JP3191244B2 - Photosensitive resin composition and image recording material using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition utilizing a photooxidation reaction of an oxazole derivative by the action of light. The present invention relates to a photosensitive resin composition having high photosensitivity to a wide range up to infrared rays. This photosensitive resin is widely applied as an image recording material such as a printing plate, a photoresist, and holography by being applied on various substrates.

[0002]

2. Description of the Related Art A photosensitive resin composition used as a printing plate or a photoresist includes a negative type and a positive type. As the negative type, a photopolymerization type using an aromatic ketone compound, a benzoin derivative, an aromatic quinone compound or the like as a photopolymerization initiator is generally used, and the photopolymerization sensitivity is sufficient for ultraviolet rays, It shows almost no sensitivity to visible light. Further, the photopolymerizable photosensitive resin composition is greatly inhibited by oxygen in the air. In addition, although the positive photosensitive resin composition is not affected by oxygen,
Sensitization from the visible light region to the near infrared light region is considered to be difficult.

On the other hand, in recent years, the development of laser plate making, printed circuit boards, optical disks, optical memories, holograms, and laser recording materials for laser lithography have been required with the advance of laser technology. At present, laser light sources that can obtain a stable output include an argon laser, a helium-neon laser, a YAG laser, and a semiconductor laser. However, the oscillation wavelengths are all long wavelengths of about 500 nm or more, and it is difficult to perform laser light recording using a photosensitive resin composition used in conventional plate making and photolithography.

[0004] In order to solve these problems, photosensitive resin compositions which are sensitive to visible light to near infrared light have been developed.

[0005]

However, although these photosensitive resin compositions exhibit photosensitivity in the visible light region, the photosensitive region is limited and the usable wavelength region is limited. It is not enough for practical use. Many of these photosensitive resin compositions are photopolymerizable resins and are affected by oxygen. Therefore, when the above-described photosensitive resin composition is used as a recording material, not only is there a limitation in the selection of a light source, but there is a problem that a special device for blocking oxygen is required. There is a need to solve these.

[0006]

Means for Solving the Problems The present inventors have considered that the type of sensitizer in the sensitized oxidation reaction ranges from the ultraviolet region to the near infrared region, and As a result of intensive research focusing on reactions,
The inventors have found that the oxazole derivative bonded to the polymer side chain is easily sensitized and oxidized not only in a solution but also in a solid state, resulting in a change in solubility in a solvent, which has led to the present invention.

That is, the present invention provides (1) a photosensitive resin composition containing a resin having an oxazole derivative in a side chain, and a triplet sensitizer that generates singlet oxygen; The present invention provides an image recording material capable of recording an image by irradiating the image recording material coated with the photosensitive resin composition with light and then developing with an aqueous amine solution.

The resin having an oxazole derivative in the side chain used in the present invention is a homopolymer of a vinyl monomer having an oxazole derivative or a copolymer with another vinyl monomer, and these polymers are azoisobutyroyl as a polymerization initiator. It can be easily synthesized by ordinary radical polymerization using nitrile or the like. These polymers need only be transparent to light having a wavelength that the sensitizer absorbs.

Here, typical examples of the vinyl monomer having an oxazole derivative for obtaining the resin having an oxazole derivative in the side chain of the present invention are shown below. However, it is not limited to these.

[0010]

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Examples of other vinyl monomers when forming a copolymer include (meth) acrylamide, N,
N-dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, (meth) acrylic acid-2-
Examples thereof include (2-methoxyethoxy) ethyl, tetrahydrofurfuryl (meth) acrylate, and (meth) acrylic acid. However, a monomer that can be radically polymerized with a vinyl monomer having an oxazole derivative may be used.

The degree of polymerization of the resin having an oxazole derivative in the side chain of the present invention is preferably 10 or more. If the degree of polymerization is less than this range, the film-forming property is poor and the coating on the substrate tends to be difficult.

The sensitizer that can be used in the present invention includes xanthene dyes, thiazine dyes, coumarin dyes, porphyrin dyes, cyanine or merocyanine dyes, and the like. More specifically, fluorescein, eosin, erythrosine, 3,3′-carbonylbis (7-diethylaminocoumarin), rose bengal, thionin, methylene blue, tetraphenylporphyrin and its zinc complex, meso-phenyltetrabenzoporphyrin and its zinc complex, Tetrakis (3,4-
Dimethoxyphenyl) porphyrin and its zinc complex,
Chlorophyll a, chlorophyll b and the like. However, it is not limited to the above as long as it is a triplet sensitizer that generates singlet oxygen.

The content of these sensitizers is preferably in the range of 0.1 to 50% by weight based on the oxazole derivative contained in the resin having an oxazole derivative in the side chain of the present invention. More preferably, it is in the range of 20% by weight. If the amount is less than this range, the generation of singlet oxygen is reduced, and the photooxidation rate of the oxazole derivative in the side chain is reduced, and the sensitivity tends to be reduced. On the other hand, if it is larger than this range, the sensitizer will be self-quenched to lower the sensitivity and to inhibit dissolution during development.

The photosensitive resin composition containing a resin having an oxazole derivative on the side chain and a sensitizer of the present invention is applied, and after irradiation with light, it can be used in an aqueous amine solution required for development. Possible amines are monoethanolamine, diethanolamine, methylethanolamine, dimethylethanolamine, monoethylamine,
Ammonia, morpholine, glycine, taurine, N, N
-Dimethylethylenediamine, N, N'-dimethylethylenediamine, 3-aminopropanol and the like. However, usable amines are not limited to these. Further, an organic solvent such as methanol may be added to the aqueous solution.

The amine content in the aqueous amine solution is preferably in the range of 0.1 to 50% by weight, and more preferably 1 to 20% by weight.
Is more preferable. If the amount is less than this range, the developability tends to be poor, a long development time is required, and image recording tends to be difficult. On the other hand, if it is larger than this range, the film may be damaged or image recording may be difficult.

As a method for producing the image recording material of the present invention, for example, a method similar to a known method for producing a printing plate (PS plate) or a photoresist substrate can be used. That is, a solution prepared by dissolving a resin having an oxazole derivative in the side chain of the present invention on the surface of a substrate such as metal or glass and a photosensitive resin composition containing a sensitizer in a suitable solvent such as toluene is used as a coater machine. Alternatively, it may be applied by a spin coater.

Usually, the photosensitive resin composition does not have an adverse effect such as corrosion on the surface of the coated substrate, but the photosensitive resin composition of the present invention comprises a resin having an oxazole derivative in a side chain and a sensitizer. The same applies to objects.

[0019]

As shown in the chemical formula, it is known that an oxazole derivative becomes a triacylamide compound by a photooxidation reaction in a dilute solution.

[0020]

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In the photosensitive resin composition of the present invention containing a resin having an oxazole derivative in the side chain and a sensitizer, not only in a solution but also in a film applied to a substrate surface such as a metal or glass, The photooxidation reaction occurs more efficiently, and the light-irradiated portion changes to a triacylamide compound.
The sensitizer that can be used here is not limited as long as it is a triplet sensitizer that causes energy transfer with oxygen to generate singlet oxygen. Therefore, by selecting a sensitizer, an image can be recorded in a wide range from visible light to near infrared light.

A photosensitive resin composition containing a resin having an oxazole derivative in a side chain and a sensitizer is coated on a substrate of the present invention, and the resultant is irradiated with light and then immersed in an aqueous amine solution. The portion converted to the triacylamide compound easily reacts with the amine, and the solubility in water increases, so that the compound is dissolved, thereby enabling image recording.

An image recording method using the image recording material of the present invention will be described in more detail with reference to FIGS. FIG.
The photosensitive resin composition of the present invention containing a resin having an oxazole derivative 1 in a side chain and a sensitizer 2 is applied on a substrate 3. Next, when light irradiation is performed as shown in FIG. 2, the oxazole derivative 1
Changes to a triacylamide compound 4 to form a latent image,
By immersing it in an aqueous amine solution, the triamide compound portion reacts with the amine and dissolves in the aqueous solution, and a positive image 5 is recorded as shown in FIG.

The light source used in the image recording method of the present invention may be a mercury lamp, a xenon lamp or the like, or an argon laser as a laser light source for stably outputting light in a wavelength range that can be absorbed by the sensitizer used. , A helium-neon laser, a YAG laser, and a semiconductor laser can be used as appropriate. When these lasers are used, it is possible to form an image by scanning exposure.

[0025]

EXAMPLES The details of the present invention will be specifically described below with reference to examples. However, the invention is not limited to these examples.

Example 1 Benzoin was reacted with acetic anhydride to form benzoin acetate, and further reacted with ammonium acetate to obtain 2-methyl-4,5-diphenyloxazole. This was stirred in THF (tetrahydrofuran) at −78 ° C. with n-butyllithium and diisopropylamine, and reacted by adding 2-iodoethyltetrahydropyranyl ether, followed by hydrolysis by adding acetic acid in methyl alcohol. , 2
-(Ω-Hydroxy) propyl-4,5-diphenyloxazole was synthesized.

This was reacted with methacrylic chloride to obtain a monomer containing an oxazole derivative. further,
This monomer and N-isopropylacrylamide were subjected to radical polymerization using azoisobutyronitrile as a polymerization initiator to synthesize a chemical substance of the formula (3).

[0028]

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A photosensitive resin composition in which 3% by weight of tetraphenylporphyrin (hereinafter simply referred to as TPP) is dissolved in 2000% by weight of chloroform with respect to 100% by weight of a resin having an oxazole derivative in a side chain represented by the following formula (3): A solution was prepared.

This solution was applied to the surface of an anodized aluminum substrate so as to have a thickness of about 2 μm using a spin coater, and dried to prepare an image recording material.

A step tablet manufactured by Kodak Co., Ltd. was brought into close contact with the image recording material, and 400 nm was taken out from the light of a 500 W high-pressure mercury lamp through a UV cut filter UV39 and an interference filter KL40 manufactured by Toshiba Glass Co., Ltd.
After irradiation with light and development using a 5% by weight aqueous solution of monoethanol, the amount of light required for image formation was determined from the number of dissolution steps. As a result, it was 70 mJ / cm ² .

Example 2 An image recording material was produced under exactly the same conditions and method as in Example 1. The sensitivity was determined in the same manner as in Example 1 except that this image recording material was replaced by KL55 that transmits light of 550 nm instead of the interference filter KL40. The result was 170 mJ / cm ² .

(Embodiment 3) Instead of TPP, 3,3'-
An image recording material was produced under exactly the same conditions and method as in Example 1 except that carbonyl bis (7-diethylaminocoumarin) was used. This image recording material is replaced with an interference filter KL40 by using KL5 that transmits 500 nm light.
The sensitivity was determined in the same manner as in Example 1 except that 0 was used. The result was 60 mJ / cm ² .

Example 4 An image recording material was produced under the same conditions and method as in Example 1 except that a zinc complex of meso-phenyltetrabenzoporphyrin was used instead of TPP. This image recording material is used as an interference filter KL
The sensitivity was determined in exactly the same manner as in Example 1 except that KL55 transmitting 550 nm light was used instead of 40. The result was 170 mJ / cm ² .

Example 5 An image recording material was produced under the same conditions and method as in Example 1, except that tetrakis (3,4-dimethoxyphenyl) porphyrin was used instead of TPP. This image recording material is replaced by an interference filter KL40 instead of KL55, which transmits 550 nm light.
The sensitivity was determined in exactly the same manner as in Example 1 except for using. The result was 170 mJ / cm ² .

Example 6 An image recording material was produced under the same conditions and method as in Example 1, except that a zinc complex of tetrakis (3,4-dimethoxyphenyl) porphyrin was used instead of TPP. The sensitivity was determined in the same manner as in Example 1 except that this image recording material was replaced with KL55 instead of the interference filter KL40. The result is
It was 80 mJ / cm ² .

Example 7 An image recording material was produced under exactly the same conditions and method as in Example 5. A step tablet manufactured by Kodak Company was brought into close contact with this image forming material,
m, and developed using a 5% by weight aqueous solution of monoethanol, the amount of light required for image formation was determined from the number of curing stages. As a result, it was 200 mJ / cm ² .

Example 8 An image recording material was produced under exactly the same conditions and method as in Example 4. A step tablet manufactured by Kodak Company is brought into close contact with the image forming material, and 632n
m, and developed using a 5% by weight aqueous solution of monoethanol, the amount of light required for image formation was determined from the number of curing stages. As a result, it was 20 mJ / cm ² .

Example 9 An image recording material was produced under exactly the same conditions and method as in Example 1. The sensitivity of this image recording material was determined in exactly the same manner as in Example 1 except that 20% by weight of methanol was added to 5% by weight of monoethanolamine. The result was 10 mJ / cm ² .

Example 10 An image recording material was produced under exactly the same conditions and method as in Example 1. The sensitivity was determined in exactly the same manner as in Example 1 except that N-methylethanolamine was used instead of monoethanolamine for this image recording material. The result was 70 mJ / cm ² .

Example 11 An image recording material was produced under exactly the same conditions and method as in Example 1. The sensitivity was determined in exactly the same manner as in Example 1 except that N, N-dimethylethylenediamine was used instead of monoethanolamine for this image recording material. The result was 70 mJ / cm ² .

Example 12 An image recording material was produced under exactly the same conditions and method as in Example 1. The sensitivity was determined in the same manner as in Example 1 except that morpholine was used in place of monoethanolamine for this image recording material. The result was 100 mJ / cm ² .

Example 13 A chemical substance of formula 4 was synthesized using N-dimethylacrylamide instead of N-isopropylacrylamide of Example 1.

[0044]

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An image recording material was produced under the same conditions and method as in Example 1 except that a resin having an oxazole derivative in the side chain was used. The sensitivity of this image recording material was determined under exactly the same conditions and method as in Example 1.
The result was 70 mJ / cm ² .

[0046]

Since the photosensitive resin composition of the present invention utilizes sensitized oxidation by oxygen having a low excitation energy, a wide range of visible light to near infrared light can be obtained by selecting a sensitizer. Has an excellent feature that an image can be formed with light having a wavelength of The photosensitive resin of the present invention can be coated on various substrates to form an image recording material, and has a wide range of uses as an image recording material for printing plates, photoresists, holography and the like.

[0047]

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing a state where a photosensitive resin composition of the present invention containing a resin having an oxazole derivative in a side chain and a sensitizer is applied on a substrate.

FIG. 2 is an explanatory diagram showing that an oxazole derivative is changed to a triacylamide compound by light irradiation.

FIG. 3 is an explanatory diagram showing that a portion of a resin that has become a triacylamide compound is eluted into an amine aqueous solution to form a positive image.

[Explanation of symbols]

 Reference Signs List 1; oxazole derivative 2; sensitizer 3; substrate 4; triacylamide compound 5;

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03F 7/039 G03F 7/004

Claims (2)

(57) [Claims] 1. A photosensitive resin composition comprising: a resin having an oxazole derivative in a side chain; and a triplet sensitizer generating singlet oxygen . 2. An image recording material capable of recording an image by applying a photosensitive resin on a substrate, irradiating the resin with light, and then developing with an aqueous amine solution. An image recording material comprising a photosensitive resin composition containing a resin having an oxazole derivative in a side chain and a triplet sensitizer generating singlet oxygen .