JPH0486667A - Visible light recording material - Google Patents

Abstract

PURPOSE:To improveme the sensitivity and heat resistance by forming this material with a specified high polymer compound, a diaryl iodonium salt and a specified p-aminobenzylidene derivative. CONSTITUTION:The material is consisting of one part of the high polymer compound composed of 30-100 mol% a structural unit expressed with formula I, 0-70 mol% a structural unit expressed with formula PI,and 0.02-0.2 parts a diaryl iodonium salt and 0.03-0.2 parts p-aminobenzylidene derivative expressed with formula III. In formula I,R1 denotes tert.-butoxycarbonyl group and tetorahydropyranyl group, and in formula PI,R2 is H,or methyl group,and R3 is 1-4C of a lower alkoxycarbonyl group, aryloxycarbonyl group,etc. In formula III,R1 and R2 is lower alkyl groups and X is H atom and phenyl group, etc., and Y is a residual group selected from acyl group,cyano group, etc., and (n) is 0 or 1. Thus the sensitivity and heat resistance are improved.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention is directed to a photosensitive material that is highly sensitive to visible light, especially laser light, has heat resistance, and has excellent resolution and storage stability. This invention relates to visible light recording materials.

<Prior Art> Visible light recording materials are used in various technologies that have a visible oscillation wavelength and use a laser as a light source. Recording using laser light can be controlled by an electronic computer, making direct writing possible.
It is used for printing plate making, optical video disk original plate production, etc. Furthermore, high-resolution hologram recording derived from the monochromaticity of laser light is also important. A recording material suitable for such purposes is required to be highly sensitive to laser light and to exhibit high resolution. Furthermore, in actual use, it is also necessary that the material has excellent storage stability over a long period of time.

Photosensitive resins have the characteristic of forming relief images, so they are useful as recording materials that take advantage of this feature, but many conventional photosensitive resins are used for photoresist materials, inks, paints, festivals, printing plate materials, etc. Their photosensitive wavelengths remained in the ultraviolet region.

Photopolymerizable and photocrosslinkable materials have been proposed as resins sensitive to visible laser light.

For example, in Japanese Patent Application Laid-open No. 52-134692,
A photopolymerizable composition comprising a polycyclic quinone and a tertiary amine, JP-A-54-151024, a composition using merocyanine and a triazine derivative as a photopolymerization initiator, JP-A-54-155292, A photopolymerization composition using an imidazolyl dimer and a cyclic ketone having an aminophenyl group as an initiator, JP-A-60-22129 discloses a sensitizing composition using a p-phenyl diacrylic acid residue and a pyrylium salt. A photocrosslinkable polymer consisting of an agent is shown. Although these are sensitive to visible light with relatively high sensitivity, they belong to the so-called negative type and have the disadvantage of poor resolution.

On the other hand, it is well known that photo-soluble resin compositions (positive type) have extremely excellent resolution, and 0-naphthoquinone diazides, which are representative examples thereof, are in practical use. . However, this photosensitive material is not known to undergo optical sensitization, and has the problem of extremely low sensitivity in the visible light region. Therefore, in recent years, 0
- Highly sensitive photo-soluble resin compositions that do not use naphthoquinone diazides have been proposed. Japanese Patent Publication No. 571760
No. 35 discloses a composition consisting of a polymer having an olefin introduced into the methacrylate side chain, mercapto acid, and a reaction initiator, and JP-A-59-45439 discloses a composition comprising a polymer having an olefin introduced into the methacrylate side chain, and JP-A-59-45439 discloses a composition comprising a polymer that undergoes hydrolysis using an acid generated by light irradiation as a catalyst. -pt-
JP-A-61-167945 discloses a composition made of butoxycarboxylstyrene, and a composition made of a compound having a silyl ether group that undergoes hydrolysis using an acid generated by light irradiation as a catalyst.

However, none of them are sensitive to long wavelength light, and even higher sensitivity has been desired for use as photosensitive materials for lasers, silver salt substitute materials, and the like. Furthermore, if a material with heat resistance can be created, resolution can be further improved.
Heat-resistant photosensitive materials for visible light have been desired since the range of use can be expanded.

<Problems to be Solved by the Invention> The present invention relates to a visible light recording material that is sensitive to visible light and has heat resistance, and which also has the characteristics of excellent photosensitive speed and resolution. It was made with the purpose of providing.

<Means for Solving the Problems> As a result of extensive research by the present inventors to obtain a recording material with high sensitivity, optical resolution, and heat resistance, the present invention was achieved. It is.

That is, the present invention comprises (A) - 30 to 100 mol% of structural units represented by the formula (1) (wherein R represents a tert-butoxycarbonyl group or a tehirahydropyranyl group); I
[) (In the formula, R7 represents a hydrogen atom or a methyl group, and R1 is selected from a lower alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a substituted carbamoyl group, a phenyl group, or a naphthyl group of Cl""' C4 1 part of a polymer compound consisting of 0 to 70 mol% of structural units represented by ) (In the formula, R,, R, represents a lower alkyl group, X is a residue selected from a hydrogen atom, a phenyl group, an acyl group, a cyano group, an ammonio group, or an alkoxycarbonyl group, and Y is an acyl group. , a residue selected from a cyano group, an ammonio group, or an alkoxycarbonyl group, and n is O or 1) 0.03 to 0.2 parts of the p-aminohenzylidene derivative (A), A visible light recording material comprising (B) and (C).

The polymer compound constituting the visible light recording material of the present invention contains maleimide as a copolymer component, which has a bond that is easily decomposed by acid.

- N (
p tert-butoxycarbonyloxyphenyl)
Examples include maleimide, N-(p-tetrahydropyranyloxyphenyl)maleimide, and the like, but are not limited thereto. A structural feature of these monomers is that their bonds are easily cleaved by acids.

In addition to polymers made only of these monomers, the polymer compounds used in the present invention include (meth)acrylic esters and (meth)acrylic esters corresponding to the structural unit represented by the general formula (■).
Copolymerized vinyl monomers such as acrylamide, substituted (meth)acrylamide, and styrene are used. By selecting the type and copolymerization ratio of these copolymerizable monomers, the properties of the desired photosensitive resin composition can be adjusted; The molecular weight change of the polymer due to acid decomposition is relatively reduced, and the relief forming ability is reduced. For this reason, −
The content of the structural unit represented by format (n) is preferably 70 mol% or less.

Component (B), diaryliodonium salt, has the property of generating an acid when irradiated with light. Compounds used in the present invention include Macromolecules, 10.
1307 (1977), for example, iodonium chlorides such as diphenyliodonium, ditolyliodonium, phenyl(p-anisiodonium, bis(p-t-butylphenyl)iodonium),
Mention may be made of bromides, borofluoride salts, hexafluorophosphate salts, and hexafluoroarse inert salts.

Component (C), a P-dialkylaminomethylhenzylidene derivative, has the function of sensitizing the photodecomposition of diaryliodonium salts. - As the dialkylaminohenzylidene compound represented by the format (II), the following compounds can be exemplified.

(b) iodonium, bis(m-nitrophenyl) The amount of component (B) (7) diaryliodonium salt contained in the photosoluble resin composition of the present invention is 1 by weight of the polymer compound diaryliodonium salt. :o, 03 to 1:0
．． A range of up to 2 is possible. Furthermore, the weight ratio of the polymer compound and the sensitized side is 1:0.02 to 1:0.
．． The range is 2.

If desired, known additives such as binders, pigments, and waxing agents may be added to the photosoluble resin composition of the present invention. The visible light-sensitive material thus prepared is coated onto a smooth substrate to form a visible light recording medium.

As light sources suitable for the photosensitive composition of the present invention, in addition to high-pressure mercury lamps, ultra-high-pressure mercury lamps, high-pressure xenon lamps, and nitrogen lamps, helium-cadmium lasers and argon lasers can be used.

After exposure for a predetermined time using these light sources, the recording medium is heated in a dark place. The heating temperature is 60 to 150°C, preferably 80 to 120°C. If it is less than this, the time required for image formation becomes extremely long, and even if it is more than this, the time required for image formation cannot be shortened. The heating time depends on the heating temperature, but is 1 to 20 minutes, preferably 2 minutes.
~10 minutes. Further, when heating is performed in a state saturated with water vapor, it is possible to shorten the exposure time required for image formation, and furthermore, it is possible to improve the sensitivity of the optical recording material of the present invention.

<Example> The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to this.

<Examples 1 to 3> 130 ml of toluene was added to 150.3 g of anhydrous maleic fi, and while stirring in an oil bath, 166.8 g of p-aminophenol dissolved in 200 ml of toluene was added, and after refluxing for 30 minutes, the reaction product became a slurry. was filtered. The obtained reaction product was washed with toluene and dried to obtain 266 g of N-(p-hydroxyphenyl)maleic acid (a).

Next, (a) 156.3g and 45.1g of sodium acetate
, 56.2 g of acetic anhydride was added, and the mixture was heated in an oil bath at 70°C for 30 min.
It was allowed to react for a minute. The reaction product was poured into 500 ml of water, and the resulting precipitate was filtered, dried, and then recrystallized using ethanol as a solvent to obtain 120 g of N(p-acetoxyphenyl)maleimide (b). methanol 184 to 60g (b)
g and additionally 150 mg of p-1-luenesulfonic acid.
was added and heated in a 90°C oil bath to remove generated methyl acetate from the system. The obtained solid was recrystallized with IPA to obtain 15 g of N-(p-hydroxyphenyl)maleimide (C).

Dissolve 5g of (C) in tetrahydrofuran, 7.4g
After adding 1-g of Boc-ON,) ethylamine and stirring, it was treated in a conventional manner to obtain 5.3 g of N-(p-tert-
Butoxycarbonyloxyphenyl)maleimide (d)
I got it.

3 g of the obtained (d) was dissolved in 30 ml of acetone, 330 mg of azobisisobutyronitrile (AIBN) was added, the mixture was placed in an ampoule, and the ampoule was replaced with argon gas and sealed.

After polymerizing this for 60°C12O hours, the reaction product was poured into methanol and filtered to obtain 2.3 g of the polymer (d). This polymer was prepared as a 20% by weight diglyme solution, and diphenyliodonium hexafluorophosphate and a sensitizer were added to the polymer in amounts of 20% and 10% by weight, respectively, to prepare a photosensitive solution. This was spin-coated onto an anodized aluminum plate, prebaked at 80°C for 10 minutes, and passed through a step tablet (No. IA manufactured by Eastman Kodak) using a xenon lamp.
Exposure was made for a minute. This was post-haked at 125°C for 110 minutes and then developed with methanol.

Table 1 summarizes the number of solubilization steps when the following three types of sensitizers were used.

(Margin below) Table 1 <Examples 4 to 6> Dissolve 10.0 g of (C) in dichloromethane, P-)
After adding 10 mg of luenesulfonic acid, while stirring,
．． 5°Og of 4-dihydro-2H-pyran was added dropwise. 1
The mixture was stirred for a period of time and treated according to the Umiya method to obtain 8 g of N-(p-tetrahydropyranyloxyphenyl)maleimide (e).

5 g of the obtained (e) and 1 g of styrene were mixed with 60 m of benzene.
Copolymer 5.3 was dissolved in Copolymer 5.3 and 660 mg of EIBN was added thereto, and placed in an ampoule in the same manner as in Examples 1 to 3.
Table 2 shows the results of evaluation using the same formulations as in Examples 1 to 3, using g as a photosensitive liquid and using the following three types.

Table 2 <Effects of the Invention> Since the visible light recording material of the present invention has excellent sensitivity and furthermore heat resistance, it can be applied to a wide range of fields such as the production of various reliefs and the production of holograms.

Claims (1)

[Claims] (1) (A) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R_1 represents a tert-butoxycarbonyl group or a tetrahydropyranyl group) Structural unit 30 represented by ~100 mol% and the general formula (I
I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R_2 represents a hydrogen atom or a methyl group, and R_
3 represents a residue selected from C_1 to C_4 lower alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, substituted carbamoyl group, phenyl group or naphthyl group) from 0 to 70 mol% of structural units represented by 1 part of a polymer compound (B) 0.02 to 0.2 parts of diaryliodonium salt (C) General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) (In the formula, R_1 and R_2 are lower represents an alkyl group; residues, n is 0
1. A visible light recording material comprising 0.03 to 0.2 parts of the p-aminobenzylidene derivative represented by (A), (B) and (C).