• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The element consists of a base, a thin layer of metal or a metal compound, and a photosensitive layer. The latter contains a polymeric binder and a photosensitising material, selected from benzophenone, a quinone, diazonium or amido compound. Said layer also has the property of reducing the interface adhesion between the metal layer and the photosensitive layer after exposure. By means of this element it is possible, by exposing and peeling off the photosensitive layer, to produce an image pattern made of metal or a metal compound.
    公开号:SU948301A3
    申请号:SU772470055
    申请日:1977-04-14
    公开日:1982-07-30
    发明作者:Мориуа Такео；Ямагата Тоси
    申请人:Кимото Энд Ко,Лтд (Фирма)；
    IPC主号:
    专利说明:

    Union of Soviet Socialist Republics
    USSR State Committee for Inventions and Discoveries
    DESCRIPTION OF THE INVENTION
    TO PA TENT (61) Additional to the patent - (22) Declared 04/14/77 (21) 2470055 / 23-04 (23) Priority - (32) 04/14/76 (31) 51-42083 (33) Japan
    Published on July 30, 2018. Bulletin No. 28
    Date of publication of the doc description. about 7.82
    (..) 948301 (51) M. Cl
    G03 C 1/72 (53) UDC 771.5 (088.8)
    (72) The inventors
    Foreigners Takeo Moriua and Toshi Yamagata • (Japan) (71) Applicant
    Foreign Firm Kimoto End Co., Ltd. (Japan)
    I  --- l 1:, g · '·· l: - ··, .. .. i ! " P - : · ..l /. ·· ί
    (54) LIGHT-SENSITIVE MATERIAL FOR PREPARING IMAGES ί
    The invention relates to photosensitive materials intended for imaging and my-! Jet be used in chemical and photo-f $ graphic industry, polygraph graphy, advertisement, when receiving reticles in photolithography in the preparation of 'metal conductive patterns in electronics and electro-f Q nick and in other industries.
    “Photosensitive” is known “· an image-acquisition material consisting of a polyethylene terephthalate substrate, an intermediate layer <5 made of vinylidene chloride, a photopolymerizable layer including a film-forming component, a monomer, a photoinitiator, an inhibitor and a dye. As a binder of film-2 compound recommended methylene chloride as photoinitiator - anthraquinone. As a result of exposure of the known material, the irradiated portions of the photopolymerizable layer 25 decrease their adhesion to the substrate and can be removed due to the difference in adhesion compared to unirradiated portions. · As a result, the colored positive relief image Γι 1 remains on the substrate.
    The disadvantage of this material is that the image about developed by the dye in the remaining sections of the layer, has a low optical density and low contrast, which does not allow the use of such material, for example, as photomasks. In addition, the obtained colored polymer image has very low electrical conductivity, while in some areas of technology there is a need to obtain metal images with high electrical conductivity (for example, in the manufacture of radio circuits).
    The purpose of the invention is to obtain a metal image and increase the optical density and contrast of the image.
    This goal is achieved by the fact that in the photosensitive material for obtaining images, consisting of a substrate, an intermediate layer and a photopolymerizing layer, including a film-forming component and a photoinitiator, an intermediate
    the exact junction of the material is made of metal selected from the series of Αί, Ag, Ni, Cu sprayed in vacuum. or precipitated by electrolysis, a.
    in the photopolymerizable layer, Α фот is used as a film-forming component, while A 4 is used as a photoinitiator, or A ^ as a film-forming component, and B ^ _ as a photo-initiator, where Αι is polyvinyl chloride, a vinyl chloride copolymer and vinyl-, nilacetate, polyvinyl butyral, poly- "vinyl alcohol; B ^ - azo compound or diazonium salt; A <j is a triple vinyl chloride copolymer. vinyl acetate and maleic anhydride, * Β (χ is benzophenone, a quinone compound, an azo compound or a diazonium salt, and the ratio of components in the photopolymerizable layer is as follows, weight.h:
    Aj 10-50.
    B ^ 0.2-0.8 either
    And a .20
    0.8-2.0
    The material for obtaining images according to the invention includes a dense substrate with a soft surface, a thin intermediate layer of metal (hereinafter referred to as a metal layer) and a photopolymerizable layer containing a polymer film-forming substance and a photoinitiator, while the photosensitive layer is able to reduce 3:
    adhesion to each other of the surface of the metal layer and the photosensitive layer after exposure to light ·. Thus, when light is exposed to the material according to the invention through a mask of the desired pattern, the adhesion of the metal layer to the irradiated portion of the photopolymerized layer decreases, and this adhesive ability 45 does not change relative to the unirradiated portion. After removing the photosensitive layer, a metal pattern remains on the substrate corresponding to the irradiated region, but the unirradiated portion of the metal layer is removed. In this regard, it is essential, but important, that the adhesion of the binder to the metal layer be stronger than the adhesion of the metal layer to the substrate. 53
    The substrates used by the consents of the Invention include a number of substances capable of supporting a thin metal layer, such as a film-forming thermoplastic polymer product, glass or metal.
    Thermoplastic materials include various synthetic resins, for example, polyesters such as polyethylene terephthalate, polycarbonates, 65 polyolefins, such as polypropylene, PVC, polystyrene, polymethyl methacrylate and their copolymers, as well as cellulose derivatives, for example diacetyl cellulose, triacetyl cellulose, propyl cellulose and mixed. Other sheet products, such as paper, woven fabric and non-woven fabric, which have been coated with the above film-forming product, may also find application.
    Various additives (pigments, dyes and fillers) can be added to the substrate in order to impart opacity, color and te accept the font.
    A thin metal layer on the surface of the substrate can be applied, for example, by vacuum coating (sputtering and cathodic spraying), chemical deposition, or a combination of the latter with an electrolytic method. The thickness of the metal layer is preferably more than 10 mmk. The thinner layer does not have sufficient maximum optical density, so that the image obtained on the substrate is almost not visible. Although the upper limit of the thickness is not critical, as a rule, apply thicknesses up to 1000 mmk, preferably from 20 to 500 mmk. For special purposes, for example, to obtain printed circuit boards, a metal layer is used successfully, with a thickness of more than 1000 mmk.
    Among the various metals suitable for vacuum coating, zinc and aluminum are most preferred. Silver, copper and nickel are less preferred.
    The chemical deposition of metal can be carried out in the usual way by sensitizing the substrate and activating it, followed by immersion in an aqueous solution containing a metal salt and a reducing agent in order to deposit the entire metal layer on the substrate. Copper, nickel, silver are suitable for this.
    In total, the vacuum deposition method is more preferable with respect to electrolytic or chemical methods due to the possibility of using a wide range of metals, carrying out the reaction in a simple way with a high speed in the complete absence or only a small amount of metal waste. The photopolymerizable layer includes a film-forming component and a photoinitiator. Since the layer is removed from the substrate by printing, it is important that the film-forming substance has good film-forming ability with high strength of the obtained film, in addition, the material is preferably selected not blocking in order to avoid blocking stacked items during storage or working with them.
    Film-forming substances suitable for use according to the invention include the above synthetic resins.
    Typically, the film-forming component is used as a solution in an appropriate organic plant, which may include, for example, methyl ethyl ketone, toluene, cyclohexanone, methanol, ethanol, isopropanol, methyl cellosolve, ethyl cellosolve and cellosolve acetate.
    When choosing a solvent, make sure that the solvent dissolves the photoinitiator used, but does not dissolve the substrate and prevent it from swelling. 20
    If as a film-forming-. If polyvinyl alcohol is used, then its aqueous solution is suitable, PVC and polyurethane can also be used in the form of an emulsion or Persian diene. 25
    It is important that the appropriate combination of a photoinitiator with a film-forming substance is chosen in order to reduce sufficiently the adhesion of the surface of the metal layer to the irradiated portion of the photocomplete * merizable layer due to the action of light rays on the element. (The declared combinations of photoinitiators with film-forming components are indicated 35 above) .
    A solution in a solvent, an aqueous solution or an emulsion containing a photoinitiator and a film-forming component can be applied to a metal layer on a substrate by any coating technique, including the usual methods of reversible coating, engraving .: and rollers. The solids content of such a coating material ί varies depending on the coating method used and the amount of applied material, being usually ’but 5-30 wt.%. The coating material is applied in such an amount that the thickness of the dried photopolymerizing layer is 0.5-100 microns. Preferably 2-20 microns.
    Any dye and pigment can be added to the photopolymerizable layer; until they have a negative effect on the transparency and photosensitizing effect of the resulting photosensitive layer. In particular, a solid pigment can be added to give a matte layer suitable for applying drawing ink and printing ink. Such material is written without difficulty by hand or with a typewriter, obtaining the required pattern, which is reproduced in the form of a metal image on a substrate by the action of light rays on an element.
    If desired, the material can be equipped on top of the photopolymerizable layer with a carrier layer to increase the mechanical strength of the subsequently removed layer. Therefore, it is preferable to use a transparent layer (film-forming or thermoplastic polyester, polypropylene, polyamide, PVC or cellulose ester, transparent paper or paper saturated with synthetic resin).
    The material for obtaining images according to the invention is exposed to light rays through a desired pattern or raster, the photopolymerizing layer is removed, after which a metal image corresponding to the irradiated areas is obtained on the substrate, the source emitted is taken as the light source; radiation from ultraviolet to visible short wavelength range *; Thus, for example, the preferred light sources are a carbon arc lamp, a high pressure mercury arc lamp, or an argon fluorescent lamp, although tungsten, xenon arc, mercury arc, or metal halide lamps can also be used. The cheapest light source is the sun. Pro-, the duration of exposure to light on the image acquisition element depends on the specific composition of the photosensitive layer, the wavelength range of the light source and the distance from it. It has been found that, for example, 30 s is a satisfactory period for a 3.0 kW coal arc lamp at a distance of 50 cm.
    On ^ figure 1 presents the proposed material for imaging, cross section; figure 2 - the state of the photopolymerizable layer, taken after exposure to light rays with the aim of drawing a picture of the image from. metal on the substrate.
    (figure 1) to obtain includes a substrate 2 kneading 3 and photopolymers
    Material: images of the talizable layer 4 are exposed to light rays through a mask M having the desired negative pattern, while the adhesion of the surfaces of the exposed portion and the metal layer to each other is reduced. Thus, by removing the layer on the substrate, a metallic figure 5 is obtained. corresponding to the irradiated area, and on the photosensitive layer - metal figure 6, corresponding to the non-irradiated registration, in other words, on the spoon 65 receive a positive picture, a. 7 on the removed photosensitive negative image.
    The metal pattern thus obtained on a substrate is used for various purposes, for example, as intermediate or Secondary originals, lithographic plates, processing films, printed boards, original copies for projection and reproduction, electrodes for electroluminescence and markings.
    It was also found that the decrease in the adhesion of the layers of the irradiated region and the metal to each other can again be increased by heat treatment of the material. Therefore, after heating the Material to obtain images exposed to light rays, the entire photopolymerizing layer can be exposed to light again, followed by the removal of the photopolymerizing layer in order to obtain a reverse pattern from the metal layer on the substrate in accordance with the initial unirradiated portion. ' ''
    Care should be taken so that the temperature and the heating time do not destroy too much the unirradiated photoinitiator. thirty
    Thus it is possible to choose; either a negative-positive or positive-positive method of obtaining the desired metal pattern on the substrate.
    The invention is illustrated in particular on sheet material, however, material on a dry imaging system can also. be filled with any complex three-dimensional shape, for example, at the following steps: by applying a thin metal layer on a three-dimensional body; by application. a photosensitive composition on a metal layer and drying to obtain a photosensitive layer) on · by applying to the photosensitive layer the desired light-protective pattern, for example, black paint.
    The material thus obtained is exposed to light, and then the photopolymerizing layer is removed to obtain a metal pattern on a three-dimensional body. The product, in particular 1 , is suitable for reproduction in electroluminescent devices.
    Specific examples of obtaining pre-. The material offered is given below (11. Weight.hours corresponds to 1 g).
    Example 1. 20 parts by weight of a copolymer of 86% vinyl chloride, 13% vinyl acetate and 1% maleic anhydride (supplied by Union Carbide Corporation, New York, · USA, under the trademark Vinnylite VMOH), 0.8 parts by weight zinc chloride 4- (p-tolyl10, 8 z mercapto) -2,5-diethoxybenzo-l-diazo- ((supplied by Kabushiki Kaisha 1 Daito Kogyosho, Tokyo, Japan, dissolved under the trademark 'WM -1500)' is dissolved in 80 weight .h methyl methyl ketone to obtain a photopolymerizable composition containing 20.63% of solid material.
    On the surface of the layer of polyethylene terephthalate film thickness; 100 microns by spraying in a vacuum, an aluminum layer (100 microns) is applied, onto which a photopolymerizable composition is applied, and dried at 90 ° C to obtain a layer with a thickness of 5 microns. !
    On the photopolymerized layer impose the original negative, all together! exposed to light from the (carbon arc lamp, * hydrochloric ustanovlen- at a distance of 80 cm, protya-:. over 30 immediately after removal from the photopolymerizable layer gave sharp risunoknegativ aluminum on polyester film and RHS sunok-positive on the photosensitive film.
    The negative picture has a resolution of 72 l / mm, a density of Vphag3, 5, high contrast (γ = 20) and good reproducibility. The product is suitable for use as a film for reproduction.
    Example 2. Analogously to example 1, a photopolymerizable composition is obtained, except that 0.8 parts by weight of zinc chloride 4 ~ (p-methoxybenzoylamino) -2,5 diethoxybenzene-diazonium are used.
    A layer of zinc (80 μm) is applied by evaporation in vacuo on the surface of a film of poly * * ethylene terephthalate with a thickness of 12 μm 40, on which a photopolymerizable composition is applied, which is dried for 1 min at 90 ° C to form a layer of 9 μm.
    The material thus obtained is exposed to light, as in Example 1, to obtain a sharp zinc negative pattern on a substrate, and a positive pattern on a photosensitive layer.
    Example 3. 29 parts by weight {used in example 1 copolymer and 2.0 parts by weight 1,4-naphthoquinone rast. steal in a mixture of 40 parts by weight methyl ethyl ketone, 35 parts by weight toluene and 5 parts by weight cyclohexanone, obtaining a 21.57% photosensitive composition.
    A 75 μm thick diethyl cellulose film was sprayed in a vacuum and a layer of aluminum (50 μm) was applied, onto which a photopolymerizable compound was applied, which was dried for 2 min at 90 ° C, obtaining a layer of 10 μm.
    The original positive is placed on the photosensitive layer, all of which are exposed to light with the approximate 35 0 0 opinion of the Ricopy 1500 electrographic machine (supplied by Rice Co., Ltd., Tokyo-Japan) equipped with a 1500 W mercury arc lamp. Duration of printing Yu on a scale,
    By removing the photosensitive layer I, a sharp aluminum negative pattern is obtained on the substrate.
    P-R and mer 4-20 weight.h. a copolymer of 87% vinyl chloride and 13% vinyl acetate (supplied under the trademark Vinylite VYHH!) and 0.8 parts by weight 4- (p-tolyl mercapto) 2,5-diethoxybeneol-diazo'onium zinc chloride is dissolved in a mixture of 40 parts by weight methyl ethyl ketone and 40 parts by weight toluene * receiving : 20.63% photopolymerization pump ..> tav. . .
    The photopolymerizable composition is applied to a silver layer (50 μm / ’on a · glass plate and dried with hot air at 9 0 ° C for 2 min, obtaining a photopolymerizable layer of 9 microns.
    Analogously to example 1, the resulting material is exposed to light through the original positive, receiving a 'silver negative pattern on a glass plate, previously removing the photosensitive layer.
    P r and. Mer 5. A film of 100 microns thick polyethylene terephthalate is immersed in a sensitizing bath for 3 minutes, rinsed thoroughly with water, then immersed in an activating bath for 3 min and thoroughly washed with running water, finally immersed in a coating bath for 35 min. . getting a layer with a thickness of 50 mmk.
    Sensitizing bath, parts by weight Sncln10
    NS140
    N g 01000
    Temperature, ° C 25 Activating bath, parts by weight
    PdCla0.5
    HC1 3 5
    H ^ O1000
    Temperature, ° C 23 Bathroom for coating, weight, h.
    i
    40 Sodium Citrate Hypophosphate 24 sodium 20 Sodium Acetate 14 Ammonium chlorideniy 5 UFO Up to 100 Photopolymerizable Composition
    obtained in example 2 is applied to the obtained layer. The material thus obtained is exposed to light using an original positive and the machine of Example 3 (value on a scale of 5). Get a sharp negative pattern on a polyester film to remove the photosensitive layer.
    Example 6. 20 parts by weight copolymer 1 and 2 parts by weight benzophenone. dissolved in 80 parts by weight methyl ethyl ketone, obtaining a photopolymerizable composition. 'By spraying in a vacuum, an aluminum layer (100 μm) is applied to one side of a polyethylene terephthalate film (100 microns), and a mixture of 10 parts by weight is applied to the other side. yellow fluorescent pigment, 5 parts by weight linear polyester resin, 38 parts by weight methyl ethyl ketone and 15 parts by weight cyclohexanone, then dried and get a yellow coating with a thickness of 10 microns.
    . The photopolymerizable composition is applied 1 to the aluminum layer and dried ~ according to Example 2. ·
    A 2Q Zivit original is applied to the coating and exposed to light using the machine of Example 3 (scale value 2).
    Upon removal of the coating, an aluminum mini-negative pattern is obtained in silver on a yellow fluorescence film. The product is thus suitable for advertising purposes.
    • Prim er 7. On one side of a polyethylene terephthalate film (188 microns) is applied in the aluminum layer 30 400 nm vakuumnymvyparivaniem, then coated fotopolimerieuyuschimsya composition of Example 1.
    A white raster-negative (300 strokes / inch) is placed on the photopolymerizing layer, all together then exposed to light using a · pneumatic printing device equipped with a 3 kW carbon arc lamp for 30 s at a distance of 30 cm. Then the photopolymerizing layer is removed to obtain aluminum raster — positive on the film.
    The product is suitable for use as a transparent electrode of an elastic electroluminescent sheet material ..
    Example 8. By mixing
    Z.ch. copolymer example
    1.1 parts by weight g ^ -di ^ '- airbenzene) · cyclohexanone, 40 parts by weight methyl ethyl ketone and 40 parts by weight toluene receive a 20.75% photopolymerization composition. On one side of the polyethylene terephthalate film: (100 microns), a layer of aluminum (100 microns) is applied by vacuum evaporation, onto which a photoforming composition is applied, followed by drying for 1 min at 90 ° C to obtain coatings with a thickness of 5 microns.
    Solution 15 parts by weight acetylbutylcellulose in 60 parts by weight toluene and 25 parts by weight of methanol are applied on top and dried for 2 minutes at 90 ° C in order to form a reinforcing 4: 15 micron thick layer.
    The material is exposed to light along with the original positive, using the machine of example 3 (value on a scale of 1.5). After removal of the coatings, an aluminum negative pattern on the polyester film 5 and a positive pattern on the photosensitive layer are obtained.
    P r and. MER · 9. Japanese silk paper (supplied by Mitsubishi Paper Mills Ltd., Tokyo, Japan, under 10 trademark Kyokuryu) with an aluminum and photopolymerizable layer according to Example 8, is dried at 60 ° C. for 3 minutes.
    On a typewriter they write letters 15 on the side covered with Japanese silk paper, then they are exposed to light rays - using; machines of example 3 for 30 s. By removing the photosensitive layer, an aluminum negative pattern is printed on typewriter letters on polyester film.
    Example 10. A photosensitive composition is obtained by dissolving 20 parts by weight. polyvinyl alcohol (supplied by Toa Gosei Chemical, Chemical Industry Co; Tokyo, Japan, under the trademark NK-20) and 0.8 parts by weight. 4- (p-tolyl mercapto) - .. -2,5-diethoxybenzene-diazonium-tet ”30 * rafluoroborate in 180 parts by weight H ^ O at a solids content of 10.36%.
    Aluminum is applied with a thickness of 100 microns by vacuum deposition on a polypropylene film of a biaxial orientation with a thickness of 75 microns. The photopolymerizable layer is deposited on an aluminum layer and dried with hot air at 100 ° С for T min, obtaining a photopolymerizable layer 3 μm thick. 40
    An original positive is applied to the photopolymerizable layer, all together exposing the light from a xenon arc lamp with a power of ^ ^ kW installed at a distance of 100 cm, 45 45 for 3 minutes. The photopolymerizable layer is removed to obtain an aluminum negative pattern on the film and a positive pattern on the photosensitive CJIOG "
    Etc. and measures 11. On one side of a polyethylene terephthalate film E 50 microns thick, pigmented with carbon black, coated aluminum layer (70 nm) by sputtering in vacuum on the other side - acrylic adge- 55 zyonny agent sensitive to pressure (supplied by Nippon Sagqp. de Industries Co., Ltd., Tokyo, Japan, under the trademark Nissetsu PEIISA) 30 microns thick, a sheet of removable paper is applied on top of 60.
    The photosensitive composition according to Example 1 is applied to the aluminum layer, / then it is heated with hot air at 90 6 C for 1 min, yielding 65 photopolymerizable layers with a THICKNESS of 5 microns.
    An original negative is applied to the material obtained in this way, all together exposing them to light. Similar to Example 1. By removing the photosensitive layer on black! the film receives a positive picture of se-: silver shade. The product can be attached to the desired location as a mark or label to remove the removable sheet of paper.
    Example 12. A photopolymerizable composition containing 1U, 18% solids, is obtained by dissolving 10 parts by weight. polyvinyl butyral containing 3% acetyl groups, 65 + 3% butyral groups and 35 ± 5% hydroxyl groups, and 0.2 parts by weight of 4- (p-tolyl mercapto) -2,5-diethoxybenzene-diazonium zinc chloride in a mixture of 45 weight parts methyl ethyl ketone, 27 parts by weight of Ch1 of toluene and 18 parts by weight of cyclohexanone.
    On a polyethylene terephthalate film (100 μm), an alumininka layer (100 μm) is applied by vacuum evaporation, onto which a photopolymerizable composition is applied, then dried for 1 min at 0 ° C, {obtaining a photopolymerizable layer! 5 microns thick. ί 'using the machine of Example 3 (value on a scale of 5), the material is exposed to light along with the original positive, then the photopolymerizable layer is removed and an aluminum negative pattern is obtained on the film. The product ·· is suitable for lithography as a plate.
    Example 13. Photopolymerizable composition is obtained by dissolving 0.4 wt.h. sodium salt of 1,2-diazonaphthol-5-sulfonic acid in 50 parts by weight PVC emulsions (supplied by Nisshin 1 Chemical Industries Co., Ltd, Tokyo, Japan, under the trademark Vinyblane 320).
    On a polyethylene terephthalate film (100 microns), a layer of aluminum with a thickness is applied by vacuum evaporation. 100 μm, then a photopolymerizable layer is applied and dried for 30 s at 100 ° C to obtain a layer 3 μm thick.
    On this layer, using an acrylic adhesive layer (supplied by Nippon Carbide Influctries Co., Ltd, under the trademark ”Nissetsu; PE115A), 12 μm polyethylene terephthalate film was applied to obtain image material.
    Analogously to example 1, the material is exposed to light, then the photopolymerizing layer is removed, receiving a negative picture on the film.
    Since the photopolymerizable layer is reinforced with a layered film, it has increased mechanical, strength, and the operation of removing Photo13 of the polymerized layer is not difficult. The resulting element is suitable for use in large-sized performance, the resulting positive pattern on the photosensitive layer is used for various purposes.
    权利要求:
    Claims (2)
    [1]
    The invention relates to photosensitive materials intended for image acquisition and can be used in the chemical photo graphic industry, printing, advertising, in photographic prints in photolithography, in the production of metallic electrically conductive patterns in radio engineering and electronics, and in other parts of the technique. .  A photosensitive imaging material is known, consisting of a polyethylene terephthalate substrate, an intermediate layer made of vinylidene chloride, a photopolymerizable layer comprising a film-forming component, a monomer, a photoinitiator, an inhibitor and a dye.  Methylene chloride is recommended as the film-forming compound, and anthraquinone as the photoinitiator.  As a result of exposure of a known material, the irradiated areas of the photopolymerizable layer reduce their adhesion to the substrate and can be removed due to the difference in adhesion compared to the unirradiated areas.  As a result, a colored positive relief image of Til remains on the substrate. The disadvantage of this material is that the image produced by the dye in the remaining areas of the layer has a low optical density and low contrast, which prevents the use of such material, for example, as photo masks.  In addition, the obtained dyed polymer image has a very low electrical conductivity, while in some areas of technology there is a need to obtain metallic images with high electrical conductivity (for example, in the manufacture of radio circuits).  The purpose of the invention is to obtain a metallic image and to increase the optical density and contrast of the image.  The goal is achieved by the fact that in a photosensitive material for obtaining images consisting of a substrate, an intermediate layer and a photopolymerizable layer comprising a film-forming component and a photoinitiator, the intermediate layer of material is made of a metal selected from the row A1, Zn Ag, Ni , Cu deposited in a vacuum.  or besieged by electrolysis / a.  in the photopolymerizable layer, A is used as the film-forming component, while B is used as the photoinitiator, or Arj is used as the photoinitiator component, and where At is polyvinyl (chloride, copolymer of vinyl chloride and vinyl acetate, polyvinyl butyl, poly vinyl alcohol; B - azo compound or diazonium salt; Aij - ternary polymer of vinyl chloride, vinyl acetate and maleic anhydride, Bfj - benzophenone, quinone compound, azo compound or diazonium salt, with the ratio of the components s in the photopolymerizable layer is the following, weight. h: A 10-50.  0.2-0.8 AO, 20 VO, 8-2, O The material for imaging according to the invention includes a dense substrate with a soft surface, a thin intermediate layer of metal (hereinafter referred to as the metal layer) and a photopolymerizable layer containing polymeric film-forming substance and photoinitiator, while the photosensitive layer is able to reduce the adhesion to each other of the surface of the metal layer and the photosensitive layer after exposure to light.  Thus, when light is exposed to a material according to the invention through a mask of the desired, metal adhesion pattern.  The layer to the irradiated area of the photopolymer of the merit layer is reduced, wherein this adhesive ability does not change with respect to the non-irradiated area.  After removing the photosensitive layer, a metal pattern corresponding to the irradiated area remains on the substrate, but the non-irradiated area of the metal layer is removed.  In this connection, it is essential that the adhesion of the binder to the metal layer is stronger than the adhesion of the metal layer to the substrate. The substrates used according to the invention include a number of substances capable of carrying a thin metal layer, such as as a film-forming thermoplastic polymer product, glass or metal.  To thermoplastic materials OTHOOfl with various synthetic resins,.  for example, polyesters such as polyethylene terephthalate, polycarbonates, polyolefins such as polypropylene, PVC, polystyrene, polymethyl methacrylate and their copolymers, as well as cellulose derivatives, such as diacetylcellulose, triacetylcellulose, propylcellulose, and mixed cellulose esters.  Other sheet products, such as paper, woven fabric and nonwoven fabric that have been coated with the above film-forming product, can also be used. Various additives (pigments, dyes and fillers) can be added to the substrate in order to give opacity, coloring and ability take font  A thin metal layer on the surface of a substrate can be applied, for example, by vacuum coating (sputtering and cathode spraying), chemical or hse coating by combining the latter with an electrolytic method.  The thickness of the metal layer is preferably greater than 10 microns.  The thinner layer does not possess a sufficient maximum optical density, so that the image obtained on the substrate is almost invisible.  Although the upper limit of the thickness is not critical, as a rule, thicknesses of up to 1000 mmk, preferably from 20 to 500 mmk, are used.  For specific purposes, such as for the production of printed circuit boards, a metal layer with a thickness of more than 1000 mmk is successfully used.  Among the various metals suitable for vacuum coating, zinc and aluminum are most preferred. Silver, copper and nickel are less preferred.  The chemical deposition of metal can be carried out in the usual way by sensitizing the substrate and activating, followed by immersion in an aqueous solution containing a metal salt and a reducing agent in order to deposit the entire metal layer on the substrate.  For this, copper, nickel and silver are suitable.  In total, the vacuum deposition method is more preferable to electrolytic or chemical methods due to the possibility of using a wide range of metals, conducting the reaction in a simple manner at high speed with no or little metal waste, the Photopolymerizable layer includes film-forming component and photoinitiator.  Since the layer is removed from the substrate upon printing, it is desirable that the film-forming substance has a good film-forming ability with high strength of the film obtained, moreover, the material is preferably chosen not to block in order to avoid blocking the stacked elements during storage or handling.  Filtered materials suitable for use in accordance with the invention include the above synthetic resins.  As a rule, the film-forming component is used in the form of a solution in an appropriate organic solvent, to which, for example, methyl ethyl ketone, toluene, cyclohexanone, methanol, ethyl salt, isopropanol, methyl delozolv, ethyl cellosolve, and cellosolve acetate can be referred.  When choosing a solvent, it is necessary to ensure that the solvent dissolves the photoinitiator used but does not dissolve the substrate and prevents it from swelling.  If polyvinyl alcohol is used as the film image for the substance, then its aqueous solution is suitable.  PVC and polyurethane can also be used in the form of an emulsion or the Persia line.  It is important that the proper combination of photoinitiator with film-forming substance is chosen in order to sufficiently reduce the surface of the metal layer to the irradiated TOT of photo-polarizing layer due to the effect of light on the element, (Determined combinations of photoinitiators with curved spm) are indicated by above).  The solvent solution, aqueous solution or emulsion containing a photo-initiator and film-forming component can be applied to the metal layer on the substrate with any coating technique, including the usual methods of reversible coating, engraving and rollers.  The solids content of such a coating material varies depending on the applied coating method and the amount of material applied, it was about 5-30 wt. %  The coating material is worn in such an amount that the thickness of the dried photopolymerizable layer is 0.5-100 microns.  Preferably 2-20 microns.  Any dye and pigment can be added to the photopolymerisation layer until they have a negative effect on the transparency and photosensitizing effect of the photosensitive layer. In particular, a solid pigment can be added that gives a matte layer suitable for applying drawing ink and printing ink.  This material is written without difficulty by hand or with a typewriter, obtaining the required pattern, which is reproduced as a metallic image on the substrate after exposure to an element of light rays.  If desired, the material can be equipped over the photopolymerizable layer with a carrier layer to increase the mechanical strength of the layer to be removed.  Therefore, it is preferable to use a transparent layer (film-forming or thermoplastic polyester, polypropylene, polyamide, PVC or polyester pulp, transparent paper or synthetic resin-saturated paper).  The material for obtaining images according to the invention is exposed to light rays through a desired pattern or raster, the photopolymerization layer is removed, after which an image of a metal corresponding to the irradiated areas is obtained on the substrate.  As a light source, the source is emitting; Ultraviolet to visible short-range beams. So I for example, the preferred light sources are coal arc lamp, high pressure mercury arc lamp or fluorescent argon lamp, although tungsten, xenon arc, mercury meadow or metal halogen lamps can also be used.  The cheapest source of light is the sun.  The duration of exposure of the light to an element for obtaining images depends on the specific composition of the photosensitive layer, the wavelength range of the light source and the distance from it.  For example, 30 seconds was found to be satisfactory for a coal arc lamp of 3.0 kW at a distance of 50 cm.  FIG. 1 presents the proposed material for imaging, a cross section; in fig. 2 - the state of the photopolymer of the zegos layer, removed after exposure to the light rays in order to obtain an image or image from. metal on the substrate.  Material 1 Sfig. 1) to obtain; images include a substrate 2 a metal layer 3 and a photopolymerizable layer 4.  The material is exposed to light rays through the mask M, which has the desired negative pattern, while the adhesion of the surfaces of the exposed area and the metal layer to each other is reduced.  Thus, by removing the layer on the substrate, a metal pattern 5 corresponding to the irradiated deposit is obtained, and on the photosensitive layer, a metal pattern b corresponding to the unirradiated strip, in other words, a positive pattern is obtained on the substrate, and a clear negative pattern is obtained on the photosensitive layer.  The metal pattern thus obtained on the substrate is used for a variety of purposes, for example, as intermediate or secondary materials, lithographic plates, films for processing, printed circuit boards,. original copies for design and reproduction / electrodes for electro-luminescence and labeling.  It was also found that the adherence of the layers of the irradiated area and the metal to each other can be enhanced again by thermal transfer of the material.  Therefore, after the material is heated to obtain images, exposed to light rays, the entire photopolymerisation layer can again be exposed to light, followed by removing the photoField tseps layer in order to obtain a ghost pattern of the 1st layer metal on the substrate in accordance with the Initial non-irradiated area.    .    .   Care should be taken to ensure that the temperature and the heating period do not destroy the irradiated photoinitizer when it is used. ; Thus, it is possible for B1d1 to take either a negative-positive or a positive-positive method of production. required metal pattern on the substrate.  The invention is illustrated, in particular, on a sheet material, however the material on a dry system for imaging is also possible.  to be filled with any complex three-dimensional shape, for example, on the following steps: applying a thin metal layer on a three-dimensional body; by applying a photosensitive composition to the metal layer and drying to obtain a photosensitive layer) by applying the desired light-cytic pattern on the photosensitive layer, for example, black ink.  The material thus obtained is exposed to light, then the photopolymerizable layer is removed to obtain a metallic pattern on the three-dimensional body.  The product, in particular, is suitable for reproduction in electroline-intensity devices.  Specific examples of the preparation of jjaraeMoro material are given below W. . Weight. h  corresponds to 1 g).  Example 1  20 wt. Copolymer: 86% vinyl chloride, 13% vinyl acetate and 1% maleic anhydride (supplied by Union Carbide Corporation, New York, London, under the trademark Vinnylite VMOH), 0.8 weight. h  zinc chloride 4- (p-tolyl | mercapto; -2,5-diztoksibenzbl-diazo-, nk (supplied by Kabushiki Kaisha Daito Kogyosho, Tokyo, Japan, under the trademark Ж / W-1500 / dissolved in 80 wt. of methyl methyl ketone to obtain a photopolymerized composition, containing 20.63% of solid material.  On the surface of a layer of polystyrene film with a thickness; 100 microns by spraying in vacuum, aluminum slides are deposited (100 microns, onto which photopolymerization composition is applied, and dried at 90 ° C to obtain a layer thickness of 5 microns.   On the photopolymer iNs layer, the ya / lagues are origi: al-negatus, all together subjected to the light from the carbon arc lamp, set at a distance of 80 cm, on the prot; a life of 30 s.  After the immediate removal of the photoplasticizing layer, a sharp aluminum drawing of a negative polyester film and a rhythm of SUN-positive on the photosensitive film are obtained.  . .  Negative drawing has a resolution of 72 l / mm, a density of 1 x 3, 5, a high neutrality () and good reproducibility.  The product is suitable for use as a film for reproduction. unit  Example 2 Analogously to Example 1, a photopolymerizing compound is obtained, except that 0.8 weight% is used. h zinc chloride 4 (g-methoxybenzoylamino) -2,5distoxybenzene diazonium.  On the surface of a poly (ethylene terephthalate) record with a thickness of 12 microns. Evaporation in vacuum of a layer of zinc (80 mmk), onto which a photopolymerizable composition is applied, which is dried for 1 minute at 90 ° C to form a layer of 9 microns.  The material thus obtained is exposed to light in the same way as Example 1, producing a sharp zinc drawing negative on the substrate, and a positive image on the photosensitive layer.  Example 3  29 wt. h  G4) The copolymer referred to in Example 1 and 2.0 wt. h  1,4-yaftoquinone plant-rooted in a mixture of 40 wt. h  methyl ethyl ketone, 35 wt. h  toluene and 5 wt. h  cyclohexanone, giving a 21.57% photosensitive composition.  A layer of aluminum (50 mmk), onto which photopolymerizable is applied, is applied onto a film of diethylcellulose of 75 microns in length in a vacuum. the composition, which is dried for 2 minutes at, obtaining a layer of 10 microns.  The positive original is placed on the photosensitive layer, all of which are exposed to light using: Ricopy 1500 (supplied by Rice Co., Ltd., Tokyo Japan / equipped with a 1500 W mercury arc lamp with a print duration of 10 on the scales After removing the photosensitive The layer gets a sharp aluminum negative pattern on the substrate.  Ave 4.  20 wt. h  copoly with 87% vinyl chloride and 13% vinyl acetate (supplied by the shopping center Zzoak Vinylite VYHH) and 0.8 wt. h  zinc 4-jri-tolylmercapto 2,5-di-9to4ssiv hl, eol-d1d3n is dissolved in a mixture of 40 wt. h  label ethylketora 9 40 wt. h  t oluol ,.  getting 20,. Photopolymerizable sostav, Photopolymerizable composition is on a silver layer (, 50 mmk / H4-glass plate and dried with hot air at: 90 ° С for 2 min, obtaining a photopolymerization 1C1ai layer of 9 microns.  Alternatively to Example 1, the material obtained is exposed to light through the original positive, obtaining a silver negative pattern on the glass plate, after removing the photosensitive layer.  And p and.  MER 5.  A 100 mec film of polyethylene terephthalate is immersed in a sensitized bath for 3 minutes, ptsimno prymivayut water, then immersed in an activating bath for 3 min and thoroughly batbt with running water, finally immersed in a bath for applying coatings for 2 min.  receiving a layer thickness of 50 MMK.  Sensitizing bath, weight. h  SnCln 10 HC140 HijO1000 Temperature, C 25 Activating bath, wt. h  PdClft0,5 HC1 5 tttlO1000 Temperature, 23 Application bath, weight, h.  Sodium citrate 24 Sodium hypophosphate 20 Sodium acetate 14 Ammonium chloride 5 100.  The photopolymerisation composition obtained in Example 2 is applied to the resulting layer.  The material thus obtained is exposed to light using the original positive and Example 3 (value on a scale of 5).  A sharp rine-negative on a polyester film is obtained by removing the photosensitive layer, Example 6.  20 wt. h, copolymer 1 and 2 wt. h  benzophenone. dissolved in 80 wt. h  Methyl ethyl ketone, obtaining a photopolymerizable composition.  By vacuum deposition on one side of a polyethylene terephthalate film (100 microns), an aluminum alloy was deposited (, 100 mmk /, and a mixture of 10 wt.%) On the other side. h  yellow flowrescent-; his pigment, 5 wt. h  linear polyester resin, 38 wt. h  methyl ethyl ketone and 15 wt. h  cyclohexanone, then dried and get a yellow coating thickness of 10 qc.  The curing composition is applied to the aluminum layer and dried by example.
    [2]
    2. Original-positive coating is applied to the coating and exposed to light using the machine of Example 3 (scale 2). By removing the coating, alumina rice is obtained: ok negative in silver on the yellow fluorescence. The product is suitable for promotional purposes. Example 7. On one side of a polyethylene terephthalate film (18188 micron), a 400 μm layer of aluminum is deposited by vacuum evaporation, a grid is coated with photopolymerization and dyeing according to Example 1. A white raster-negative (300 strokes / inch) is placed on the photopolymerizing layer, then all together are subjected to impact using a pneumatic printing device equipped with a coal; E {3 kW lamp for 30 s at a distance of 30 cm. The photopolymerizable layer is then removed to obtain an aluminum-screen-positive raster on the film. The product is suitable for use as a transparent electrode of an elastic electroluminescent sheet material ... Example 8. By mixing. H. copolymer of example 1.1 weight.h. 2,6-di (4-azidobenzal) cyclohexanone, 40 weight.h. methyl ethyl ketone and 40 weight.h. toluene get 20,75% photopolymerizable composition. On one side, polyethylene terephthalate film i (100 microns / by vacuum evaporation is applied a layer of aluminum (100 mmk), on which the 1st is deposited a photopolymerizing composition followed by drying for 1 minute while obtaining coatings 5 microns thick. Solution 15 weight Acetylbutylcellulose in 60 parts by weight of toluene and 25 parts by weight of methanol are applied from above and dried for 2 minutes at 90 ° C in order to form a 15 μm thick reinforcing layer.The material is exposed to light, together with the original -positive machine of example 3 (value on the scale of 1.5K YET Aluminum pattern negative on polyester film and pattern positive on the photosensitive layer.Materi-9o Japanese silk paper is supplied by Mitsubishi Paper Mills Ltd., Tokyo, Japan, Example 8 is dried at 60 ° C for 3 minutes Letters are written on a typewriter on the side covered with silk paper, then subjected to “Amplification of light rays using the machine of Example 3 for 30 s. On removal of the photosensitive layer, aluminum negative pattern of typewritten letters on polyester film is burnt. Example 1 &amp; Photosensitive composition is obtained by dissolving 20 weight parts. polyvinyl alcohol (supplied -Toa G6s.ei Chemicai, Chemical Industry Okio, Japan, under the trademark NK-20) and 0.8 parts by weight. 4- (p-tolylmercapto) -g -2,5-distox benzene-diazonium-tetrafluoroborate in iSO wt.h. pk. solids content of 10.36%. Aluminum is deposited with a thickness of 100 microns by vacuum deposition on a polypropylene film of biaxial orientation with a thickness of 75 microns. The photopolymerizable layer is applied onto the aluminum layer and dried with hot air at 100 ° C for 1 min. To obtain a photopolymerizable layer of 3 microns. A positive pattern is applied to the photopolymerizable layer, all together under the influence of light from a xenor arc lamp with a power of 2 kW installed on the distance 100 cm for 3 mic. The photopolymerizable layer is removed to obtain aluminum. Negative drawing on film and drawing positive on photosensitive layer. EXAMPLE C. On one side of a 50 µm thick polyethylene terephthalate film pigmented with soot, a layer of alynin 170 mmk was applied by spraying in vacuum, on the other side an acrylic adhesive sensitive to pressure (supplied by Nippon Cagf. 4e Industries Co., Ltd., Tokyo, Japan, under the trademark NissetSU PEIISA (30 microns) thick, a sheet of removable paper is placed on top. A photosensitive composition as in example 1 is applied to the aluminum layer, / then heated with hot air for 1 minute to obtain a photopolymerized film with a thickness. 5 microns. On the material thus obtained impose the original-negative, all together exposed to light; as in example 1. After removing: the photosensitive layer on the black I film, a positive silver tint is obtained. The product can be Ricked to a desired place as a label or tag after removing the removable bui1agi sheet. Example 12: A photopolymerisable composition containing 1U, 18% solids is obtained by dissolving 10 parts by weight. polyvinyl butyral containing 3% acetyl groups, 65 ± 3% butyral groups and 35 ± .5% hydroxyl groups, and 0.2 weight parts. zinc chloride 4- (ti -tolylmercapto) 2,5-diethoxybenzene-gdiazoni in a mixture of 45 parts by weight methyl ethyl ketone, 27 weight parts. toluene and 18 weight parts. cyclohexanone. A polyethylene terephthalate field: zh (.100 microns) was vacuum evaporated and an aluminic layer (mmk) was put on which photopolymerization composition was applied, then dried for 1 min. To obtain a 5 micron thick photopolymer. (Using the machine. According to example 3 (value on a scale of 5), the material is exposed to light together with the positive original, then the photopolymerization layer is removed and an aluketnius-negative image is obtained on the film. The product is suitable dL lithographer1 and as a plate. 13. Photopolymerouc Kys composition is obtained by dissolving (if 4 parts by weight from sodium salt of 1,2-diazonaphl-5-sulfonic acid in 50 parts of PVC emulsion (supplied by Nisshin i Chemical Industries Co, Ltd, Tokyo, Japan, Under the trademark Viny Co 320) .On the polystyrene terephthalate film (100 microns) vacuum By evaporation, a layer of AGNI is applied, with a thickness of 103 mmk, then a photopolymerizable1 layer is applied and dried for 30 s, obtaining a layer of 3 µ o thick. On this layer using an acrylic adhesive layer (supplied by Nippon Carbide InBuctries Co., Ltd, under the 12 µl of polyethylene terephthalate film was applied with the Nissetsu; PEll5A | film to form an image material. Similarly to Example 1, the material was exposed to light, then the photopolymerization layer was removed to obtain a negative-pattern film. Because the photopolymerizable layer is reinforced with a laminated film, it has an increased mechanical strength and the removal operation of the Photopolymerizable layer presents no difficulties. The resulting element is suitable for use in a large-sized design, the resulting positive picture on the photosensitive layer is used for various purposes. Formula of the invention A photosensitive material for imaging, consisting of a substrate, an intermediate layer and a photopolymerizable layer including a film-forming component and a photoinitiator, distinguishing and the fact that, in order to obtain a metal image density and increase the optical density and contrast of the image, the intermediate layer of the material The shaft is made of a metal selected from A1, Zn, Ag, Ni, Cu deposited in vacuum or precipitated by electrolysis, and in the photopolymerizing layer it contains L as a film-forming component, while it contains B as a photoinitiator. film-forming component it contains Ag, and as a photoinitiator Bij, where A is polyvinyl chloride, a copolymer of vinyl chloride and vinyl acetate, polyvinyl butyral, polyvinyl alcohol; azo compound or diazon salt; AO is a ternary copolymer of vinyl oride, vinyl acetate and maleic anhydride; vg-benzophenone, quinone compound, azo compound, or diazonium salt, and the ratio of xc to n in the photopolymerizable layer is as follows, parts by weight 10-50 0.2-0.8 20 0.8-2.0 Sources of information taken into account during the examination 1. Patent QUA W 3060023, class 96-28, published. 1962 (prototype).
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    同族专利:
    公开号 | 公开日
    CA1094377A|1981-01-27|
    DE2716422C2|1987-10-01|
    FR2371706B1|1980-04-25|
    JPS5613305B2|1981-03-27|
    CH628160A5|1982-02-15|
    NL185425C|1990-04-02|
    AU1946676A|1978-06-29|
    BE853618A|1977-08-01|
    GB1563010A|1980-03-19|
    NL7704083A|1977-10-18|
    FR2371706A1|1978-06-16|
    NL185425B|1989-11-01|
    DE2716422A1|1977-11-03|
    IT1094789B|1985-08-02|
    DD130507A5|1978-04-05|
    SE435214B|1984-09-10|
    JPS52126220A|1977-10-22|
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    JP2009032912A|2007-07-27|2009-02-12|Sony Corp|Method of manufacturing semiconductor device, and method of manufacturing organic light-emitting device|
    CN105829970B|2013-10-30|2020-07-14|荷兰应用自然科学研究组织Tno|Substrate comprising a circuit pattern, method and system for providing a substrate comprising a circuit pattern|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP4208376A|JPS5613305B2|1976-04-14|1976-04-14|
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