JPH0816783B2 - Visible light recording material - Google Patents

Description

TECHNICAL FIELD The present invention is highly sensitive to visible light, particularly laser light, and forms a surface relief image only after heating without using a developing solution after exposure. In addition, the present invention relates to a visible light recording material excellent in resolution and storage stability.

2. Description of the Related Art Visible light recording materials are used in various technologies using a laser having a visible oscillation wavelength as a light source. Since recording by laser light can be controlled by an electronic 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 the monochromaticity of laser light is also important. A recording material suitable for such a purpose is 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.

Photosensitive resins are useful for recording materials that take advantage of this feature because they are characterized by relief image formation, but most conventional photosensitive resins are used for photoresist materials, inks, paints, varnishes, printing plate-making materials, etc. However, their photosensitive wavelengths remained in the ultraviolet range. As a resin sensitive to visible laser light, photopolymerization type and photocrosslinking type materials have been proposed so far. For example, in JP-A-52-134692, a photopolymerization composition comprising a polycyclic quinone and a tertiary amine, in JP-A-54-151024, a composition using a merocyanine and a triazine derivative as a photopolymerization initiator, JPA
No. 54-155292, a photopolymerization composition using an imidazolyl dimer and a cyclic ketone having an aminophenyl group as an initiator, and in JP-A No. 60-22129, a p-phenylenediacrylic acid residue and a pyrylium salt, etc. A photocrosslinkable polymer composed of a sensitizer of the above is shown. Although these are sensitive to visible light with relatively high sensitivity, they belong to a so-called negative type and have a drawback that they are inferior in resolution.

On the other hand, it is well known that the photo-soluble resin composition (positive type) has very excellent resolution, and o-naphthoquinonediazides as typical examples thereof are put to practical use. . However, this photosensitive material is not known to perform optical sensitization, and has a problem that it has extremely low sensitivity in the visible light region. So in recent years
A high-sensitivity photosoluble resin composition that does not use o-naphthoquinonediazides has been proposed. JP 57-176035
In JP-A-59-45439, a composition comprising a polymer having an olefin introduced into the methacrylate side chain, a mercapto acid and a reaction initiator is used. In JP-A-59-45439, poly-pt which causes hydrolysis using an acid generated by light irradiation as a catalyst -Butoxycarboxylstyrene composition, JP-A-61-167945 discloses a composition comprising an acid generated by light irradiation and a compound having a silyl ether group which causes hydrolysis as a catalyst. However, none of them are sensitive to long-wavelength light, and even higher sensitivity has been desired for use as a light-sensitive material for laser, a silver salt substitute material, and the like. Furthermore,
If the developing process can be performed in a dry manner, the resolution can be further improved and the recording forming process can be simplified. Therefore, a material capable of forming a recording only by heat treatment has been desired.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention relates to a visible light recording material which is exposed to visible light and can be developed by a heat treatment, and moreover, a photosensitive material which has both excellent characteristics of photosensitivity 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, high resolution, and capable of forming an image only by heat treatment, and as a result, the present invention was achieved. It has come.

That is, the present invention provides (A) general formula [Wherein R ¹ represents a 2-aryl-2-propyl group or a diarylmethyl group (wherein aryl may be substituted with a hydrocarbyl group or an alkoxyl group)] And the general formula (In the formula, R ² is a hydrogen atom or a methyl group, R ³ is a carbon atom of 1 to
4 represents a lower alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a substituted carbamoyl group, a phenyl group or a naphthyl group), and a polymer unit of 0 to 70 mol% B) General formula (Wherein R ⁴ and R ⁵ are lower alkyl groups, X is a hydrogen atom, phenyl group, acyl group, cyano group, ammonio group or alkoxycarbonyl group, Y is an acyl group, cyano group, ammonio group or alkoxycarbonyl group, The present invention provides a visible light recording material comprising 3 to 20 parts by weight of the p-aminobenzylidene derivative represented by the formula (2) and 2 to 20 parts by weight of the (C) diaryl iodonium salt.

The polymer compound used as the component (A) in the visible light recording material of the present invention contains a methacrylic acid ester having an ester bond that is easily decomposed by an acid as a copolymerization component. As the monomer giving the structural unit of the general formula (I), specifically, 2-phenyl- of methacrylic acid is used.
2-propyl ester, 2- (p-anisyl) -2-propyl ester, 2- (p-tolyl) -2-propyl ester, 2- (p-biphenyl) -2-propyl ester, diphenylmethyl ester, bis ( p-anisyl)
Methyl ester and the like can be mentioned, but not limited thereto. The structural characteristics of these monomers are not only that the ester bond is easily cleaved by an acid, but that the alcohol moiety forming these esters has a remarkably large molecular weight. In other words, acid degradation is accompanied by a large molecular weight change. As the polymer compound used in the present invention,
In addition to polymers consisting of these monomers alone, the general formula (I
Polymerized vinyl monomers such as (meth) acrylic ester, (meth) acrylamide, substituted (meth) acrylamide, and styrene corresponding to the structural unit represented by I) are used. The characteristics of the desired photosensitive resin composition can be adjusted by selecting the type and copolymerization ratio of these copolymerizable monomers.
If the ratio of the units is too high, the change in the molecular weight of the polymer due to the decomposition by the acid is relatively reduced, and the relief forming ability is reduced. Therefore, the structural unit represented by the general formula (II) is preferably 70 mol% or less.

The diaryl iodonium salt used as the component (C) in the visible light recording material of the present invention has a property of generating an acid upon irradiation with light. Examples of the compound used in the present invention include those described in Macromolecules, 10, 1307 (1977), for example, diphenyliodonium, ditolyliodonium, phenyl (p-anisyl) iodonium, bis (m-nitrophenyl) iodonium, bis ( p-t-
Examples thereof include chlorides of iodonium such as butylphenyl) iodonium, bromides, borofluoride salts, hexafluorophosphate salts, and hexafluoroarsenate salts.

The p-aminobenzylidene derivative used as the component (B) in the visible light recording material of the present invention has a function of sensitizing the photolysis of the diaryl iodonium salt. Examples of the dialkylaminobenzylidene compound represented by the general formula (II) include the following compounds.

The amount of the diaryl iodonium salt of the component (C) contained in the visible light recording material of the present invention can range from 1: 0.02 to 1: 0.2 in terms of the weight ratio of the polymer compound: the diaryl iodonium salt. is there. Further, the weight ratio of the polymer compound and the sensitizer of the component (B) is in the range of 1: 0.02 to 1: 0.2.

If desired, known additives such as binders, pigments and plasticizers may be added to the visible light recording material of the present invention.
The visible light recording material thus adjusted is applied onto a smooth substrate to obtain a visible light recording material.

As a light source suitable for the visible light recording material 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.

After exposing 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 8
0-120 ° 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 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 further the sensitivity of the optical recording material of the present invention can be improved.

EFFECTS OF THE INVENTION The visible light recording material of the present invention forms a relief image only by heat treatment after exposure and has excellent sensitivity, so that it can be applied to a wide range of fields such as production of various reliefs and production of holograms. .

EXAMPLES Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

Examples 1 to 3 2-phenyl-2-propanol (17.8 g) and methacrylic acid chloride (20.6 g) were stirred in the presence of triethylamine (26.6 g) with ethyl acetate (30 ml) for 20 hours at room temperature. The reaction product was washed with 0.1N hydrochloric acid, a 1N sodium hydroxide aqueous solution and water, and then distilled under reduced pressure to obtain 13.1 g of α, α-dimethylbenzyl methacrylate. After 9.0 g of this ester was dissolved in 90 ml of benzene, azobisisobutyronitrile (AIBN) (1.0 mg) was added to the ampoule, which was 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 a polymer.
6.5 g was obtained. This polymer was prepared into a 20% by weight diglyme solution, and diphenyliodonium hexafluorophosphate and the sensitizer shown in Table 1 were added to the polymer so as to be 20% by weight and 10% by weight, respectively. It was used as a photosensitive liquid. This was spin-coated on a glass plate to a film thickness of 1.0 to 1.5 μm, and prebaked at 80 ° C. for 10 minutes. This was exposed with a xenon lamp through a line and space mask of about 50 μm. Then 15 at 120 ° C
Post-baked for a minute. When the surface condition obtained after the post-baking was measured by a Tarry step (RANK TAYLOR HOBSON), each exposed part was reduced by about 30% and a surface relief image was formed. In addition, the post bake temperature
When changing the temperature to 130 ° C and measuring the film loss in the exposed area, it was about 40
% (Fig. 1).

Example 4 The dimethyl benzyl methacrylic acid ester obtained in Example 1 was copolymerized 1: 1 with methyl methacrylate, and 0.5 g of this copolymer was added to 0.05 g of the sensitizer used in Example 1 and diphenyliodonium hexafluoro. It was dissolved in diglyme with 0.05 g of phosphate. The solution was spin-coated on a glass plate in the same formulation as in Example 1 to a film thickness of about 1 μm,
Prebaking was performed at 10 ° C for 10 minutes. This was exposed with a xenon lamp through a 50 μm line-and-space mask. When post-baked at 120 ° C. for 20 minutes, a surface relief image was formed.

Example 5 10.4 g of 4,4'-dimethoxybenzohydrol was added to THF50
36 ml of a hexane solution of 1.8 M n-butyllithium was added dropwise with stirring in a nitrogen atmosphere while stirring. 30 minutes later TH
4.5 g of methacrylic acid chloride diluted with 20 ml of F was added dropwise,
After stirring at room temperature for about 1 hour, cool the reaction vessel with water.
0 ml was added. The reaction solution was treated by a conventional method to obtain 4.7 g of methacrylic acid 4,4'-dimethoxybenzohydryl ester. The obtained ester was polymerized using AIBN as an initiator in the same manner as in Example 1, and 0.5 g of this polymer was converted to diglyme together with 0.05 g of the sensitizer used in Example 1 and 0.05 g of diphenyliodonium hexafluorophosphate. Dissolved. The solution was spin-coated on a glass plate in the same formulation as in Example 1 to a film thickness of 1.1 μm, and prebaked at 80 ° C. for 10 minutes. This was exposed with a xenon lamp through a 50 μm line-and-space mask. When post-baked at 130 ° C. for 20 minutes, a surface relief image was formed.
The exposed area showed a film loss of about 45%.

Example 6 2- (p-biphenyl) in 79.9% yield by Grignard reaction of 4-acetylbiphenyl with methyl iodide
2-Propanol was synthesized and used as the corresponding methacrylic acid ester in the same manner as in Example 1. 0.5 g of the radical polymer obtained from this was used in Example 1 as a sensitizer.
It was dissolved in diglyme together with 06 g and 0.06 g of diphenyliodonium hexafluorophosphate. This solution was coated on a glass plate with the same formulation as in Example 1 to obtain a film thickness of 1.4 μm.
Was spin coated and prebaked at 80 ° C. for 10 minutes. This was exposed with a xenon lamp through a 50 μm line-and-space mask. When post-baked at 130 ° C. for 20 minutes, a surface relief image was formed. Exposed area is about 45
% Film loss.

Example 7 In the same manner as in Example 1, a polymer was obtained by radical polymerization using 2- (p-tolyl) -2-propanol as a methacrylic acid ester. 0.5 g of this polymer was dissolved in diglyme together with 0.05 g of the sensitizer used in Example 1 and 0.06 g of diphenyliodonium hexafluorophosphate. The solution was spin-coated on a glass plate in the same formulation as in Example 1 to a film thickness of 1.3 μm, and prebaked at 80 ° C. for 10 minutes. This was exposed with a xenon lamp through a 50 μm line-and-space mask. Post-baking at 120 ° C. for 10 minutes formed a surface relief image.
The exposed area showed a film loss of about 45%.

[Brief description of drawings]

Fig. 1 shows that poly (methacrylic acid α, α-dimethylbenzyl ester) was added with diphenyliodonium hexafluorophosphate and 1-benzoyl-2- (p-dimethylaminophenyl) propenenitrile at 20% by weight and 10% by weight, respectively. The following shows the state of film loss when post-baking was performed at each temperature after the addition and irradiation of a 1.0 μm thin film of this photosensitive composition with light from a xenon lamp.

Claims (1)

[Claims] 1. A general formula (A) [Wherein R ¹ represents a 2-aryl-2-propyl group or a diarylmethyl group (wherein aryl may be substituted with a hydrocarbyl group or an alkoxyl group)] And the general formula (In the formula, R ² is a hydrogen atom or a methyl group, R ³ is a carbon number of 1 to 4
A lower alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a substituted carbamoyl group, a phenyl group or a naphthyl group), which is 0 to 70 mol% of the structural unit represented by the formula (B) ) General formula (Wherein R ⁴ and R ⁵ are lower alkyl groups, X is a hydrogen atom, phenyl group, acyl group, cyano group, ammonio group or alkoxycarbonyl group, Y is an acyl group, cyano group, ammonio group or alkoxycarbonyl group, n is 0 or 1) A visible light recording material comprising 3 to 20 parts by weight of a p-aminobenzylidene derivative represented by the formula: and 2 to 20 parts by weight of a (C) diaryl iodonium salt.