JPH03124770A - Visible light-sensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain a visible light-sensitive resin compsn. with high sensitivity, high resolution and good storage stability by compounding a specified polymer compd. with a p-aminobenzylidene deriv. and a diaryliodonium salt. CONSTITUTION:1 pt. polymer compd. (A) with at least one structural unit of formula I (wherein R is 2-tetrahydrofuryl or 2-dihydropyranyl) and a mol.wt. of 1,000-1,000,000 is compounded with 0.03-0.3 pt. p-aminobenzylidene deriv. (B) of formula II (wherein R1 and R2 are each a lower alkyl; X is H, a phenyl, an acyl, a cyano, an ammonio or an alkoxycarbonyl; Y is an acyl, a cyano, an ammonio or an alkoxycarbonyl; (n) is 0 or 1) (e.g. a compd. of formula III, IV, etc.) and 0.02-0.3 pt. diaryliodonium salt (C) (e.g. diphenyliodonium, etc.). A visible light-sensitive soluble resin compsn. with more excellent sensitivity than that of the conventional visible light-sensitive resins is obtd. and it is applicable to a wide range of fields such as printing materials for lithography and letterpress, and preparation of various reliefs and a hologram.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a photo-soluble resin composition that exhibits excellent photosensitivity, and more specifically, to a photo-soluble resin composition that can generate a strong acid when irradiated with light and a substance that can be easily hydrolyzed by an acid. The present invention relates to a visible light-sensitive resin composition containing a polymeric substance having a functional group that can be activated.

Conventional technology-sensitive visible light resin compositions are used in various technologies in which a laser having a visible oscillation wavelength is used as a light source. Recording by laser light is
Since it can be controlled by an electronic computer, direct drawing is possible, and 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 can be used as recording materials that take advantage of this feature, but many conventional photosensitive resins can be used for photoresist materials, inks, paints, festivals, printing plate materials, etc. The wavelengths of light they are sensitive to remain in the ultraviolet range. Photopolymerizable and photocrosslinkable materials have been proposed as resins sensitive to visible laser light. For example, JP-A-52-1346
No. 92 discloses a photopolymerizable composition comprising a polycyclic quinone and a tertiary amine, and JP-A-54-151024 discloses
Composition using merocyanine and triazine derivative as a photopolymerization initiator, JP-A-155-1989 polymerization composition, JP-A-1989-1999-
No. 22129 discloses a photocrosslinkable polymer comprising a p-phenylene diacrylic acid residue and a sensitizer such as a biryllium salt. 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 be optically sensitized 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. 57-176
No. 035 discloses a composition comprising a polymer having an olefin introduced into the methacrylate side chain, mercapto acid, and a reaction initiator, and JP-A No. 59-45439 discloses a composition comprising a polymer having an olefin introduced into the methacrylate side chain, and JP-A No. 59-45439 discloses a poly-p- Composition consisting of t-butoxycarboxylstyrene, JP-A-61-1
No. 67945 discloses a composition comprising 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.

-GOORCI) (wherein, R represents a 2-tetrahydrofuryl group or a 2-dihydropyranyl group)
1 part of a polymer compound in the range of oo to 1ooooooo and (B) general formula Problems to be solved by the invention ゛The present invention relates to a resin composition that is solubilized by being exposed to visible light, Furthermore, the invention was made with the aim of providing a photosensitive material that has both excellent photosensitive speed and resolution.

Means for Solving the Problems The present inventors have completed the present invention as a result of intensive research to obtain a visible light-sensitive resin composition that has high sensitivity, high resolution, and good storage stability. This is what led to this.

That is, the present invention provides a compound of the general formula (A) (wherein R, R1 represents a lower alkyl group, and X is selected from a hydrogen atom, a phenyl group, an acyl group, a cyano group, an ammonio group, or an alkoxycarbonyl group) p-aminobenzylidene derivative o, 03-0 .3 parts and (C) diaryliodonium salt 0.02 to 0.3 parts.

Examples of the polymer compound having at least one ester residue constituting the photo-soluble resin composition of the present invention include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid, which have the characteristic of cleavage of ester bonds. It is something. Specifically, 2-tetrahydrofuryl ester and 2-dihydropyranyl ester of these carboxylic acids can be mentioned. In addition to polymers made only of these monomers, the polymer compounds used in the present invention include polymers containing vinyl monomers such as (meth)acrylic ester, (meth)acrylamide, substituted (meth)acrylamide, and styrene. A copolymerized product is used. By selecting the type and copolymerization ratio of these copolymerizable monomers, the desired characteristics of the photosensitive resin composition can be adjusted.

Component B, diaryliodonium salt, has the property of generating acid when irradiated with light. Compounds used in the present invention include Macromolecules, 10.13
07 (1977), such as diphenyliodonium, ditolyliodonium, phenyl (p-
chlorides of iodonium, such as anilyl) ionium,
Mention may be made of bromide or borofluoride salts, hexafluorophosphate salts, and hexafluoroarsenate salts.

Component C, a p-dialkylaminobenzylidene derivative, has the function of sensitizing the photodecomposition of diaryliodonium salts. Examples of compounds represented by general formula (II) are shown below.

The amount of the diaryliodonium salt of component B contained in the photosoluble resin composition of the present invention is determined by the weight ratio of the polymer compound diaryliodonium salt from 0.03 to t:o.3.
It can range up to.

If desired, known additives such as binders, pigments, and plasticizers may be added to the photosoluble resin composition of the present invention.

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 cannon lamps, and halogen lamps, helium-cadmium lasers and argon lasers can be used. After exposure for a predetermined time using these light sources,
Heat the resin composition in the dark. Heating temperature is 60-150
℃, preferably 80 to 130℃. 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 to 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. After heating, the exposed area is solubilized by developing with a solvent containing a polar solvent such as water or alcohol, and a high-resolution image is formed.

Effects of the Invention The sensitive and visible light-soluble resin composition of the present invention has a sensitivity superior to that of conventional photosensitive resins, so it can be used in the production of plate-making materials for planography and letterpress, the production of various reliefs, and the production of holograms. It can be applied to a wide range of fields.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

Examples 1 to 3 26.3 g of methacrylic acid and 50 ml of methylene chloride. p-
) 3,4-dihydropyran 32.) Added 0.8 g of pyridine luenesulfonic acid salt, stirred, and diluted with 30 ml of methylene chloride. Of was added dropwise, and the mixture was stirred at room temperature for about 2 hours. After treating the reaction solution in a conventional manner, it was distilled under reduced pressure to obtain tetrahydropyranyl methacrylate 39.3E.
I got it. 2.4 g of the obtained ester was radically polymerized with 0.6 g of phenyl methacrylate in 15 ml of benzene to obtain 2.6 g of a copolymer. This copolymer was added with 10% by weight of the sensitizer shown in Table 1, and spin-coated onto an anodized aluminum plate. After prebaking at 80° C. for 10 minutes, it was exposed to xenon light for 20 seconds through a Step Tablet (manufactured by Eastman Kodak). This was post-baked at 125° C. for 10 minutes and then developed with methanol. Table 1 shows the number of solubilization stages in detail.

Example 4 0.5 g of the copolymer of tetrahydropyranyl methacrylate and phenyl methacrylate obtained in Example 1 was mixed with 0.5 g of the sensitizer o used in Example 1 and 0.1 g of diphenyliodonium hexafluorophosphate ( The solution was spin-coated onto a glass plate to a film thickness of about 1 μm, and prebaked at 80°C for 10 minutes. After exposure with an optical system as shown in Figure 1 at an intersection angle of 22°, the product was post-baked at 100°C for 10 minutes and developed with a mixture of l-butanol:methanol = 1:1. 1 (sensitivity using various sensitizers=31673.Mw/Mn=6.45) was synthesized and fractionated into 10 fractions by a precipitation method using benzene as a solvent and hexane as a precipitant.

The four fractions with high recovery rates were mixed with a sensitizer and diphenyliodonium hexafluorophosphate in the same composition as in Example 1 to form a photosensitive composition, and holograms were produced in the same manner as in Example 4 for each fraction. Obtained. Table 2 summarizes the weight average molecular weight, dispersity, exposure energy, and diffraction efficiency of each fraction.

Table 2 Effect of Molecular Weight on Hologram Formation Holograms were obtained by rinsing with sun.

The diffraction efficiency of this hologram is
The maximum value was 17.5% when mJ/cm''.

Examples 5-8

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram schematically showing an example of an apparatus used for producing a hologram in the present invention. 1: Laser oscillator 2: Collimator 3: Reflection mirror 4: Beam splitter 5: Photosensitive material 6: Laser beam

Claims (1)

[Scope of Claims] (A) A compound having a molecular weight of 10 having at least one structural unit represented by the general formula -COOR (wherein R represents a 2-tetrahydrofuryl group or a 2-dihydropyranyl group)
(B) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 and R_2 represent a lower alkyl group, and X represents a hydrogen atom or a phenyl group.) , an acyl group, a cyano group, an ammonio group, or an alkoxycarbonyl group, Y is a residue selected from an acyl group, a cyano group, an ammonio group, or an alkoxycarbonyl group, and n is 0
or 1) 0.03 to 0.3 parts of a p-aminobenzylidene derivative represented by (C) 0.02 to 0.3 parts of a diaryliodonium salt,
A visible light-sensitive resin composition comprising: