a titanocene. The compound of formula I is extremely useful as a photosensitizer and is combined with the titanocene compound to give a photopolymerization initiator composition high in sensitivity to visible light. Both the compounds are excellent in compatibility with a base resin, are soluble in a coating solution of general use and are capable of providing a substrate with a uniform and smooth coated face. A photosetting material obtained from a visible light photosensitive resin composition using a photopolymerization initiator composition containing both the compounds can be exposed by high-speed scanning by the laser. The prepared image has extremely high resolution.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a visible light-sensitive resin composition having high sensitivity to light in the visible light region, and more particularly to a visible light characteristic of a photopolymerization initiator composition. The present invention relates to a photosensitive resin composition.

[0002]

2. Description of the Related Art Polymerizable compounds having an ethylenically unsaturated double bond (monomers, oligomers, polymers and copolymers thereof) have the property of being crosslinked or polymerized in the presence of a photopolymerization initiator. Using this,
It is widely used as a so-called photopolymer or photoresist for producing printing plates, printed boards, ICs, and the like. In recent years, in the field of information or image recording using photopolymerization reaction, instead of the conventional recording method by ultraviolet rays using film originals, etc., electronically edited originals by computer are directly output directly using high-power laser. However, the method of recording is being considered. This method
The direct writing with a laser has an advantage that the recording and image forming processes can be greatly simplified.

Currently, most of the commonly used high-power and stable laser light sources have their output wavelengths in the visible region. Specifically, the wavelengths of 488 nm and 51
An argon laser having a stable oscillation line at 4.5 nm, a YAG laser having a bright line at 532 nm as a second harmonic (abbreviated as SHG), and the like are widely used. Therefore, a photopolymerization initiator composition having high sensitivity to those wavelengths is desired, but a photopolymerization initiator composition for ultraviolet ray which has been conventionally used can be used because of its low sensitivity in the visible region. There wasn't. Although it is possible to improve the sensitivity in the visible region by adding a pyrylium salt or a thiopyrylium salt, the storage stability of the photosensitive layer is low and it is difficult to use.

The photopolymerization initiator composition usually comprises two or more compounds such as a polymerization initiator and a photosensitive compound (photosensitizer). An example of using a 3-keto-substituted coumarin as a sensitizer in a photopolymerization initiator composition is disclosed in JP-A-52-11.
2681, and also JP-A-5-289335.
And JP-A-6-43642 describe combinations of 3-substituted coumarin compounds and titanocene compounds. However, these still have insufficient sensitivity.

[0005]

SUMMARY OF THE INVENTION The present invention provides an argon laser or a YA which is a high power and stable laser light source.
It is intended to provide an initiator composition and a photosensitive resin composition which are highly sensitive to a laser beam in the visible light region such as G laser (SHG) and have excellent compatibility with resins and excellent storage stability.

[0006]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that the use of a certain coumarin compound in combination with a titanocene compound provides excellent effects. The present invention has been completed. That is, the present invention is a photosensitive resin composition containing a polymerizable compound having an ethylenically unsaturated double bond and a photopolymerization initiator composition, which can be crosslinked or polymerized by irradiation with visible light. The present invention relates to a visible light-sensitive resin composition comprising a 3-keto-substituted coumarin compound represented by the following general formula (1) (Chemical formula 7) and a titanocene compound. .

[0007]

Embedded image Wherein R ₁ and R ₂ are each a hydrogen atom, an alkyl group,
It represents an alkoxyalkyl group, an alkenyl group, a hydroxyalkyl group, an aralkyl group, an aryl group or an alkoxycarbonylalkyl group, which may be bonded to each other or bonded to a benzene nucleus substituted with an amino group in the skeleton to form a ring. , R ₃ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxyalkyl group, a hydroxyalkyl group, a halogenoalkyl group, a hydroxyl group, an alkoxy group, an alkoxyalkoxy group, an alkylthio group, an arylthio group or a sulfonic acid group, and R ₄ represents hydrogen. Atom, halogen atom,
Alkyl group, halogenoalkyl group, hydroxyl group, alkoxy group, cycloalkoxy group, cyano group, carboxyl group,
Alkoxycarbonyl group, cycloalkoxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, aralkyloxycarbonyl group, alkoxycarbonylalkoxycarbonyl group, alkylcarbonylalkoxycarbonyl group, or the following general formula (2
a) to (2c), which represents any of the substituents represented by Chemical formula 8,

[0008]

Embedded image (Here, Q _{1 to} Q ₄ are each a hydrogen atom, an alkyl group,
Shows a hydroxyalkyl group, a hydroxyalkoxyalkyl group, an alkoxyalkyl group, a cycloalkyl group,
n, m, p, and q each represent an integer of 1 to 5) R ₅ is any substituent represented by the following general formulas (3a) to (3d) (formula 9).

[0009]

Embedded image (Here, aromatic rings A to F may be substituted)

In the present invention, in the 3-keto-substituted coumarin compound represented by the general formula (1), R ₃ is hydrogen atom, R ₄ is hydrogen atom, cyano group, carboxyl group, alkoxycarbonyl group, cycloalkoxy. A carbonyl group, an aryloxycarbonyl group, an alkenyloxycarbonyl group, or any substituent represented by the general formulas (2a) to (2c), and R ₅ is a general formula (3a) to (3d).
Which is any of the substituents represented by (wherein aromatic rings A to F are substituted with one or more alkoxy groups, aryloxy groups, alkylamino groups or arylamino groups). A photosensitive resin composition, or an ink for a visible light photosensitive material containing the visible light photosensitive resin composition and a solvent, or a visible light photosensitive resin composition having a visible light photosensitive resin composition on a substrate. Material, in the general formula (1), R ₄ is a cyano group, a carboxyl group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an aryloxycarbonyl group, an alkenyloxycarbonyl group, an aralkyloxycarbonyl group,
The present invention relates to a novel 3-keto-substituted coumarin compound which is an alkoxycarbonylalkoxycarbonyl group, an alkylcarbonylalkoxycarbonyl group, or any substituent represented by the general formulas (2a) to (2c).

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The visible light-sensitive resin composition of the present invention means a polymerizable compound having an ethylenically unsaturated double bond (hereinafter abbreviated as an ethylenic compound) and a photopolymerization initiator composition (hereinafter, an initiator composition and Abbreviated) and, if necessary, a solvent or other photocurable resin. The initiator composition is a composition capable of initiating crosslinking or polymerization of an ethylenic compound by irradiation with light.
The composition contains a radical polymerization initiator and a photosensitizer, and may further contain substances called activators and initiation aids.

The photopolymerization initiator composition used in the visible light-sensitive resin composition of the present invention contains a 3-keto-substituted coumarin compound useful as a photosensitizer and a titanocene compound known as a photoinitiator. To do. Although the titanocene compound has absorption in the visible region, it has insufficient sensitivity by itself, and its absorption at 500 nm or more is slight. Therefore, 514.5 nm argon laser and 532 nm YAG laser are used. With (SHG), polymerization and crosslinking of ethylenic compounds cannot occur.
On the other hand, among the coumarin compounds generally known as photosensitizers, the 3-keto-substituted coumarin compounds have a sensitivity of 400 to 400 that can be exposed to an argon laser or a YAG laser (SHG).
It has absorption at 600 nm. The present invention is based on the finding that an initiator composition having high sensitivity to laser light in the visible light region can be obtained by combining these. The 3-keto-substituted coumarin compound used in the present invention is a compound having a partial structure represented by the following formula (4) (formula 10).

[0013]

Embedded image

Among these compounds, those having an amino substituent are preferable from the viewpoint of absorption wavelength and sensitivity, as compared with the compound having an alkoxy group at the 5, 6, 7 or 8 position. However, from the viewpoint of sensitivity as an initiator composition,
Those having an amino substituent at the 5, 6 or 8 position have poor sensitivity. Therefore, a 3-keto substituted coumarin compound having an amino substituent at the 7-position is most suitable. Among them, the compound having higher sensitivity is the compound represented by the general formula (1). In the high-sensitivity visible light-sensitive resin composition of the present invention, the titanocene compound means the following general formula (5)
It can be represented by 1).

[0015]

Embedded image (In the formula, P ₁ and P ₂ each represent a cyclopentadienyl group which is unsubstituted or substituted with 1 to 2 methyl groups,
P ₃ and P ₈ are each a fluorine atom, a —CF ₃ group or —
Indicates CF ₂ CH ₃ group, P ₄ to P ₇ and P ₉ to P ₁₂ are each a hydrogen atom, a fluorine atom, -CF ₃ group, -CF ₂ CH
₃ groups, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a 1-pyrrolyl group are shown) As preferred specific examples, the following formulas (6a) to (6d)
A compound represented by (Chemical Formula 12) can be given.

[0016]

Embedded image

3 represented by the general formula (1) used in the present invention
-A keto-substituted coumarin compound will be described. In the general formula (1), examples of R ₁ and R ₂ are each independently or identically a hydrogen atom; an alkyl group having 1 to 6 carbon atoms; methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, γ-ethoxy. Alkoxyalkyl groups such as propyl group; alkenyl groups such as allyl, 2-butenyl, 2-pentenyl group; hydroxymethyl, hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl,
Hydroxyalkyl group such as 2-hydroxybutyl group; aralkyl group such as benzyl and phenethyl group; phenyl, p-methylphenyl, m-methylphenyl, o-methylphenyl,
An aryl group such as a 2,4-dimethylphenyl group; an alkoxycarbonylalkyl group such as a methoxycarbonylmethyl, ethoxycarbonylmethyl, and ethoxycarbonylethyl group. R ₁ and R ₂ are bonded to each other,
Also, together with the benzene nucleus substituted with an amino group in the skeleton,
You may form the ring like General formula (7a)-(7e) (Chemical formula 13) below.

[0018]

Embedded image (Wherein, R ₂ and R ₃ represents the same meaning as in the general formula (1), Q ₅ ~Q ₈ 1-6 hydrogen atoms or carbon atoms
Represents the alkyl group of

R ₁ and R ₂ are preferably an alkyl group, an alkoxyalkyl group, an alkenyl group, a hydroxyalkyl group, an alkoxycarbonylalkyl group, or a substituent represented by the general formulas (7a) to (7e). , And more preferably an alkyl group or the general formula (7a) to (7
It is a substituent represented by e), more preferably a methyl group or an ethyl group. In the general formula (1), R
Examples of ₃ are hydrogen atom; halogen atom; carbon number 1 to
10 alkyl groups; methoxymethyl, methoxyethyl,
Alkoxyalkyl groups such as ethoxymethyl, ethoxyethyl and γ-ethoxypropyl groups; hydroxyalkyl groups such as hydroxymethyl, hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl and 2-hydroxybutyl groups; chloromethyl, dichloromethyl, Fluoromethyl, trifluoromethyl, pentafluoroethyl, nonafluorobutyl and other halogenoalkyl groups; hydroxyl groups; C1-10 alkoxy groups; methoxymethoxy, methoxyethoxy, ethoxymethoxy, ethoxyethoxy, n
-Alkoxyalkoxy groups such as propoxyethoxy; sulfonic acid groups and the like.

In the general formula (1), examples of R ₄ include hydrogen atom; halogen atom; alkyl group having 1 to 10 carbon atoms; methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, γ-ethoxypropyl group, etc. Alkoxyalkyl group of hydroxymethyl, hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-
Hydroxyalkyl group such as hydroxybutyl group; halogenoalkyl group such as chloromethyl, dichloromethyl, fluoromethyl, trifluoromethyl, pentafluoroethyl, nonafluorobutyl group; hydroxyl group; alkoxy group having 1 to 10 carbon atoms; 4 to 8 carbon atoms A cycloalkoxy group; a cyano group; a carboxyl group; an alkoxycarbonyl group having 2 to 11 carbon atoms, a cycloalkoxycarbonyl group having 5 to 9 carbon atoms, a phenoxycarbonyl group, a p-methylphenoxycarbonyl group, an m-methylphenoxycarbonyl group, o
-Aryloxycarbonyl groups such as methylphenoxycarbonyl group, 2,4-dimethylphenoxycarbonyl group, 2,6-dimethylphenoxycarbonyl group, 2,4,6-trimethylphenoxycarbonyl group and 4-phenylphenoxycarbonyl group; propeno Alkenyloxycarbonyl groups such as oxycarbonyl group and 2-butenoxycarbonyl group;

Aralkyloxycarbonyl groups such as benzyloxycarbonyl, methylbenzyloxycarbonyl and phenethyloxycarbonyl groups; methoxycarbonylmethoxycarbonyl, ethoxycarbonylmethoxycarbonyl, n-propoxycarbonylmethoxycarbonyl,
Alkoxycarbonylalkoxycarbonyl groups such as iso-propoxycarbonylmethoxycarbonyl group; alkylcarbonylalkoxycarbonyl groups such as methylcarbonylmethoxycarbonyl and ethylcarbonylmethoxycarbonyl group; hydroxymethoxycarbonyl, hydroxyethoxycarbonyl, 2-hydroxypropoxycarbonyl, 3-hydroxy Hydroxyalkoxycarbonyl group such as propoxycarbonyl group; hydroxypolyethercarbonyl group such as hydroxyethoxyethoxycarbonyl, hydroxypropoxypropoxycarbonyl, hydroxyethoxyethoxyethoxycarbonyl group; methoxymethoxycarbonyl, methoxyethoxycarbonyl, ethoxymethoxycarbonyl, ethoxyethoxycarbonyl, γ-ethoxypro Alkoxycarbonyl group, methoxyethoxy ethoxycarbonyl, group represented by the general formula and polyether group such as ethoxyethoxy ethoxyethoxycarbonyl (2a);

Hydroxyalkylcarbonyl groups such as hydroxymethylcarbonyl, hydroxyethylcarbonyl and hydroxypropylcarbonyl; hydroxyalkoxyalkylcarbonyl groups such as hydroxymethoxymethylcarbonyl, hydroxyethoxypropylcarbonyl and hydroxybutoxypentylcarbonyl; hydroxymethoxyethoxyethylcarbonyl and hydroxy Hydroxypolyetheralkylcarbonyl groups such as ethoxypropoxypropylcarbonyl and hydroxyethoxyethoxyethoxyethylcarbonyl; alkoxyalkylcarbonyl groups such as methoxyethylcarbonyl, ethoxymethylcarbonyl, propoxymethylcarbonyl; methoxyethoxymethylcarbonyl, propoxyethoxyethoxyethylethylcarbonyl , A group represented by the general formula (2b) such as a polyetheralkylcarbonyl group such as butoxymethoxy, butoxymethoxyethoxyethoxyethylcarbonyl; an aminocarbonyl group; a monoalkylaminocarbonyl group having 1 to 6 carbon atoms; a dialkyl having 2 to 12 carbon atoms Aminocarbonyl group;
Mono (hydroxyalkyl) aminocarbonyl group such as hydroxyethylaminocarbonyl, 2-hydroxypropylaminocarbonyl, 3-hydroxypropylaminocarbonyl group; di (hydroxyethyl) aminocarbonyl,
Di (2-hydroxypropyl) aminocarbonyl, di (3-
A di (hydroxyalkyl) aminocarbonyl group such as a hydroxypropyl) aminocarbonyl group;

Mono (hydroxyalkoxyalkyl) aminocarbonyl groups such as hydroxyethoxyethylaminocarbonyl, hydroxypropoxyethylaminocarbonyl and hydroxypropoxypropylaminocarbonyl groups; di (hydroxyethoxyethyl) aminocarbonyl, di (hydroxypropoxyethyl) aminocarbonyl , Di (hydroxyalkoxyalkyl) aminocarbonyl group such as di (hydroxypropoxypropyl) aminocarbonyl group; mono such as methoxymethylaminocarbonyl, methoxyethylaminocarbonyl, ethoxymethylaminocarbonyl, ethoxyethylaminocarbonyl, propoxyethylaminocarbonyl group (Alkoxyalkyl) aminocarbonyl group; di (methoxymethyl) aminocarbonyl, di ( Tokishiechiru) aminocarbonyl, di (ethoxymethyl) aminocarbonyl, di (ethoxyethyl) aminocarbonyl, di (propoxyethyl) di (alkoxyalkyl such as an amino group)
Aminocarbonyl group; a group represented by the general formula (2c) such as a cycloalkylaminocarbonyl group having 4 to 8 carbon atoms, and the like.

Preferably, a hydrogen atom; a halogen atom; an alkyl group having 1 to 10 carbon atoms; a halogenoalkyl group; a hydroxyl group; an alkoxy group having 1 to 10 carbon atoms; a cyano group; a carboxyl group; an alkoxycarbonyl group having 2 to 11 carbon atoms. Group;
Cycloalkoxycarbonyl group; aryloxycarbonyl group; alkenyloxycarbonyl group; alkylcarbonylalkoxycarbonyl group; aralkyloxycarbonyl group; alkoxycarbonylalkoxycarbonyl group; alkylcarbonylalkoxycarbonyl group; or represented by the general formulas (2a) to (2c). Is a substituted group.
More preferably hydrogen atom; halogen atom; carbon number 1 to 3
Alkyl group; halogenoalkyl group; hydroxyl group; carbon number 1
~ 3 alkoxy group; cyano group; carboxyl group; C2-11 alkoxycarbonyl group; cycloalkoxycarbonyl group; aryloxycarbonyl group; alkenyloxycarbonyl group; aralkyloxycarbonyl group; alkoxycarbonylalkoxycarbonyl group; alkylcarbonyl An alkoxycarbonyl group; or a substituent represented by any one of formulas (2a) to (2c).

More preferably, a hydrogen atom; carbon number 1 to
An alkyl group of 3; a halogenoalkyl group; a cyano group; a carboxyl group; an alkoxycarbonyl group having 2 to 11 carbon atoms; a cycloalkoxycarbonyl group; an aryloxycarbonyl group; an alkenyloxycarbonyl group; or the general formulas (2a) to (2c). Is a substituent represented by. Most preferably, a hydrogen atom; a cyano group; a carboxyl group; an alkoxycarbonyl group; a cycloalkoxycarbonyl group; an aryloxycarbonyl group; an alkenyloxycarbonyl group; or a substituent represented by any of the general formulas (2a) to (2c). .

In the general formula (1), R ₅ is the general formula (3
a) to (3d), and the aromatic rings A to F may be substituted. These aromatic rings may be substituted with one substituent or simultaneously with two or more substituents.
As the groups which may be substituted, a halogen atom, an alkyl group, an alkoxy group, a nitro group, an amino group,
An alkylamino group, an arylamino group, an alkoxyalkylamino group, a cyano group or an aryloxy group, preferably an alkyl group, an alkoxy group, an amino group, an alkylamino group, an arylamino group, an alkoxyalkylamino or an aryloxy group. And more preferably an alkoxy group, an alkylamino group, an arylamino group, an alkoxyalkylamino group or an aryloxy group, and most preferably an alkoxy group or an alkylamino group. The aromatic rings A to F are preferably substituted with one or more alkoxy groups, alkylamino groups, arylamino groups, alkoxyalkylamino groups or aryloxy groups, rather than unsubstituted,
More preferably, it is substituted with an alkoxy group or an alkylamino group. In the general formula (1), a compound in which R ₄ is not a hydrogen atom is a novel compound. The 3-keto-substituted coumarin compound of the present invention can be prepared by a known method (for example,
The method disclosed in U.S. Pat. No. 4,147,552), for example, according to the following reaction formulas (8) and (14).

[0027]

Embedded image

3-acetyl-7-substituted aminocoumarins and aldehyde compounds are prepared, for example, with methanol, ethanol,
In a polar solvent such as N, N-dimethylformamide (hereinafter abbreviated as DMF), dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone (hereinafter abbreviated as DMI), the reaction product
A catalytic base of about one-half the amount of a weak base (for example, amines such as piperidine, pyrrolidine, pyridine and aniline is preferable) is added, and the mixture is mixed at 0 to 100 ° C., preferably 6
By reacting at 0 to 80 ° C for 1 to 12 hours, 3-
A keto-substituted coumarin compound is obtained.

In the compound represented by the general formula (1) of the present invention, R ₄ is a cyano group, a carboxyl group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an aryloxycarbonyl group, an alkenyloxycarbonyl group,
Aralkyloxycarbonyl group, alkoxycarbonylalkoxycarbonyl group, alkylcarbonylalkoxycarbonyl group, or the above general formulas (2a) to (2c).
In the case of a substituent represented by the following reaction formula (9)
As shown in 5), it can be obtained, for example, by cyanating a 3-keto-substituted coumarin compound in which R ₄ is a hydrogen atom, and then derivatizing it to a different substituent.

[0030]

Embedded image

Cyanation is described in "Dyes and Pigments, Vol.
1, p.3 to 15, (1980) ”, the method for cyanating a coumarin compound is used as a reference, followed by reaction with NaCN in DMF and then oxidation with bromine. The cyano group in the compound is
It can be converted to a carboxyl group by heating with hydrolysis at 70 to 100 ° C. using 50 to 98% by weight of sulfuric acid.
Further, a compound containing a carboxyl group is once converted into an acid chloride with a chlorinating agent and then reacted with alcohols, amines, alkyl halides, various tosylates, phenols, or the like, or a compound containing a carboxyl group. In the presence of an acid catalyst, a dehydrating agent, or no catalyst,
Depending on the heating method, R ₄ has an alkoxycarbonyl group,
A cycloalkoxycarbonyl group, an aryloxycarbonyl group, an alkenyloxycarbonyl group, an aralkyloxycarbonyl group, an alkoxycarbonylalkoxycarbonyl group, an alkylcarbonylalkoxycarbonyl group, or a substituent represented by the above general formulas (2a) to (2c), etc. Can be introduced.

Further, concentrated sulfuric acid is added dropwise to a mixture of alcohols or the like containing a cyano compound in an equimolar amount of water in an amount of 50 to 10
Similar substituents can be introduced by the method of heating to 0 ° C. Further, in order to introduce a substituent other than the above into the substituent represented by R ₄ in the general formula (1), for example, R
_A 3-keto-substituted coumarin compound in which ₄ is a hydrogen atom is subjected to halogenation such as bromination, and then converted to an alkyl group, a hydroxyl group, an alkoxy group, a halogenoalkyl group or the like. The 3-keto-substituted coumarin compound represented by the general formula (1) used in the present invention is 400 to 700.
The compound is a compound that is excited by absorbing light in the visible light region of nm, particularly light of 400 to 600 nm, and interacts with a photocurable resin or a polymerization initiator. The term "interaction" as used herein includes energy transfer and electron transfer from the excited compound of the present invention to the photocurable resin or the polymerization initiator.

When the 3-keto-substituted coumarin compound used in the present invention is combined with a titanocene compound which is a polymerization initiator, a close interaction occurs and the sensitivity to visible light is greatly improved. For this reason, the visible light-sensitive resin composition containing the photopolymerization initiator composition of the present invention is extremely useful. In the visible light-sensitive resin composition of the present invention, the photo-curable resin is not particularly limited as long as it is a photo-curable resin having a photosensitive group that can be crosslinked or polymerized by light irradiation that is generally used. However, for example, an ethylenic compound or a (meth) acryloyl group as a photosensitive group described in JP-A-3-223759, page 2, lower right column, line 6 to page 6, lower left column, line 16 is included. Examples thereof include an anionic photocurable resin, a photocurable resin containing a cinnamoyl group as a photosensitive group, and a photocurable resin containing an allyl group as a photosensitive group.

The ethylenic compound is a compound having at least one ethylenically unsaturated double bond in its chemical structure, and is an oligomer such as a monomer, a prepolymer, a dimer or a trimer, or a compound thereof. And mixtures and copolymers thereof. Monofunctional and polyfunctional acrylates,
Methacrylates are generally used, and further, unsaturated carboxylic acids and salts thereof, esters of unsaturated carboxylic acids with aliphatic alcohol compounds or aliphatic polyol compounds, and the like, page 3 of JP-A-58-15503. The photocurable resin described on page 4 can be mentioned. The photocurable resin has different reactivity, viscosity and the like depending on the type thereof, and thus two or more types may be used in combination.

In the visible light-sensitive resin composition of the present invention, the amount of the 3-keto-substituted coumarin compound used is different depending on the kind and the kind of the photocurable resin component to be interacted with, but usually the photocurable resin is used. Per 100 parts by weight of the solid component,
It is 0.1 to 10 parts by weight, preferably 0.3 to 5 parts by weight. When the amount of the 3-keto-substituted coumarin compound used is less than 0.1 part by weight, the photosensitivity of the formed film tends to decrease, and when it is more than 10 parts by weight, the composition becomes uniform from the viewpoint of solubility. It tends to be difficult to maintain good condition. Further, in the present invention, the 3-keto-substituted coumarin compound represented by the general formula (1) may be mixed with other known photosensitizers. Other known photosensitizers are not particularly limited as long as they are commonly used photosensitizers, and examples thereof include ketocoumarin, coumarin-6 and coumarin compounds described in JP-A-4-18088. .

The amount of the titanocene compound, which is a polymerization initiator used in the present invention, is not critical and can be varied within a wide range depending on the kind thereof. Generally, the above-mentioned photocurable resin is used. It is 0.1 to 30 parts by weight, preferably 0.2 to 20 parts by weight, per 100 parts by weight of the solid component. If it is used in a large amount exceeding 30 parts by weight, the stability of the obtained composition tends to be lowered. The weight ratio of the 3-keto-substituted coumarin compound to the titanocene compound can range from about 1: 1 to about 1: 300, preferably about 1: 1 to about 1:30. .

Next, the use of the visible light-sensitive resin composition of the present invention will be described. The visible light-sensitive resin composition of the present invention can be handled in the same manner as a commonly used known photosensitive material. For example, the ink (photosensitive liquid) for the visible light-sensitive material of the present invention is obtained by dissolving the visible light-sensitive resin composition of the present invention in a solvent (finely dispersing the pigment when a pigment is used as a coloring agent). To be Further, the visible light-sensitive material of the present invention can be obtained by a method of coating the photosensitive liquid on a substrate using a coating device such as a roller, a coat coater or a spin coater and drying.

Examples of the solvent used include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (ethyl acetate, butyl acetate, methyl benzoate, methyl propionate, etc.), ethers (tetrahydrofuran, dioxane, etc.). Dimethoxyethane, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, diethylene glycol monomethyl ether, etc.),
Aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.), halogenated hydrocarbons (chloroform,
(Trichloroethylene, dichloromethane, etc.), alcohol (ethyl alcohol, benzyl alcohol, etc.), and others (dimethylformamide, dimethylsulfone oxime, etc.) and the like. Further, as the base material, for example,
Examples thereof include a sheet of a metal such as aluminum, magnesium, copper, zinc, chromium, nickel and iron or an alloy containing them, or a printed circuit board whose surface is treated with these metals, plastic, glass or a silicon wafer, carbon and the like.

Further, the visible light-sensitive composition of the present invention can be handled in the same manner as an ordinary photosensitive material for electrodeposition coating, and can also be used as a coating material for electrodeposition coating. In that case, the photocurable resin is first made into a water-dispersed product or a water-soluble product. Water-dispersed or water-solubilized photocurable resin is neutralized with an alkali (neutralizing agent) when an anionic group such as a carboxyl group in the photocurable resin is introduced, or an amino group or the like. When the cationic group of is introduced, it is carried out by neutralizing with an acid (neutralizing agent). Examples of the alkali neutralizer used at that time include, for example, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; alkylamines such as triethylamine, diethylamine, monoethylamine, diisopropylamine, trimethylamine and diisobutylamine; Alkyl alkanolamines such as dimethylaminoethanol; alicyclic amines such as cyclohexylamine; alkali metal hydroxides such as sodium hydroxide and sodium hydroxide; ammonia; Examples of the acid neutralizer include monocarboxylic acids such as formic acid, acetic acid, lactic acid and butyric acid. These neutralizing agents can be used alone or in combination. The amount of the neutralizing agent used is generally in the range of 0.2 to 1.0 equivalent, particularly 0.3 to 0.8 equivalent per equivalent of the ionic group contained in the photocurable resin.

In order to further improve the fluidity of the water-solubilized or water-dispersed resin component, a hydrophilic solvent such as methanol, ethanol, isopropanol, n-butanol, t- Butanol,
Methoxyethanol, ethoxyethanol, butoxyethanol, diethylene glycol monomethyl ether,
Dioxane, tetrahydrofuran and the like can be added. The amount of the hydrophilic solvent to be used can be generally up to 300 parts by weight, preferably up to 100 parts by weight, per 100 parts by weight of the resin solid component. Further, in order to increase the amount of coating on the object to be coated, the above photocurable resin,
Hydrophobic solvents, for example, petroleum solvents such as toluene and xylene; ketones such as methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate and butyl acetate;
Alcohols such as ethylhexyl alcohol and benzyl alcohol can also be added. The compounding amount of these hydrophobic solvents is usually 100 parts by weight of the resin solid component,
It can be up to 200 parts by weight, preferably 100 parts by weight or less.

The visible light-sensitive composition as an electrodeposition coating composition can be prepared by a conventionally known method. For example, a photocurable resin solubilized by the above neutralization, a photosensitizer represented by the general formula (1), a polymerization initiator, and, if necessary, a solvent, a nitrogen-containing compound and other components are often added. It can be prepared by mixing and adding water. The composition thus prepared is further diluted with water by a conventional method, for example, within a pH range of 4 to 9, and a bath concentration (solid content concentration) of 3 to 25% by weight, preferably 5 to 5. The electrodeposition paint (or electrodeposition bath) can be within the range of 15% by weight.

The electrodeposition paint prepared as described above is
The coating can be performed on the surface of the conductor to be coated as follows. That is, first, the pH and bath concentration of the bath are adjusted to the above ranges, and the bath temperature is 15 to 40 ° C., preferably 15 to 30.
Control at ℃. Next, in the electrodeposition coating bath controlled in this way, the conductor to be coated is immersed in a conductor to be coated as an anode when the electrodeposition coating is of an anionic type and as a cathode when the electrodeposition coating is of a cationic type. Apply DC current. A suitable energization time is 30 seconds to 5 minutes, and the obtained film thickness is a dry film thickness, generally 0.5 to 50 μm, and preferably 1 to 15 μm.
μm. After the electrodeposition coating, the object to be coated is taken out of the electrodeposition bath and washed with water, and then moisture and the like contained in the electrodeposition coating film are dried and removed with hot air or the like. As the conductor, metal, carbon,
It can be used by a conductive material such as tin oxide, or a person who fixes these to a plastic or glass surface by laminating, plating or the like.

The visible light-sensitive material formed on the substrate obtained as described above and the visible light-sensitive electrodeposition coating film obtained by electrodeposition coating are exposed to visible light according to the image. An image can be formed by curing, and removing the non-exposed portion by a developing process. As the light source for the exposure, a light source obtained by each light source such as an ultra-high pressure, high pressure, medium pressure, low pressure mercury lamp, chemical lamp, carbon arc lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, sunlight, etc. Among them, a light beam in the visible region in which ultraviolet rays are cut by an ultraviolet cut filter, various lasers having an oscillation line in the visible region, and the like can be used. An argon laser or a YAG laser (SHG) is preferable as a high-power and stable laser light source.

The development treatment is carried out by washing with an aqueous alkali solution when the non-exposed film is anionic and with an aqueous acid solution having a pH of 5 or less when it is cationic. Alkaline aqueous solutions are generally capable of imparting water solubility by neutralizing free carboxylic acids in the coating, such as caustic soda, sodium carbonate, caustic potash, and ammonia water, and acid aqueous solutions include acetic acid, formic acid, lactic acid, and the like. Can be used. In the case of a photocurable resin having no ionic group, development processing is performed by dissolving an unexposed portion using a solvent such as 1,1,1-trichloroethane, tricrene, methyl ethyl ketone, or methylene chloride.
After development, the coating film is washed with water and then dried with hot air, etc.,
An intended image is formed on the conductor. If necessary, the printed circuit board can be manufactured by performing etching to remove the exposed conductor portion, and then removing the resist film. The composition of the present invention includes a photoresist, a plate-making material for a flat plate or letterpress, a PS plate for offset printing,
It can be applied to a wide range of applications such as information recording materials and relief image forming materials.

[0045]

EXAMPLES The present invention will be described below with reference to specific examples, but these are illustrative, and the present invention is not limited to these examples. Parts in Examples are parts by weight, and% means% by weight. Synthesis Example 1 4-Acetyl-7-diethylaminocoumarin 26 parts, 4-diethylaminocinnamaldehyde 20 parts and piperidine 2
Part was added to 600 ml of ethanol and refluxed for 5 hours.
After allowing to cool, it was filtered and dried. The reaction mixture thus obtained is
Separation and purification by column chromatography gave 37 parts of the compound of formula (A) The results of analyzing the compound of formula (A) were as follows.・ Absorption spectrum; absorption maximum [λ max] 485 nm (in chloroform) ・ FDMS spectrum; m / z = 444 (M ⁺ ) ・ Elemental analysis value (C ₂₈ H ₃₂ N ₂ O ₃ ) C (%) H (%) N (%) calculated value 75.65 7.25 6.30 measured value 75.59 7.21 6.32

[0046]

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Example 1 Compound of formula (B) (Chemical formula 17) obtained in the same manner as in Synthesis Example 1
38 parts were suspended in 200 parts DMF, into which 30% NaCN was added.
After 66 parts of an aqueous solution was added dropwise at room temperature and the reaction was continued for 1 hour, 36 parts of bromine was added dropwise at 0 to 10 ° C. and stirred for 2 hours. The precipitate is filtered, washed well with water, dried, and then the compound of formula (C)
36 parts of the compound of Chemical formula 17 was obtained. The results of the absorption spectrum and elemental analysis of the compound of formula (C) were as follows. -Absorption spectrum; absorption maximum [λmax] 510 nm (in chloroform) -FDMS spectrum; m / z = 415 (M ⁺ ) -Elemental analysis value (C ₂₅ H ₂₅ N ₃ O ₃ ) C (%) H (%) N (%) Calculated value 72.27 6.06 10.11 Measured value 72.29 6.13 10.08

[0048]

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Example 2 14 parts of the compound of the formula (C) obtained in Example 1 are treated with 98% sulfuric acid in 100 parts of diethylene glycol monomethyl ether.
The mixture was reacted with 21.6 parts at 80 ° C. for 4 hours, allowed to cool, and then discharged into 300 parts of water for neutralization. The precipitated crystals were filtered, washed well with water, and dried to obtain 10 parts of the following compound (D) (Chemical Formula 18).
The results of the absorption spectrum and elemental analysis of the compound of formula (D) were as follows. - absorption spectrum; absorption maximum [λmax] 465 nm (in chloroform), FDMS spectrum; m / z = 536 (M +) · Elemental analysis _{(C 30 H 36 N 2 O} 7) C (%) H (%) N (%) Calculated value 67.15 6.76 5.22 Measured value 67.09 6.75 5.26

[0050]

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Example 3 As a photocurable resin (polymer binder), methyl methacrylate / methacrylic acid / hydroxyphenyl methacrylate / benzyl methacrylate = 50/20/10
100 parts of the polymer of the / 20 mixture, 55 parts of trimethylolpropane triacrylate, 20 parts of the titanocene compound of the above formula (6a) as a polymerization initiator, and various 3-type compounds obtained in Synthesis Example 1 as photosensitizers. A photosensitive solution was prepared using 5 parts of a keto-substituted coumarin compound and 160 parts of methyl cellosolve as a solvent. This photosensitive solution was dried at a film thickness of 3.
A photosensitive layer was obtained by coating the laminated copper plate with a spinner so as to have a weight of 5 g / m ² . 5 mJ / in the above photosensitive layer
It was confirmed that the resin was rapidly cured when irradiated with an argon laser having a cm ² intensity. After exposure, development was carried out with a 0.5% aqueous solution of sodium carbonate. The obtained pattern was a good pattern having no film loss by the developing solution and no resist residue in the unexposed portion. Xenon lamp and Y
The same result was obtained by irradiation with the second harmonic wave (532 nm) of the AG laser.

Example 4 As the 3-keto-substituted coumarin compound in Example 3,
A photosensitive layer was obtained in the same manner as in Example 3 except that the compound obtained in Example 1 was used instead of the compound obtained in Synthesis Example 1. It was confirmed that the resin in this photosensitive layer was quickly cured with an argon laser having an intensity of 5 mJ / cm ² . The photosensitive layer obtained in the same manner was further exposed to an argon laser of 2.5 mJ / cm ² ,
Subsequent development gave a good pattern.

Example 5 Using the compound obtained in Example 2, a photosensitive layer was obtained in the same manner as in Example 4 and evaluated in the same manner. As a result, 5 mJ / cm ²
And a 2.5 mJ / cm ² argon laser gave good patterns. Examples 6 to 29 In the same manner as in Synthesis Example 1 and Examples 1 and 2, various 3-keto-substituted coumarin compounds shown in Table 1 (Table 1, Table 2 and Table 3) were synthesized. Using these compounds, Example 3
The evaluation was performed in the same manner as in Table 5 and the results are also shown in Table 1. 5m
It was developed by scanning exposure with an argon laser of J / cm ² and 2.5 mJ / cm ² . The state of the obtained pattern was evaluated as follows.

[0054]

[Table 1]

[0055]

[Table 2]

[0056]

[Table 3]

[0057]

INDUSTRIAL APPLICABILITY The 3-keto-substituted coumarin compound represented by the general formula (1) of the present invention is a compound having extremely high usefulness as a photosensitizer, and when combined with a titanocene compound, To provide a highly sensitive photopolymerization initiator composition. Conventionally, in the field of information recording using a photopolymerization reaction, a method of directly outputting an original document electronically edited by a computer directly using a laser and recording the same has a low stability of a photosensitive layer with time and a low sensitivity. However, there were problems in solubility, storage stability and the like. However, the 3-keto-substituted coumarin compound and the titanocene compound used in the present invention have good compatibility with the base resin, and dissolve in a general-purpose coating solvent to give a uniform and smooth coating surface on the substrate. You can A photopolymerization initiator composition containing a 3-keto-substituted coumarin compound and a titanocene compound used in the present invention is
This photopolymerization initiator has extremely high sensitivity to general-purpose visible lasers such as an argon laser having a stable oscillation line at 488 nm and 514.5 nm and a YAG laser having an emission line at 532 nm as a second harmonic. The light-sensitive material obtained from the visible light-sensitive resin composition of the present invention using the composition can be subjected to high-speed scanning exposure with these lasers. Further, the image obtained by high-speed scanning exposure has extremely high resolution.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C07D 491/16 C07D 491/16 C08F 2/50 MDN C08F 2/50 MDN // G11B 7/26 501 7303-5D G11B 7/26 501 (72) Inventor Keisuke Takuma 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (5)

[Claims] 1. A photosensitive resin composition containing a polymerizable compound having an ethylenically unsaturated double bond and a photopolymerization initiator composition, which is capable of being crosslinked or polymerized by irradiation with visible light. The thing is the following general formula (1)
A visible light-sensitive resin composition comprising a 3-keto-substituted coumarin compound represented by (Chemical Formula 1) and a titanocene compound. Embedded image Wherein R ₁ and R ₂ are each a hydrogen atom, an alkyl group,
It represents an alkoxyalkyl group, an alkenyl group, a hydroxyalkyl group, an aralkyl group, an aryl group or an alkoxycarbonylalkyl group, which may be bonded to each other or bonded to a benzene nucleus substituted with an amino group in the skeleton to form a ring. , R ₃ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxyalkyl group, a hydroxyalkyl group, a halogenoalkyl group, a hydroxyl group, an alkoxy group, an alkoxyalkoxy group, an alkylthio group, an arylthio group or a sulfonic acid group, and R ₄ represents hydrogen. Atom, halogen atom,
Alkyl group, halogenoalkyl group, hydroxyl group, alkoxy group, cycloalkoxy group, cyano group, carboxyl group,
Alkoxycarbonyl group, cycloalkoxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, aralkyloxycarbonyl group, alkoxycarbonylalkoxycarbonyl group, alkylcarbonylalkoxycarbonyl group, or the following general formula (2
a) to (2c), which represents any of the substituents represented by Chemical Formula 2, (Here, Q _{1 to} Q ₄ are each a hydrogen atom, an alkyl group,
Shows a hydroxyalkyl group, a hydroxyalkoxyalkyl group, an alkoxyalkyl group, a cycloalkyl group,
n, m, p and q each represent an integer of 1 to 5) R ₅ is any substituent represented by the following general formulas (3a) to (3d) (Chemical Formula 3). (Here, aromatic rings A to F may be substituted) 2. A 3-keto-substituted coumarin compound represented by the general formula (1), wherein R ₃ is hydrogen atom, R ₄ is hydrogen atom, cyano group, carboxyl group, alkoxycarbonyl group, cycloalkoxycarbonyl group, aryl. An oxycarbonyl group, an alkenyloxycarbonyl group, or any substituent represented by the general formulas (2a) to (2c),
R ₅ is any of the substituents represented by the general formulas (3a) to (3d) (provided that the aromatic rings A to F are substituted with one or more alkoxy groups, aryloxy groups, alkylamino groups or arylamino groups). The visible light-sensitive resin composition according to claim 1, wherein 3. An ink for a visible light-sensitive material comprising the visible light-sensitive resin composition according to claim 1 or 2 and a solvent. 4. A visible light-sensitive material comprising the visible light-sensitive resin composition according to claim 1 or 2 on a substrate. 5. A compound represented by the following general formula (1) (formula 4):
A keto-substituted coumarin compound. Embedded image Wherein R ₁ and R ₂ are each a hydrogen atom, an alkyl group,
It represents an alkoxyalkyl group, an alkenyl group, a hydroxyalkyl group, an aralkyl group, an aryl group or an alkoxycarbonylalkyl group, which may be bonded to each other or bonded to a benzene nucleus substituted with an amino group in the skeleton to form a ring. , R ₃ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxyalkyl group, a hydroxyalkyl group, a halogenoalkyl group, a hydroxyl group, an alkoxy group, an alkoxyalkoxy group, an alkylthio group, an arylthio group or a sulfonic acid group, and R ₄ is a cyano group. Group, carboxyl group, alkoxycarbonyl group, cycloalkoxycarbonyl group, aryloxycarbonyl group, alkenyloxycarbonyl group, aralkyloxycarbonyl group, alkoxycarbonylalkoxycarbonyl group, alkylcarbonylalkoxycarbal Bonyl group or a substituent represented by the following general formulas (2a) to (2c) (chemical formula 5): (Here, Q _{1 to} Q ₄ are each a hydrogen atom, an alkyl group,
Shows a hydroxyalkyl group, a hydroxyalkoxyalkyl group, an alkoxyalkyl group, a cycloalkyl group,
n, m, p and q each represent an integer of 1 to 5), and R ₅ is a substituent represented by the following general formulas (3a) to (3d) (chemical formula 6). (Here, aromatic rings A to F may be substituted)