JPH06102670A - Visible light sensitive resin composition - Google Patents

Abstract

PURPOSE:To provide the visible light sensitive resin composition having excellent sensitivity and high resolving property in a visible ray region and having wide application in the field such as plate making material for plarographic and relief printing and for the fabrication of hologram by combining the specified high polymer compd. having at least one ester residual group constituting the resin composition sensitive to light in visible region with specified diaryl iodonium salt. CONSTITUTION:The composition is composed of the combination of the polymer having at least one or more of structure unit expressed by formula I and the mol.wt. within a 1000-1000000 range and the diaryl iodonium salt expressed by formula II. In formula I, R1 is tert-butyl, 2-aryl-2-propyl, diarylmethyl, tetrahydropyranyl group. In formula II, R2 is lower alkyl group, X is the residual group selected among hydrogen atom, phenyl, cyano group, etc., Y is the residual group selected among acyl, cyano, amonio or alkoxycarbonyl group, (n) is 0 or 1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photo-soluble resin composition having excellent sensitivity, and more specifically, it has a substance capable of generating a strong acid upon irradiation with light and a functional group capable of easily undergoing hydrolysis by an acid. The present invention relates to a visible light resin composition containing a polymer substance.

[0002]

2. Description of the Related Art Visible light resin compositions have been applied to various techniques using a laser having a visible oscillation wavelength as a light source. Since recording by laser light can be controlled by a computer, direct drawing is possible, and it is used for printing plate making, optical video disc original plate making, and the like. Furthermore, high-resolution hologram recording derived from monochromatic laser light is also important. Recording materials suitable for such purposes are required to be highly sensitive to laser light and exhibit high resolution. Further, in actual use, it is also necessary to have excellent storage stability for a long period of time.

Since the photosensitive resin is characterized by relief image formation, it is useful as a recording material that takes advantage of this point. However, most of the conventional photosensitive resins are photoresist materials, inks, and
It is used in paints, varnishes, printing plate-making materials, etc., and their photosensitive wavelengths remained in the ultraviolet region. So far, as a resin that is sensitive to visible laser light, photopolymerization type,
Photocrosslinkable materials have been proposed. For example, JP-A-52
No. -134692, a photopolymerization composition comprising a polycyclic quinone and a tertiary amine; in JP-A No. 54-151024, a composition using a merocyanine and a triazine derivative as a photopolymerization initiator; and JP-A No. 54-155292. Japanese Patent Application Laid-Open No. Sho 60-2, which discloses a photopolymerization composition using an imidazolyl dimer and a cyclic ketone having an aminophenyl group as an initiator.
No. 2129 discloses a photocrosslinkable polymer comprising a p-phenylenediacrylic acid residue and a sensitizer such as a pyrylium salt. These are those that are sensitive to visible light with relatively high sensitivity, but belong to the so-called negative type,
It has a drawback of poor resolution.

On the other hand, the photo-soluble type recording material (positive type) is very excellent in resolution, and it is well known that o-naphthoquinonediazides as typical examples thereof are put to practical use. On the street. However, this photosensitive material is not known to perform optical sensitization, and has a problem that it has extremely low sensitivity in the visible region.

In recent years, high-sensitivity photosoluble resin compositions which do not use o-naphthoquinonediazides have been proposed. In JP-A-57-176035, a composition comprising a polymer having an olefin introduced into a methacrylate side chain, a mercapto acid and a reaction initiator, and in JP-A-59-45439, hydrolysis is carried out using an acid generated by light irradiation as a catalyst. In Japanese Patent Laid-Open No. 167945/1986, a composition comprising a compound having a silyl ether group that causes hydrolysis using an acid generated by light irradiation as a catalyst is disclosed. It is shown. However, none of them senses visible light, and even higher sensitivity has been demanded for use as a light-sensitive material for laser, a silver salt substitute material, and the like.

[0006]

DISCLOSURE OF THE INVENTION The present invention relates to a resin composition which is solubilized by being exposed to visible light,
Moreover, it was made for the purpose of providing a light-sensitive material having a combination of excellent characteristics of photosensitivity and resolution.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems and comprises (A) general formula (I)

[0008]

[Chemical 3]

(In the formula, R ₁ is a tert-butyl group, 2-
(Which represents an aryl-2-propyl group, a diarylmethyl group, or a tetrahydropyranyl group) having a molecular weight of at least one structural unit of 1,000 to 1,000,000
A polymer in the range of

(B) General formula (II)

[0011]

[Chemical 4]

(In the formula, R ₂ represents a lower alkyl group, and X 2
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 a residue selected from an acyl group, a cyano group, an ammonio group or an alkoxycarbonyl group. , N is 0 or 1), which is a combination of diaryl iodonium salts.

The polymer compound having at least one ester residue constituting the visible light resin composition of the present invention is characterized in that the ester bond is cleaved by the presence of an acid and heating. Specific examples thereof include esters of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like. Specific examples thereof include tert-butyl, 2-aryl-2-propyl group, diarylmethyl group and tetrahydropyranyl ester of these carboxylic acids. As the polymer compound used in the present invention, in addition to these monomers, vinyl-based monomers such as (meth) acrylic ester, (meth) acrylamide, substituted (meth) acrylamide, styrene, and methylstyrene are used. A polymerized product is used.
By selecting the type of these copolymerizable monomers and the copolymerization ratio, the characteristics of the intended photosensitive resin composition can be adjusted.

The diaryliodonium cation represented by the general formula (II) as the component (B) has a property of generating an acid upon irradiation with light. Examples of the compound used in the present invention include Macromolecules, 10, 1307.
(1977). A compound described in, for example, diphenyliodonium, ditolyliodonium, (p-anisyl).
Examples thereof include cations such as phenyliodonium, bis (m-nitrophenyl) iodonium, and bis (p-tert-butylphenyl) iodonium.

The sulfonium anion represented by the general formula (II) as the component (B) has a function of spectrally sensitizing the photolysis of the diaryliodonium salt. Examples of the sulfonium anion represented by the general formula (II) include the following compounds.

[0016]

[Chemical 5]

The amount of the diaryl iodonium salt of the component (B) contained in the visible light resin composition of the present invention is from 1: 0.03 by weight ratio of the compound of the polymer compound (A): the diaryl iodonium salt. It is possible to have a range of 1: 0.2.

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

As a light source suitable for the visible light resin composition of the present invention, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a high pressure xenon lamp, a halogen lamp, a helium-cadmium laser and an argon laser can be used.

Next, the method of use will be described. First, a photosensitive solution obtained by dissolving a mixture of a polymer compound (A) and a diaryl iodonium salt (B) in a solvent is applied on a support by a method such as spin coating to form a photosensitive layer,
The one exposed for a predetermined time is heated in a dark place. The heating temperature is 60 to 150 ° C, preferably 90 to 110 ° C.
If it is less than this, the time required for image formation becomes remarkably long, and even if it is longer than this, the time for image formation cannot be shortened. The heating time depends on the heating temperature, but
20 minutes, preferably 5 to 10 minutes. When heating is performed in an atmosphere saturated with water vapor, the exposure time required for image formation can be shortened, and the sensitivity of the recording material of the present invention can be improved. After heating, the exposed area is solubilized to form an image by developing with a solvent containing a lower alcohol or an alkaline aqueous solution.

[0021]

Since the visible light-sensitive resin composition of the present invention has a higher sensitivity than the conventional visible light-sensitive resin, it can be used in a wide variety of fields such as plate-making materials for planographic printing and letterpress, various reliefs, holograms, etc. Can be applied to.

[0022]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. <Examples 1 to 6>

Copolymers shown in Table 1 were obtained by radical polymerization of methacrylic acid ester monomer in benzene solvent using azobisisobutyronitrile (AIBN) as an initiator.

[0024]

[Table 1]

These copolymers were dissolved in diethylene glycol dimethyl ether, and a diphenyliodonium salt (formula III) was added to the solution in an amount of 5 and 5, respectively.
A photosensitive solution was prepared by adding 10% by weight. This was spin-coated on an anodized aluminum plate, prebaked at 80 ° C. for 10 minutes, and exposed through a step tablet (Eastman Kodak Company No. 2) with a xenon lamp for 1 minute. This was post-baked at 110 ° C. for 10 minutes and then developed with an aqueous sodium hydroxide solution. The number of solubilization stages is summarized in Table 1.

[0026]

[Chemical 6]

<Examples 7 to 10>

The methacrylic acid ester copolymers shown in Table 2 were dissolved in diethylene glycol dimethyl ether,
A diphenyliodonium salt (formula III) was added to the solution in an amount of 10% by weight based on the copolymer to prepare a photosensitive solution. This was spin-coated on a glass plate to a film thickness of 1 μm, and prebaked at 80 ° C. for 10 minutes. Using the 488 nm emission line of an argon laser,
After exposing with an optical system as shown in FIG. 1 at a crossing angle of 34 °, 110
What was post-baked at 10 ° C. for 10 minutes was developed with an aqueous sodium hydroxide solution and washed with water to obtain a diffraction grating.
Table 2 shows the maximum diffraction efficiency of this diffraction grating and the exposure energy at that time.

[0029]

[Chemical 7]

[0030]

[Table 2]

[0031]

The visible light resin composition of the present invention has excellent sensitivity in the visible light region and further has high resolution.
It can be applied to a wide range of fields such as plate-making materials for planographic printing and letterpress printing, making various reliefs, and making holograms.

[0032]

[Brief description of drawings]

FIG. 1 is an explanatory view schematically showing an example of an apparatus used for producing a diffraction grating in the present invention.

[Explanation of symbols]

 1 Laser oscillator 2 Collimator 3 Reflection mirror 4 Beam splitter 5 Photosensitive material 6 Laser beam

Claims (1)

[Claims] 1. (A) General formula (I): (In the formula, R ₁ is a tert-butyl group, 2-aryl-2
-A propyl group, a diarylmethyl group, a tetrahydropyranyl group) and a polymer having a molecular weight in the range of 1,000 to 1,000,000 and having at least one structural unit represented by the general formula (II) ] (In the formula, R ₂ represents a lower alkyl group, X is a hydrogen atom,
It is a residue selected from 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) in combination with a diaryl iodonium salt.