JPS5876832A - Metallic image forming material - Google Patents

Abstract

PURPOSE:To permit sharp etching of thin metallic layers in a short time without using any powerful etching soln. by providing >=1 layer of the vapor deposited metallic layers wherein the angles of vapor deposition with respect to a substrate increase gradually. CONSTITUTION:Vapor deposited metallic layers wherein angles theta of vapor depositon with respect to a substrate 1 incrase gradually are provided in >=1 layers on the substrate 1. Al is more preferable as the metal to be used, and the angle theta1 of initial vapor deposition is set at theta1<45 deg., and it is more preferable to set the angles in such a way that there is >=10 deg. in the changing range between said angle theta1 and the angle thetan of vapor deposition at the end of the vapor deposition. A photosensitive resin layer is provided on said vapor deposited metallic layers, and is patterned by pattern exposure and developing; thereafter, the vapor deposited metallic layers are etched by an aq. NaOH soln., etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a material for forming metal images, and more specifically, a novel four-metal image having high contrast image forming ability and suitable for fine line images and halftone images. Regarding forming materials.

Generally, when using a metal image-forming material consisting of an image-forming layer such as a photosensitive resin layer and a layer of a workpiece such as a metal, corrosion-resistant material having a certain image or design on the metal or non-metallic plate that is the workpiece is generally used. A technique in which a tactile film is formed using photographic techniques, etc., and then the exposed parts of the workpiece are dissolved chemically or electrochemically to obtain a desired metal image, or to perform drilling or groove processing. As a method, there is a photoetching method (hereinafter referred to as photoetching method).

In conventional metal image-forming materials, in the photo-etching method using a thin metal layer, a coating layer (hereinafter referred to as resist) having corrosion-resistant properties in the photosensitive resin layer on which the image is formed is immersed in an etching solution. There is a tendency to
If the etching solution is too weak to be immersed, the thin metal layer will be less likely to be etched by the etching solution, which usually results in longer etching times. Therefore, in order to increase efficiency, a strong etching solution must be used, which poses operational and environmental hazards, and the resist must be extremely corrosion resistant. Moreover.

It is difficult to obtain sharp images with strong etching liquids or weak resists, and as etching progresses, it progresses both vertically and laterally to the surface of the workpiece.
There is an inconvenience that so-called side etch occurs, causing disturbances in the etch of the image.

In addition, when printing a desired image onto the photosensitive resin layer using an ultraviolet lamp or the like, the light that has passed through the photosensitive resin layer is reflected on the underlying thin metal layer, causing scratching. Reproducibility was a problem.

The object of the present invention is to provide a metal image forming method that can etch a thin metal layer in a short time without using a strong etching solution, and can obtain a sharp image. We are here to provide you with a method.

The above-mentioned object of the present invention is to provide at least one metal vapor deposited layer on a support whose vapor deposition angle with respect to the support increases continuously, and a photosensitive resin layer on the metal vapor deposition layer. This is achieved by a metal imaging material characterized in that it is provided with.

According to a preferred embodiment of the present invention, the metal vapor deposition layer of the present invention has a 1# structure, and the metal vapor deposition layer is an aluminum vapor deposition layer.

The details of the present invention will be explained below by taking the case of the one-layer structure as an example, but the present invention is not limited thereto.

For example, the metal vapor deposited layer of the present invention may be composed of two or more multilayers. In this case, the metal vapor deposited layer below the top layer does not need to be the vapor layer of the present invention, and is fixed. Even if the metal vapor deposition layer has a vapor deposition angle of O0,
It may be a metal vapor deposited layer.

Furthermore, the present invention is not limited to the following layer configurations, and the photosensitive resin layer may be divided into two or more layers as necessary, or an intermediate layer, a protective layer, a Halley anti-silver layer, and/or an undercoat layer (for example, a water-based It is possible to use one or more resins that are soluble or have an affinity for the processing liquid.
It is Noh. Furthermore, the metal vapor deposited layer in the present invention is
The layer may include a mixture of the metal and an organic substance that can be vapor deposited.

The metal thin layer in the metal image forming material according to the present invention is a metal vapor deposition layer, and examples of the metal used in the metal vapor deposition layer include aluminum as described in detail in JP-A-50-139720. Mainly metals and JP-A-1988
-65927, 48-65928, 50-29
Tellurium, molyftene, boronium, cobalt, zinc, steel, nickel, iron, tin, vanadium, germanium, flUtU silver emulsion as described in each publication of No. 25 and No. 50-14161, and Examples include chromium, titanium, and alloys.

A preferred thin metal layer in the present invention is an aluminum thin layer.

The metal thin layer is a metal vapor-deposited layer formed by vapor-depositing a metal such that the vapor-deposition angle θ with respect to the support (the angle between the vertical axis of the support surface and the incident direction of the vapor-deposited particles) continuously increases. It is.

The evaporation angle that is continuously increased as an operation when forming a metal evaporation layer on the support is determined by the initially set initial evaporation angle and the variation range of the evaporation angle. Preferably, the initial evaporation angle θ1 is set to θ1. The width of change between this θ1 and the evaporation angle [0n at the end of evaporation is at least 10＠
6 is preferred.

The thickness of the metal vapor deposited layer of the present invention is determined by the optical density required for the resulting image, but the two are almost proportional; for example, if the image is a line drawing or halftone dot, a relatively high density is required. In particular, when the material of the present invention is used as a mask for printing onto a PS printing plate, an optical density of at least 2.0 is required, and an optical density of at least 3.0 is required. Since it is necessary, the thickness is determined accordingly. The optical density at this time is a value measured using a Macbeth transmission densitometer for a film having a metal vapor deposited layer.

The relationship between the overall thickness of the metal vapor deposited layer and the optical density may differ somewhat depending on the method of forming the metal vapor layer, for example, the conditions of vacuum vapor deposition, but is generally the same. Although it is not particularly prohibited to increase the thickness of the metal vapor deposited layer more than necessary in order to obtain the desired optical density, it is not prohibited to increase the thickness of the metal vapor deposited layer more than necessary. This is not desirable because it takes time. Furthermore, considering that excessive etching time may deteriorate the resist, it is better to avoid making the metal vapor layer thicker than necessary. The thickness of the metal vapor deposited layer formed by vapor deposition is 100A to 3
000A is good, but in order to obtain the optical density required according to the application, the film thickness is preferably 400A to 1
500A is desirable.

The support used in the present invention has a metal vapor deposited layer as an image forming layer provided directly or indirectly (via another layer) thereon, and is constructed using the support. The metal image forming material of the present invention can be made into various forms depending on the intended use. For many applications requiring this metal imaging material, which will normally occur to those skilled in the art from prior experience, the support is preferably in the form of a plate, sheet or film. , can be transparent, semi-transparent or opaque depending on its use. In addition, the support is not affected by the etching solution that corrodes the metal vapor deposited layer, and the adhesion to the layer that is disposed on it is likely to peel or peel off due to etching. It should not be something that becomes a problem.

Many conventionally known materials can be used as the material for the support, including ceramics, amorphous glass, crystalline glass, metals, alloys, plastics, and composite materials thereof. Some of these materials are opaque or transparent, but if necessary, colorants or opacifying agents can be added to the transparent materials to make them translucent or opaque. However, many possible areas of application are in which the imaging materials of the present invention are imaged by a metallized layer, allowing light to pass through non-image areas where there is no metallized layer and the support is exposed to the screen; The area is a so-called light-transmitting type application field in which light is blocked by a metal vapor deposited layer, and in the case of a metal image forming material used in such a field, the support thereof must be transparent. On the other hand, in applications where a formed image is recognized by reflected light, the substrate does not need to be transparent. It is also effective to use surface treatment techniques such as corona discharge, bombardment, and plasma treatment to improve the adhesion between the support and the metal deposited layer.

The photosensitive resin layer in the present invention can be formed using various conventionally known photosensitive resins for resist formation. When this photosensitive resin is irradiated with radiation iI (near ultraviolet i11 or visible light), its molecular structure changes chemically in a short period of time, resulting in physical properties such as solubility or stickiness in solvents. It includes all compounds and compositions such as monomers, prepolymers, and polymers in which the photosensitive resin changes. (It is common knowledge in the industry that the concept of "photosensitive resin" includes the above monomers and prepolymers. 10 The above photosensitive resins are broadly classified into solvent-dissolved type and peelable type based on the mode of development, and further classified into positive working type and negative working type, respectively. From the content of chemical changes, some photosensitive resins undergo a crosslinking reaction via metal ions when exposed to radiation, and some photosensitive resins undergo photocrosslinking which dimerizes themselves, while others exist together when exposed to radiation. Photodegradable substances decompose and undergo cross-linking reactions via the decomposed products, and those that are exposed to radiation.

These are classified as those that initiate polymerization, and any of these can be used to prepare the metal imaging material of the present invention. Although there are many known types of these photosensitive resins, the present invention applies to photosensitive resins that will be developed in the future that can form photosensitive resist films, regardless of their classification, in the same way as well-known ones. of metal imaging materials.

From the viewpoint of actual use of photosensitive resins, it is desirable to give an overview of the photosensitive resins used, focusing on classification based on the development mode rather than on the content of chemical changes. below,
Let's focus on and explain them.

In the case of photosensitive resins that form solvent-soluble layers, positive-working resins are decomposed by light irradiation to produce five-membered ring compounds with carboxyl groups, such as those seen in 0-quinone diazides, which are dissolved in alkaline solution. 】°Soruwei Tonashi,
It is a mold that acts so that the resin layer in the exposed area is removed by development with an alkaline solution, and the photosensitive resin layer in the unexposed area remains to form the desired image area.On the other hand, the mold made by Negative Working For example, those that become insolubilized by light irradiation, such as photocrosslinking represented by cinnamoyl groups and diazonium groups, and photopolymerization represented by acrylamide and acrylic esters, due to the enlargement of molecules and the formation of network structures. By using an appropriate solution, the unexposed portions of the photosensitive resin layer are removed, and the insolubilized exposed portions remain as desired image areas.

These solvent-soluble photosensitive resins are widely used as photosensitive liquids for P8 plates, wipe-on plates, photo-etching resists, and the like.

As a positive working type photosensitive resin, L2-
For example, z-mi-4-trioxybensif enone-bis [su7-toquinone-1,2-diazide-55-sulfonic acid ester] described in Japanese Patent Publication No. 37-18015, Kosho 37-3627
2-[naphthoquinone-L2-diazide-5-
sulfonyloxy]-7-hydroxynaphthalene, s7toquinone-L2-diazide-5-sul7anilide described in Japanese Patent Publication No. 37-1954, naphthoquinone-L2-diazide-sulfonic acid novolak described in Japanese Patent Publication No. 45-9610 There are esters, etc. And, as for 9 commercially available products, KPR (type 3)
(Eastman Kodak, USA); AZ-340
, AZ-1350, 'AZ-111, AZ-119 (A
zoplate-5hipley); Kall
Copin of eAktingesell-schaft
g Lacquer-p; Photosol, 7 Otonol B, 7 Otonol E (Tokyo Ohka Kogyo ■); FPPR-
300, FPPR-700, EPPR-1000 (Fuji Pharmaceutical Co., Ltd.); and the like.

Among negative working type photosensitive resins, there are water-soluble photosensitive liquids commercially available from companies such as Hiro, Kaihon Kagaku Kogyo, Fuji Yakuhin Kogyo, and Shiwa Sangyo, but PVA-ammonium dichromate-based ones are Most of them are reeds, but there are also four types: glue weight ammonium chromate type and casein-ammonium dichromate type. Many other photosensitive substances such as diazonium salts, azide compounds, and compounds having a cinnamoyl group are known as other useful photosensitive resins, but diazonium salts used as negative working type photosensitive resins include P- Paraformaldehyde condensate of diazodiphenylamine, U.S. Patent No. 1,762,0
1-diazo-4-dimethylaminobenzene-hydrofluoroborate, 1-diazo-3-methyl- described in No. 33
4-dimethylaniline sulfate, 1-diazo-3
-monoethylnaphthylamine, etc. Examples of the azide compounds include p-7 enylene bis azide, p-azidobenzophenone, bay-diazide benzophenone, and 44'-diazi-1zo-enylmethane described in U.S. Patent No. 2,852,379 and U.S. Patent No. z94Q853. 44'-Diazidostilbene, 44'-Diazidocalco/, z6-
Z-(4'-azidobenzal) Schiff-hexanone, 2.
Examples include 6'-cy(4/-azidobenzal)-4-methylcyclohexanone.

These azide compounds are usually mixed into a rubber solution and used as a "rubber photosensitive liquid," but the rubber used at this time can be natural rubber or synthetic rubber. Polyisoprene described in No.-22084 is often used.

Examples of polymers having an azide group in the molecule include vinyl polyazidobenzoate, vinyl polyazido heptatalate, and polyvinylazidobenzalacetal described in Japanese Patent Publication No. 40-28499 and Ichikawa No. 45-22085.

As a photosensitive resin having a cinnamoyl group as a photosensitive group, there is polyvinyl cinnamate. Cinnamylidene acetate derivatives of PVA are also used. Examples include polyvinyl cinnamylidene acetate, polyvinyl cinnamate, cinnamylidene acetate, polyvinylethoxycarbonylmethyl lupamate cinnamylidene acetate, polyvinyl acetate cinnamylidene acetate, and the like. Many other negative working photosensitive resins currently on the market are known, including those using acryloyl groups, those using acrylamides, and those using acrylates, such as KPR, KTFR%KM
ER (manufactured by Eastman Kodik, USA); Western Wipe-on (Western Litho P, USA)
Wipe-〇-sensitizer (manufactured by Litho Chemical & 5upply, USA)
; Other foreign products include Dynachem Corpo.
ration of DCR (Dynachem photo
Re5ist).

Phllip, Hunt Chemical Cor
WPR (waycoatphoto)
Re5ist), Kal Akting
esel 1schaf tq) CopingLa
Domestic products such as cuquer-N include hPPR.
.

OMR, TP (manufactured by Tokyo Ohka Kogyo ■); Negative Coat 7 Disuper Resist (manufactured by Fuji Pharmaceutical Co., Ltd.); Wipe Thor Resist S (manufactured by Kaihon Kagaku Kogyo ■); and KY Resist (manufactured by Kaihon Kagaku Kogyo ■).
Yamatoya Shoten), etc.

On the other hand, in the case of a photosensitive resin that has a peelable layer, for example, Japanese Patent Publications No. 38-9663, No. 41-15932, No. 4
No. 3-22901, No. 48-43126, Japanese Unexamined Patent Publication No. 1973
-7728, 47-33623, 48-589
As described in No. 09 and No. 48-101117, the photosensitive polymer, that is, the portion that was irradiated with light or the portion that was not irradiated with light, is connected to the lower layer, that is, the metal vapor deposited layer or intermediate layer adjacent to the support side. Polymers that have the property of decreasing or losing their adhesion to the underlying layer, or photosensitive monomers that polymerize and harden when exposed to light, increasing, decreasing or eliminating their adhesion to the underlying layer. Specifically, there are a wide variety of substances or compositions, and they can be appropriately selected in consideration of their characteristics.

To prepare the metal image-forming material according to the present invention, first, a desired metal vapor deposition layer is formed on the surface of a specified support by a method such as a vacuum evaporation method, a sputtering method, or an ion blasting method. An example of the method is as follows. FIGS. 1 and 2 are schematic diagrams of a vacuum evaporation apparatus showing an example of an embodiment of the present invention in which a metal evaporation layer is formed on a support by a vacuum evaporation method.

In the figure, the support l facing the evaporation source 2 is tilted to the substrate holder 5 so that the initial evaporation angle is 01, and is installed at θ1 (45@) at a constant evaporation rate (0).
At the same time as the shutter 4 is opened, the evaporation angle is gradually changed until the desired film thickness is reached at the evaporation end point (Fig. 2, angle on after the evaporation angle changes). Then, rotate the motor 6. In this way, the deposition angle with the support is gradually increased from 01, and a deposited film ending at θn is obtained.

The vapor deposition speed and motor 60 rotation speed line may not always be constant depending on the physical properties of the vapor deposited film.

Next, a photosensitive resin layer is formed thereon. In this case, the coating liquid for forming the photosensitive resin layer is selected from the various photosensitive resins mentioned above and is 7'C
One or more resins are dissolved in a solvent to form a solution or dispersion, and a necessary sensitizer and various additives are added to form a coating liquid. The coating solution prepared in this way is coated on the metal layer by a known coating method such as a roller coating method, an air knife coating method, a dipping method, a curtain coating method, a spray coating method, etc., and then allowed to dry. This forms a photosensitive resin layer. The dry thickness of the photosensitive resin layer may be about 0.1 to 10 μm. If it is too thin, the resist layer will be weak; if it is too thick, etching will take an excessively long time, and the resist layer may not form an accurate image corresponding to the exposed image. The prepared metal image forming material is subjected to imagewise exposure to the photosensitive resin layer using a known technique, and the photosensitive resin layer is developed with an etching solution that serves as both a developing solution and an etching solution, for example. At the same time (1
(bath method or two-bath method) After etching the metal vapor deposited layer or developing the photosensitive resin layer with a developing treatment solution and etching the metal vapor deposited layer with the etching solution, if desired, remove the resist using the photosensitive resin layer. By subtracting, the desired metal image can be obtained.

The etching solution used for etching the metal image forming material of the present invention may be either an acid or an alkali, and is appropriately selected depending on the type of metal deposited layer.

According to the present invention, the metal vapor deposition layer provided on the support has a continuously larger vapor deposition angle in the upper layer than in the lower layer, so that the surface of the metal vapor deposition layer becomes finely uneven. Second, the adhesion retention ability of the photosensitive resin layer provided thereon in a later step is improved, and the etching solution quickly penetrates into the exposed portion of the metal vapor deposited layer after image formation, resulting in extremely high etching speed.

Therefore, etching can be performed even with a not very strong etching solution. The reason why the etching time is short is because the resist is not immersed and there is less side etching, so it is related to the good processability of image development processing.
Images with good edge sharpness of corroded areas can be obtained, and even fine line images and halftone dot images can be processed with good reproducibility and high precision.

In addition, since the deposition angle is different between the upper layer and the lower layer of the metal vapor deposited layer deposited on the support, the surface reflectance is different on the front and back of the film. For example, even if the support surface has a metallic luster, the upper layer The surface is black or brown, so
Effective for distinguishing between the front and back sides of film-like metal image forming materials. Furthermore, it is also effective in preventing halation during exposure of the photosensitive resin layer.

The present invention will be illustrated below with reference to examples, but the embodiments of the present invention are not limited to these examples.

Example 1 A roll of polyethylene terephthalate film support in the form of a long strip and having a thickness of 100 μm was deposited at a deposition angle of 6 in a semi-continuous deposition apparatus.
The simulation was performed by heating aluminum placed in a carbon crucible under a vacuum of 5 x 10-' Torr and arranged so that 1 to on changes continuously from θ to 80 degrees. and the film is 4
A metal vapor deposition layer is formed using a semi-continuous vapor deposition apparatus that is conveyed at a speed of 0 m1. That is, aluminum is vacuum deposited on the support, and the deposition angle is set to θ from 01 to on so that the transmission density of the film is 35 on a Macbeth transmission densitometer.

to 80" to obtain an aluminum vapor deposited layer. Next, the following photosensitive resin composition was applied onto the film surface of this aluminum vapor deposited layer so that the film thickness after drying was 2.0 μm. The coated layer was coated with a whirler so as to be evenly coated, and dried for 5 minutes in a dryer at 100°C.

A sample of the photosensitive material thus obtained was pattern-exposed for 20 seconds through a halftone original using a bright room printer Up-6 (3KW Metal No. 1 Ride Lamp, Ueno Kagaku Wari). Immersed in IN sodium hydroxide water bath solution. At this time, at a liquid temperature of 25°C and an immersion time of 30 seconds, the aluminum evaporation layer in the unexposed area is completely removed, while the aluminum evaporation layer in the bright area is almost completely reversed in brightness from the original. Due to the effect of cooling, the side of the photosensitive layer exhibited black color, and an image with metallic luster on the side of the support was obtained. Furthermore, the sharpness of the halftone dot edges was also good, and sharp images were obtained with good reproducibility.

On the other hand, a sample having an aluminum vapor deposited layer with a transmission density of 3.5 was prepared by a single vapor deposition operation with the vapor deposition angle 01 to θn being only 00 in the variation table, a photosensitive resin layer was similarly provided, and the sample was exposed and developed. When etching was performed, it took a long time to develop (4 minutes), the sharpness of the halftone dot edges was poor, and the aluminum evaporated layer had a metallic luster, and the halftone dots became thicker due to the halation. Ta.

Example 2 In the same manner as in Example 1, the deposition angle 01~θn was 40°~
A film having the desired aluminum vapor deposited layer was obtained by operating the film continuously at 80°.

Next, AZ-13 was applied on the film surface of this aluminum vapor deposited layer.
50 (positive resist, photosensitive liquid manufactured by 8hi'play)
was coated with a whirler so that the film thickness after drying was 1.5μ, and dried for 5 minutes in a drying oven at 100°C.

The sample of the photosensitive material thus obtained was pattern-exposed for 45 seconds through a dot original using a bright room printer Up-5, and then developed with a developer for AZ-1360.
A resist of an image corresponding to the original was formed on the photosensitive resin layer.

This film was then heated to 0. When immersed in an IN sodium hydroxide aqueous solution, the resist was removed and the exposed portion of the aluminum evaporation layer was completely removed at a temperature of 25°C and an immersion time of 20 seconds, while the remaining aluminum evaporation layer of the resist was removed. It has been confirmed that there is almost complete correspondence between brightness and darkness.

[Brief explanation of drawings]

FIGS. 1 and 2 are schematic diagrams showing an example of a vacuum evaporation apparatus used to obtain the metal evaporation layer of the present invention. θ1 represents the initial deposition angle, and θn represents the final deposition angle. 1 is a support, 2 is an evaporation source, 3 is a vapor deposition sample, 4 is a shutter, 5 is a substrate holder, and 6 is a motor. 7 indicates a vacuum deposition container. Patent applicant: Roku Konishi Photo Industry Co., Ltd. Agent: Hiroaki Sakaguchi (and one other person) Figure 1 Figure 2 Figure 265~

Claims (1)

[Claims] At least one metal vapor deposited layer is provided on the support, the vapor deposition angle of which is continuously increasing with respect to the support, and a photosensitive resin layer is provided on the metal vapor deposition layer. Characteristic metal image forming materials.