JPH0813850B2 - Photopolymerizable resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a photopolymerizable resin composition, and more specifically to a photopolymerizable resin composition containing a photosensitive resin and a polymerization initiator. And a novel 4-substituted carbonyl coumarin compound as a photosensitizer.

[Problems to be Solved by Prior Art and Invention]

In recent years, in the field of information recording using photopolymerization, instead of the conventional recording method using ultraviolet rays using film originals,
A method in which a document electronically edited by a computer is directly output using a laser and recorded is being studied. However, most of the commonly used high-power and stable laser light sources at present have an output wavelength in the visible region, such as an argon laser. , It could not be used because of its low sensitivity in the visible range. Although the sensitivity in the visible region can be improved by adding a pyrylium salt or thiapyrylium salt, it is difficult to use because the photosensitive layer thereof has low stability over time.

Conventionally, a 7-alkylaminocoumarin derivative has a maximum absorption wavelength of about 400 to 450 nm when the 4-position is unsubstituted, but a generally used laser light source wavelength has a longer wavelength than that. In many cases, sufficient sensitivity could not be obtained for that reason.

For example, 7-diethylamino-3-benzothiazoylcoumarin and 3,3'-carbonylbis (7-diethylaminocoumarin) have a maximum absorption wavelength of around 450 nm, which is 30-40 nm shorter than 488 nm of an argon laser. This is the wavelength and leaves room for improvement in sensitivity. Further, within a certain range, a positive correlation is established between the rate of introduction of the sensitizer into the resin and the sensitivity. Therefore, it is preferable that the sensitizer be stably dissolved in as much resin as possible within the range. desirable. Regarding this, it can be said that the two compounds given as examples leave room for improvement in sensitivity.

Further, if the 4-position is cyanated, it is possible to shift the maximum absorption wavelength of the compound to a longer wavelength side (hereinafter, simply referred to as longer wavelength), but the solubility in the resin and the storage stability are impaired. There were many cases.

[Means for solving the problem]

As a result of intensive studies to solve the above problems, the present inventors have found a novel 4-substituted carbonylcoumarin compound represented by the general formula (I), and have identified this compound as a photosensitive resin and a photopolymerization initiator. The present invention has been completed by finding that the compound containing the compound has excellent properties as a photosensitizer.

That is, the present invention provides a photopolymerizable resin composition containing a photosensitive resin, a photopolymerization initiator, and a photosensitizer, as a photosensitizer, represented by the general formula (I): [In the formula, R ₁ and R ₂ are the same or independently of each other, and each independently represent a hydrogen atom, an alkyl group, an alkoxyalkyl group, an alkenyl group, a hydroxyalkyl group, an aralkyl group, an aryl group or an alkoxycarbonylalkyl group, and , May be bonded to a benzene nucleus substituted with an amino group in the skeleton to form a ring, R ₃ is a hydrogen atom, an alkyl group, an alkoxyalkyl group, a hydroxyalkyl group,
Represents a halogenoalkyl group, a hydroxyl group, an alkoxy group, an alkoxyalkoxy group, an alkoxycarbonyl group, a sulfonic acid group, a halogen atom, X represents a hydrogen atom, an alkyl group,
Cycloalkyl group, alkoxy group having 5 to 22 carbon atoms, cycloalkoxy group, hydroxyl group, aryl group, alkenyl group,
An aryloxy group, an alkenyloxy group, an aralkyl group, an aralkyloxy group, an alkylcarbonylalkoxy group, or the following substituents are shown.

R ₄ and R _{5 each} represent an alkyl group, a cycloalkyl group, a hydroxyalkyl group, an alkoxyalkyl group or an aryl group, and n and m each represent an integer of 1 to 5]. A photopolymerizable resin composition comprising a compound.

The uniquely used sensitizer in the composition of the present invention is a novel coumarin compound useful as a sensitizer. That is, by introducing a substituted carbonyl group at the 4-position of the coumarin skeleton, a long maximum absorption wavelength and high solubility in a resin were realized at the same time. It is an extremely useful compound as a photopolymerizable or photocrosslinkable compound having at least one saturated bond in the molecule and a sensitizer applicable to photocuring using a photopolymerization initiator. Further, the sensitivity of conventional sensitizers fluctuates greatly depending on the coating method, but the sensitizer of the present invention shows stable sensitivity in any of the methods, and is one which satisfies market demand sufficiently. is there.

 Hereinafter, the present invention will be described in detail.

The sensitizer used in the composition of the present invention has the general formula (I) And has a substituted carbonyl group at the 4-position of the coumarin skeleton.

In formula (I), R ₁ and R ₂ represent a hydrogen atom, an alkyl group, an alkoxyalkyl group, an alkenyl group, a hydroxyalkyl group, an aralkyl group, an aryl group or an alkoxycarbonylalkyl group, which may be the same or different. Good.

Specifically, hydrogen atom; methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-
Alkyl groups such as butyl, t-butyl, n-pentyl, n-hexyl groups; methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, γ-methoxypropyl,
Alkoxyalkyl groups such as γ-ethoxypropyl group; alkenyl groups such as allyl, 2-butenyl and 2-pentenyl groups; hydroxy such as hydroxymethyl, hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl and 2-hydroxybutyl groups. Alkyl groups; aralkyl groups such as benzyl and phenethyl groups; phenyl, p-methylphenyl, m-methylphenyl, o-methylphenyl, 2,4
An aryl group such as a dimethylphenyl group; and an alkoxycarbonylalkyl group such as a methoxycarbonylmethyl, methoxycarbonylethyl, ethoxycarbonylmethyl and ethoxycarbonylethyl group.

Further, R ₁ and R ₂ may be bonded to each other or to a benzene nucleus substituted by an amino group in the skeleton to form the following ring.

(In these rings, R ₂ and R ₃ are each represented by the general formula (I)
In the general formula (I), R ₃ is a hydrogen atom, an alkyl group,
An alkoxyalkyl group, a hydroxyalkyl group, a halogenoalkyl group, a hydroxyl group, an alkoxy group, an alkoxyalkoxy group, an alkoxycarbonyl group, a sulfonic acid group and a halogen atom, specifically a hydrogen atom; methyl, ethyl, n-propyl, Alkyl groups such as iso-propyl and n-butyl groups; alkoxyalkyl groups such as methoxymethyl, methoxyethyl, ethoxymethyl and ethoxyethyl groups; hydroxy such as hydroxymethyl, hydroxyethyl, 2-hydroxypropyl and 3-hydroxypropyl groups Alkyl group; halogenoalkyl group such as chloromethyl, 2-chloroethyl, dichloromethyl, trifluoromethyl group; hydroxyl group; methoxy, ethoxy, n-propoxy,
Alkoxy group such as n-butoxy group; methoxymethoxy,
Alkoxyalkoxy groups such as methoxyethoxy, ethoxymethoxy, ethoxyethoxy, n-propoxyethoxy groups; methoxycarbonyl, ethoxycarbonyl, n-
Examples thereof include alkoxycarbonyl groups such as propoxycarbonyl and n-butoxycarbonyl groups.

Similarly, in the general formula (I), X is a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group having 5 to 22 carbon atoms, a cycloalkoxy group, a hydroxyl group, an aryl group, an alkenyl group, an aryloxy group, an alkenyloxy group, An aralkyl group, an aralkyloxy group, an alkylcarbonylalkoxy group, or the following substituents are shown.

(Here, R ₄ and R ₅ represent an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, a cycloalkyl group, and an aryl group, and n and m each represent an integer of 1 to 5.) Specifically, a hydrogen atom Methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-
Butyl, t-butyl, n-pentyl, n-hexyl, n
-Alkyl group such as heptyl and n-octyl group; cycloalkyl group such as cyclopentyl and cyclohexyl group; having 5 to 22 carbon atoms such as n-pentyloxy, n-hexyloxy, n-heptyloxy and n-octyloxy groups Alkoxy group; cycloalkoxy group such as cyclopetyloxy and cyclohexyloxy group; hydroxyl group; aryl group such as phenyl, p-methylphenyl, m-methylphenyl, o-methylphenyl group and methoxyphenyl group; allyl, 2-
Alkenyl groups such as butenyl and 2-pentenyl groups; phenoxy, p-methylphenoxy, m-methylphenoxy,
o-methylphenoxy, 2,4-dimethylphenoxy, 2,6
An aryloxy group such as dimethylphenoxy, 2,4,6-trimethylphenoxy and 4-phenylphenoxy group;
Alkenyloxy groups such as propenyloxy and 2-butenyloxy groups; aralkyl groups such as benzyl and phenethyl groups; aralkyloxy groups such as benzyloxy, methylbenzyloxy and phenethyloxy groups; alkylcarbonyl such as methylcarbonylmethoxy and ethylcarbonylmethoxy groups Alkoxy group; polyether group such as hydroxyethoxyethoxyethyl, ethoxyethoxyethyl, hydroxyethoxyethoxyethoxy group, methoxyethoxyethoxyethoxy group; amino group; methylamino, ethylamino, n-propylamino, n-butylamino, n
A monoalkylamino group such as -pentylamino, n-hexylamino, n-octylamino group; dimethylamino,
Diethylamino, dipropylamino, dibutylamino,
Dialkylamino groups such as dipentylamino, dihexylamino, dioctylamino groups; mono (hydroxyalkyl) amino groups such as hydroxyethylamino, 2-hydroxypropylamino, 3-hydroxypropylamino groups; di (hydroxyalkyl) amino, di ( 2-hydroxypropyl) amino, di (3-hydroxypropyl)
Di (hydroxyalkyl) amino groups such as amino groups; mono (hydroxyalkoxyalkyl) amino groups such as hydroxyethoxyethylamino, hydroxypropoxyethylamino, hydroxypropoxypropylamino groups; di (hydroxyethoxyethyl) amino, di (hydroxypropoxy) Di (hydroxyalkoxyalkyl) amino groups such as ethyl) amino and di (hydroxypropoxypropyl) amino groups; mono (alkoxyalkyl) groups such as methoxymethylamino, methoxyethylamino, ethoxyethylamino, ethoxyethylamino and propoxyethylamino groups Amino group; di (methoxymethyl) amino, di (methylethyl) amino, di (ethoxymethyl) amino, di (ethoxyethyl) amino, di (propoxyethyl) amino group and the like di ( Turkey alkoxyalkyl) amino group;
Examples thereof include cycloalkylamino groups such as cyclopentylamino and cyclohexylamino groups.

The compound used in the composition of the present invention is a novel compound described in the end of the literature and can be produced, for example, by the reaction route shown below.

4-Substituted aminosalicylaldehyde (II) as a raw material
And 2-cyanomethylbenzothiazole, for example, methanol, ethanol, N, N-dimethylformamide (hereinafter D
(Abbreviated as MF), 1: 1 in a polar solvent such as dimethyl sulfoxide, and a catalytic amount of about 1/10 of a weak base is added. As the weak base, amines such as piperidine, pyrrolidine, pyridine and aniline are preferable.

The mixture is reacted at 0 to 80 ° C for 1 to 12 hours to obtain the compound (III). The compound (IV) is obtained by boiling this with 5 to 20 times the weight of 1 to 5% by weight of dilute hydrochloric acid for 2 to 6 hours.
Also, instead of 2-cyanomethylbenzothiazole, 2-
When alkoxycarbonylmethylbenzothiazole is used to react by the above method, compound (IV) can be obtained without passing through compound (III).

Cyanation was carried out by converting the obtained compound (IV) to "Dyes and Pigme
nts 1 3-15 (1980) ”in the DMF.
After reacting with, bromine is added dropwise to obtain a cyano compound (V).

The method for obtaining the novel compound (I) from the cyano compound (V) is
After heating to 70-100 ° C with 50-80% by weight of sulfuric acid to hydrolyze the cyano group to form a carboxylic acid (VI), alcohols, aminos, alkyl halides, various tosylates, or phenols There is a method in which the acid chloride is once converted into an acid chloride with a chlorinating agent and then reacted, or is heated in the presence of an acid catalyst, a dehydrating agent or in the absence of a catalyst. The compound (I) can be directly obtained by dropping concentrated sulfuric acid into a mixture of contained alcohols and heating the mixture at 50 to 100 ° C.

Further, in order to directly introduce a carbon atom into carbonyl, it can be obtained by reacting a cyano group with a Grignard reagent such as BrMaX by a conventional method.

The photosensitive resin used in the photopolymerizable resin composition of the present invention is a photopolymerizable or photocrosslinkable monomer, oligomer or prepolymer having at least one ethylenic unsaturated bond in one molecule, Specifically, for example, acrylic acid of monohydric or polyhydric alcohol such as ethyl acrylate, butyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, and dipentaerythritol hexaacrylate. Ester or methacrylic acid ester; polyester acrylate or polyester polymer obtained by reacting acrylic acid or methacrylic acid with a polyester prepolymer obtained by condensing a polyhydric alcohol and a monobasic or polybasic acid Acrylate; polyurethane acrylate or polyurethane methacrylate obtained by reacting acrylic acid or methacrylic acid with a reaction of a compound having a polyol group and two isocyanate groups; reacting an epoxy resin with acrylic acid or methacrylic acid Epoxy acrylate or epoxy methacrylate obtained by the above; other than this, a usual photopolymerized resin using styrene, acrylonitrile, methacrylonitrile, acrylamide, a monomer having a cinnamylidene group in its side chain or terminal, etc. is used.

Furthermore, examples of the photopolymerization initiator used in the photopolymerizable resin composition of the present invention include methyl ketone peroxide, acetylacetone peroxide, t-butyl peroxide, cumene hydroperoxide, α,
α′-bis (t-butylperoxyisopropyl) benzene, t-butylperoxyisopropyl carbonate, benzoyl peroxide, di (t-butylperoxy) isophthalate, t-butylperoxybenzoate, 3,3 ′, 4 4,4'-tetra (t-butylperoxycarbonyl) benzophenone and the like can be mentioned.

These polymerization initiators are used in an amount of 0.1 to 10 per 1 part by weight of the 4-substituted carbonylcoumarin compound represented by the general formula (I).
Parts by weight, preferably 0.5 to 2.0 parts by weight are used.

The 4-substituted carbonylcoumarin compound represented by the general formula (I) and the polymerization initiator are used in a total amount of 0.5 to 30 parts by weight based on 100 parts by weight of the photosensitive resin.

Further, the photopolymerizable resin composition of the present invention may contain a binder, and in this case, polymethacrylic acid ester or a partial hydrolyzate thereof, polyvinyl acetate or a hydrolyzate thereof, polystyrene, polyvinyl butyral. ,
Polychloroprene, polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylpyrrolidone, a copolymer of styrene and maleic anhydride or a half ester thereof, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, acrylamide, A copolymer having a glass transition point of 35 ° C. or higher selected from a group of copolymerizable monomers such as acrylonitrile is used. These binders are used in the range of 10 to 300 parts by weight, preferably 30 to 150 parts by weight, based on 100 parts by weight of the photosensitive resin.

At the time of use, the photopolymerizable resin composition of the present invention can be made into a photosensitive liquid capable of forming a film by using an appropriate solvent.

[Action and effect]

In the field of information recording using a photopolymerization reaction, in a method of directly outputting an original document electronically edited by a computer directly using a laser for recording, the stability of the photosensitive layer with time is low, and the sensitivity is low, and the solubility is low. There were problems such as storage stability.

However, the photosensitive film obtained by applying the photosensitive resin composition of the present invention is excellent in sensitivity and stability over time, and the present invention is extremely useful in practice.

〔Example〕

 Hereinafter, the present invention will be described in more detail with reference to Examples.

 Parts in the examples are parts by weight and% is% by weight.

Example 1 20 parts of 4-diethylaminosulfylaldehyde and 18 parts of 2-ethoxycarbonylmethylbenzothiazole were added with 1 part of piperidine, and the mixture was reacted in an ethanol solvent at room temperature for 12 hours. After filtration, the crystals were thoroughly washed with ethanol, After drying, 33 parts of 3- (benzothiazo-2-yl) -7-diethylaminocoumarin was obtained.

This compound was designated as "Dyes and Pigments 1 , 3-15 (198
0) ”and cyanated to give 3- (benzothiaz-2-yl) -4-cyano-7-diethylaminocoumarin.

9 parts of this cyanide was hydrolyzed in 70% sulfuric acid at 100 ° C. for 8 hours to obtain 8.5 parts of 3- (benzothiazo-2-yl) -7-diethylaminocoumarin-4-aminocarboxylic acid. This compound was reacted with 8.5 parts of methoxyethyl tosylate in the presence of potassium carbonate in 40 parts of DMF at 80 ° C. for 3 hours to give 3- (benzothiazo-2-yl) -4-methoxyethoxyethoxycarbonyl-7-. 9 parts of diethylaminocoumarin were obtained.

Polyvinylpyrrolidone as binder polymer 10
0 part, 100 parts of pentaerythritol triacrylate,
5 parts of the above coumarin compound, 3,3 ', 4,
A composition was obtained by mixing 4 parts of 4'-tetra (t-butylperoxycarbonyl) benzophenone (hereinafter abbreviated as BTTB). Using this, methyl cellosolve 10
The photosensitive solution was prepared by using 00 parts.

This was applied onto a laminated copper plate using a spinner so that the dry film thickness was 1 μm.

Then, the sensitivity of the above-mentioned photosensitive layer was measured using visible light and visible laser light.

The measurement method was performed by measuring the minimum irradiation energy required for photocuring the coating film.

The light source used for the measurement was a xenon lamp for visible light and a scanning argon laser (488 nm) for laser light.

After the exposure, the unexposed portion was eluted with a sodium silicate solution (0.1%), and the presence or absence of curing was measured.

Sensitivity of the photosensitive layer, 0.01 mJ / cm ² visible light, showed a good sensitivity is 0.08mj / cm ² with a laser beam.

Further, the sensitizing solution was hermetically stored in a dark room at 30 ° C., and when the time-dependent change was observed, no decrease in sensitivity was observed even after 35 days.

Example 2 To 20 parts of 4-diethylaminosulfylaldehyde and 17.5 parts of 2-cyanomethylbenzothiazole, 1 part of piperidine was added, and the mixture was added to a solvent of N, N-dimethylformamide at room temperature for 8 hours.
After reacting for a time and separating by filtration, the crystals are thoroughly washed with ethanol,
After drying, 28 parts of 3- (benzothiazo-2-yl) -7-diethylaminocoumarin-2-imine was obtained.

This compound was boiled in 400 parts of 2% hydrochloric acid for 8 hours and
28 parts of-(benzothiazo-2-yl) -7-diethylaminocoumarin was obtained. This compound was cyanated in the same manner as in Example 1, and 9 parts of this cyanide was added to 100% in 70% hydrochloric acid.
When hydrolyzed at ℃ for 8 hours, 3- (benzothiazo-2-
Yl) -7-diethylaminocoumarin-4-carboxylic acid
8.5 copies were obtained.

This was reacted with 4 parts of dicyclohexylcarbodiimide in 100 parts of dehydrated tetrahydrofuran at room temperature for 1 hour,
Then, 10 parts of m-cresol was added dropwise at 10 ° C for 30 minutes,
The reaction was carried out at the same temperature for 3 hours, and 3- (benzothiazo-2-yl) -4- (3-methylphenoxy) carbonyl-7-
8.5 parts of diethylaminocoumarin was obtained.

A composition similar to that of Example 1 was prepared using this coumarin compound, a photosensitive solution was prepared using the composition, and the same test as in Example 1 was conducted to measure the sensitivity of the photosensitive layer.
01mj / cm ^2, good sensitivity 0.09Mjcm ² was obtained with a scanning laser beam, was also not observed reduction in sensitivity due to aging.

Example 3 Using 5 parts of the coumarin compound of Example 1, 100 parts of polymethyl methacrylate as a binder, 100 parts of pentaerythritol trimethacrylate as a photopolymerizable resin, 4 parts of BTTB as a polymerization initiator, and 1300 parts of dichloromethane as a solvent. photosensitive solution to adjust the composed, was measured for sensitivity in the same manner as in example 1, the sensitivity is 0.02 mJ / cm ² visible light was 0.11mj / cm ² with a scanning laser beam. In addition, no decrease in sensitivity was observed due to changes with time.

Examples 4 to 16 The sensitivity of the photosensitive layer was measured using the coumarin compound, the polymerization initiator, the photosensitive resin, and the binder resin shown in Table 1 with the same solvent as in Example 1 and the measurement light source.

The results showed good sensitivity as shown in Table 1, and no deterioration in sensitivity due to aging was observed.

Claims (1)

[Claims] 1. A photopolymerizable resin composition comprising a photosensitive resin, a photopolymerization initiator and a photosensitizer, wherein the photosensitizer is represented by the general formula (I). [In the formula, R ₁ and R ₂ are each the same or independently a hydrogen atom,
An alkyl group, an alkoxyalkyl group, an alkenyl group, a hydroxyalkyl group, an aralkyl group, an aryl group, and an alkoxycarbonylalkyl group are shown, which are bonded to each other or to a benzene nucleus substituted with an amino group in the skeleton to form a ring. R ₃ is a hydrogen atom, an alkyl group,
An alkoxyalkyl group, a hydroxyalkyl group, a halogenoalkyl group, a hydroxyl group, an alkoxy group, an alkoxyalkoxy group, an alkoxycarbonyl group, a sulfonic acid group, a halogen atom, X is a hydrogen atom, an alkyl group, a cycloalkyl group, or a carbon number of 5 22 represents an alkoxy group, a cycloalkoxy group, a hydroxyl group, an aryl group, an alkenyl group, an aryloxy group, an alkenyloxy group, an aralkyl group, an aralkyloxy group, an alkylcarbonylalkoxy group, or the following substituents. R ₄ and R ₅ represent an alkyl group, a cycloalkyl group, a hydroxyalkyl group, an alkoxyalkyl group or an aryl group,
n and m each represent an integer of 1 to 5], which is a photopolymerizable resin composition containing a novel 4-substituted carbonylcoumarin compound.