JP2949205B2 - Visible light recording material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial application field> The present invention is sensitive to visible light, especially laser light, has high heat resistance, and has excellent resolution and storage stability. And a visible light recording material.

<Conventional Technology> Visible light recording materials are used in various technologies for forming a laser light source having a visible oscillation wavelength. Since recording by laser light can be controlled by an electronic computer, direct drawing becomes possible,
It is used for printing plate making and optical video disk master making. Furthermore, high-resolution hologram recording derived from the monochromaticity of laser light is also important. A recording material suitable for such a purpose is required to be sensitive to laser light with high sensitivity and exhibit high resolution. Further, in actual use, it is necessary to have excellent storage stability over a long period of time.

Photosensitive resins are useful for recording materials that take advantage of this feature because they have features in relief image formation, but many conventional photosensitive resins are used for photoresist materials, inks, paints, varnishes, printing plate making materials, etc. And their photosensitive wavelengths remained in the ultraviolet region.

As a resin that is sensitive to visible laser light,
Photopolymerizable and photocrosslinkable materials have been proposed.

For example, JP-A-52-134692 discloses a photopolymerizable composition comprising a polycyclic quinone and a tertiary amine.
No. 1024 discloses a composition using a merocyanine and a triazine derivative as a photopolymerization initiator, and JP-A No. 54-155292 discloses a photopolymerization using an imidazolyl dimer and a cyclic ketone having an aminophenyl group as an initiator. Composition, JP
JP-A-60-22129 discloses a photocrosslinkable polymer comprising a p-phenylenediacrylic acid residue and a sensitizer such as a pyrylium salt. Although they are sensitive to visible light with relatively high sensitivity, they belong to the so-called negative type and have a disadvantage that they have poor resolution.

On the other hand, the photo-soluble resin composition (positive type) has extremely excellent resolution, and it is well known that o-naphthoquinonediazides as typical examples are practically used. . However, this photosensitive material is not known to perform optical sensitization, and has a problem that the sensitivity is extremely low in a visible light region. So in recent years,
There has been proposed a high-sensitivity photo-soluble resin composition which does not use o-naphthoquinonediazides. JP-A-57-176035
In JP-A-59-45439, a composition comprising a polymer having an olefin introduced into a methacrylate side chain, a mercapto acid and a reaction initiator is disclosed. Composition comprising pt-butoxycarboxylstyrene, JP-A-61-1679
No. 45 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 higher sensitivity has been desired for use as a photosensitive material for laser or a silver salt substitute material. Furthermore, if a material with heat resistance can be made,
A heat-resistant photosensitive material for visible light has been desired because the resolution can be further improved and the range of use can be expanded.

<Problem to be Solved by the Invention> The present invention relates to a visible light recording material which is sensitive to visible light and has heat resistance, and which has both excellent speed and resolution. It was made for the purpose of providing.

<Means for Solving the Problems> The present inventors have conducted intensive studies to obtain a recording material having high sensitivity, photoresolution, and heat resistance, and as a result, have accomplished the present invention. It is.

That is, the present invention provides: (Wherein R ₁ represents a tert-butoxycarbonyl group or a tetrahydropyranyl group) 30 to 100 mol% of a structural unit represented by the following general formula (II): (Wherein, R ₂ represents a hydrogen atom or a methyl group, and R ₃ represents C _1-
C ₄ lower alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a substituted carbamoyl group, a polymer comprising a structural unit 0-70 mol% represented by a residue selected from a phenyl group or a naphthyl group) Compound 1 part (B) Diaryliodonium salt 0.02 to 0.2 part (C) General formula (III) (Wherein R ₁ and R ₂ represent a lower alkyl group, X is a residue selected from a hydrogen atom, a phenyl group, an acyl group, a cyano group, an ammonium 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).
03 to 0.2 part A visible light recording material comprising (A), (B) and (C).

The polymer compound constituting the visible light recording of the present invention contains, as a copolymerization component, a maleimide having a bond that is easily decomposed by an acid.

As a monomer giving the structural unit of the general formula (I), N-
Examples thereof include (p-tert-butoxycarbonyloxyphenyl) maleimide and N- (p-tetrahydropyranyloxyphenyl) maleimide, but are not limited thereto. A structural feature of these monomers is that the bond is easily cleaved by the acid.

The polymer compound used in the present invention includes, in addition to a polymer composed of only these monomers, (meth) acrylic ester, (meth) acrylamide, ) Those obtained by copolymerizing vinyl monomers such as 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, but the ratio of the unit of the general formula (II) is too high. The change in the molecular weight of the polymer due to decomposition by an acid is relatively reduced, and the ability to form a relief is reduced. Therefore, the content of the structural unit represented by the general formula (II) is desirably 70 mol% or less.

The diaryliodonium salt as the component (B) has a property of generating an acid by light irradiation. Examples of the compound used in the present invention include compounds described in Macromolecules, 10, 1307 (1977), for example, diphenyliodonium, ditolyliodonium, phenyl (p-anisyl) iodonium, bis (m-nitrophenyl) iodonium, bis ( (t-butylphenyl) iodonium, iodonium chloride, bromide or borofluoride;
Hexafluorophosphate salts and hexafluoroarsenate salts can be mentioned.

The p-dialkylaminomethylbenzylidene derivative as the component (C) has a function of sensitizing the photolysis of the diaryliodonium salt. As the dialkylaminobenzylidene compound represented by the general formula (II), the following compounds can be exemplified.

Component (B) contained in the photosoluble resin composition of the present invention
The amount of the diaryliodonium salt can range from 1: 0.02 to 1: 0.2 by weight of the polymer compound: diaryliodonium salt. Further, the weight ratio of the polymer compound to the sensitizer is in the range of 1: 0.03 to 1: 0.2.

If necessary, known additives such as a binder, a pigment, and a plasticizer may be added to the photo-soluble resin composition of the present invention. The visible light-sensitive material thus adjusted is applied on a smooth substrate to obtain a visible light recording medium.

As a light source suitable for the photosensitive composition of the present invention, a helium-cadmium laser and an argon laser can be used in addition to a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a high-pressure xenon lamp, and a halogen lamp.

After exposure for a predetermined time using these light sources, the recording medium is heated in a dark place. The heating temperature is 60-150 ° C, preferably 8
0-120 ° C. Below this, the time required for image formation becomes extremely long, and even longer, the time for image formation cannot be reduced. The heating time depends on the heating temperature, but is 1 to 20 minutes, preferably 2 to 10 minutes.
Further, when the heating is performed in a state of being saturated with water vapor, the exposure time required for image formation can be shortened, and the sensitivity of the optical recording material of the present invention can be improved.

<Examples> Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

<Examples 1 to 3> 130 ml of toluene was added to 150.3 g of maleic anhydride, and a solution prepared by dissolving 166.8 g of p-aminophenol in 200 ml of toluene was added with stirring in an oil bath. Filtered. The obtained reaction product was washed with toluene and dried to obtain 266 g of N- (p-hydroxyphenyl) maleic acid (a).

Next, 156.3 g of (a), 45.1 g of sodium acetate, and 56.2 g of acetic anhydride were added, and reacted in an oil bath at 70 ° C. for 30 minutes. The reaction product was poured into 500 ml of water, the resulting precipitate was filtered, dried and recrystallized from ethanol to give 120 g of N- (p-
Acetoxyphenyl) maleimide (b) was obtained. 184 g of ethanol was added to 60 g of (b), 150 mg of p-toluenesulfonic acid was further added, and methyl acetate generated by heating in an oil bath at 90 ° C. was removed from the system. The resulting solid is IPA
To give 15 g of N- (p-hydroxyphenyl) maleimide (c).

Dissolve 5 g of (c) in tetrahydrofuran and add 7.4 g of 2
After adding 1 g of -tert-butoxycarbonyloxyimino-2-phenylacetonitrile and triethylamine and stirring,
This was treated in a conventional manner to obtain 5.3 g of N- (p-tert-butoxycarbonyloxyphenyl) maleimide (d).

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

After polymerizing this at 60 ° C. for 20 hours, the reaction product was poured into methanol and filtered to obtain 2.3 g of the polymer (d). This polymer was prepared in a diglyme solution of 20% by weight, and diphenyliodonium hexafluorophosphate and a sensitizer were added so as to be 20% by weight and 10% by weight, respectively, based on the polymer to obtain a photosensitive solution. This is spin-coated on an anodized aluminum plate, pre-baked at 80 ° C for 10 minutes,
Step tablet (Eastman Kodak N
o.1A) for 1 minute with a xenon lamp. This is 125
After post-baking at 10 ° C. for 10 minutes, it was developed with methanol. When the following three types were used as sensitizers,
Table 1 summarizes the number of solubilization stages.

<Examples 4 to 6> 10.0 g of (c) was dissolved in dichloromethane, and after adding 10 mg of p-toluenesulfonic acid, 5.0 g of 3.4-dichtoro-2H-pyran was added dropwise with stirring. After stirring for 1 hour, the mixture was treated according to a conventional method to obtain 8 g of N- (p-tetrahydropyranyloxyphenyl) maleimide (e). 5 g of (e) obtained
Then, 1 g of styrene was dissolved in 60 ml of benzene, and the mixture to which 660 mg of AIBN had been added was placed in an ampoule. 5.3 g of the copolymer was used as a photosensitive solution in the same manner as in Examples 1 to 3, and evaluated using the same formulation as in Examples 1 to 3. The results obtained are shown in Table 2 for the cases where the following three types were used.

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

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-36240 (JP, A) JP-A-63-139343 (JP, A) JP-A-60-92302 (JP, A) JP-A 60-92 257444 (JP, A) JP-A-60-258204 (JP, A) JP-A-3-98051 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03F 7/00-7 / 18

Claims (1)

(57) [Claims] (A) The general formula (I) (Wherein R ₁ represents a tert-butoxycarbonyl group or a tetrahydropyranyl group) 30 to 100 mol% of a structural unit represented by the following general formula (II): (Wherein, R ₂ represents a hydrogen atom or a methyl group, and R ₃ represents C _1-
C ₄ lower alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a substituted carbamoyl group, a polymer comprising a structural unit 0-70 mol% represented by a residue selected from a phenyl group or a naphthyl group) Compound 1 part (B) Diaryliodonium salt 0.02 to 0.2 part (C) General formula (III) (Wherein R ₁ and R ₂ represent a lower alkyl group, X is a residue selected from a hydrogen atom, a phenyl group, an acyl group, a cyano group, an ammonium 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 0.2 parts of a p-aminobenzylidene derivative represented by the above (A), ( A visible light recording material comprising: B) and (C).