JP2007086152A - Photosensitive resin laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high-quality photosensitive resin laminate held between an IR absorbing metal layer and a support made of metal. <P>SOLUTION: The photosensitive resin laminate comprises at least a support, a photosensitive resin layer, a non IR-sensitive polymer resin layer, an IR ablation layer, and a cover film, and the laminate is water developable, wherein the support is made of metal and the non IR-sensitive polymer resin layer has the thickness of 0.1 m to less than 2.0 μm. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a photosensitive resin laminate having an IR ablation layer used when a relief printing plate or a relief plate is produced by a computer plate making technique.

  In recent years, computer plate making technology (computer-to-plate (CTP) technology), also known as digital image forming technology, has become very common in the fields of letterpress and flexographic printing. In CTP technology, a photographic mask (also referred to as a photomask or negative film) conventionally used to cover a non-polymerized region of a photosensitive printing plate replaces a mask that is formed and integrated in the printing plate. It has been. There are two technologies in the market for obtaining such an integrated mask. One is a method of printing a mask with an ink jet printer on a photosensitive printing original plate, and the other is substantially opaque to ultraviolet rays (that is, substantially not passing ultraviolet rays) on the photosensitive layer, and A layer that can be ablated by irradiation with an IR laser (this layer is generally called an “IR ablation layer” or an “infrared ablation layer”, and is referred to as an “IR ablation layer” in this specification. And a mask is formed by forming an image on the layer with an IR laser. By using these techniques, an image (mask) is directly formed on the plate, and in the next step, ultraviolet rays are irradiated through the image (mask) to reach the plate making.

  By the way, in the photosensitive printing original plate having the IR ablation layer, a composition containing a large amount of carbon black in a polymer binder is generally used for the IR ablation layer. In general, a cover film is provided on the IR ablation layer to protect the IR ablation layer when the original is stored or handled. This cover film is provided before the IR laser irradiation or after the IR laser irradiation. (Usually after main exposure and before development). However, after IR ablation, the main exposure with ultraviolet rays is performed, and when developing with the developer, the carbon black is transferred to the developer and the developer is likely to become dirty, and the developer must be replaced for each plate making operation. This has caused an increase in printing costs.

  Therefore, an IR ablation laminate in which the above-mentioned conventional problems are solved, a high-quality printed image can be obtained, the contamination of the developer can be reduced, and the present invention can also be applied to various photosensitive resin layers. In order to meet this demand, a photosensitive resin laminate in which the IR ablation layer includes an IR absorbing metal layer has been proposed.

  Most of the problems could be solved by the proposal of the IR-absorbing metal layer-containing photosensitive resin laminate. However, depending on the type of printing, it is necessary to use a metal plate as a support. In this case, since a photosensitive layer exists between the IR-absorbing metal layer and the metal support, oxygen permeability is poor and polymerization is performed. There was a problem that was going too far. In such a state, sufficient development cannot be performed, which adversely affects image reproducibility and quality.

  In view of the above circumstances, an object of the present invention is to provide a photosensitive resin laminate having an IR ablation layer and a metal support, in which a higher-quality printed image can be obtained.

  As a result of intensive studies to solve the above problems, the present inventors have finally completed the present invention. That is, the present invention relates to (1) a photosensitive resin laminate having at least a support, a photosensitive resin layer, a non-IR sensitive polymer resin layer, an IR ablation layer, and a cover film, wherein the support is a metal, and A water-developable photosensitive resin laminate, wherein the IR-sensitive polymer resin layer has a thickness of less than 0.1 to 2.0 μm. (2) The photosensitive resin laminate according to the above (1), wherein the IR ablation layer is an IR absorbing metal layer. (3) The photosensitive resin laminate according to (1), wherein the IR ablation layer is an aluminum vapor deposition layer. (4) The photosensitive resin laminate according to any one of (1) to (3), wherein the IR ablation layer is disposed in contact with the photosensitive resin layer.

  The photosensitive resin laminate of the present invention has an IR-absorbing metal layer and a metal support, has no adverse effect on quality, and can obtain a CTP plate with excellent image reproducibility, thus contributing to the industry. It ’s big.

  The IR ablation layer in the present invention contains an IR-absorbing metal, and the “IR-absorbing metal” means a metal, an alloy or a metal-containing compound that can be ablated by absorbing IR. The alloy in (2) includes not only a fusion of two or more metal elements but also a fusion containing elements other than the metal elements together with two or more metal elements. The “IR absorbing metal” may be a single material or a combination of two or more materials.

Preferable examples of the IR absorbing metal include Al, Zn, and Cu. Preferred examples of the alloy include Ca, Sc, Tl, V, Sb, Cr, Mn, Al, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ag, In, Sn, An alloy of two or more kinds of metals selected from Ta, W, Au, Bi and Pb, and these two or more kinds of metals, and further, nonmetallic elements (carbon, silicon, etc.) and / or rare earth elements (Nd, Sm, Gd) , Tb, etc.). In addition, as the metal-containing compound, various compounds such as metal oxides and metal nitrides can be used as long as they can be ablated by absorbing IR. Among them, copper chromite, chromium oxide, Dark inorganic pigments such as cobalt aluminate-chromium are preferred.
From the viewpoint of preventing the IR ablation layer from being broken or scratched (film strength), it is preferable to use a metal or an alloy as the IR absorbing metal, and particularly preferably an Al, Zn, Cu, or Bi—In—Cu alloy. Especially preferred is Al.

  As the support for the photosensitive printing original plate, a material that is flexible but excellent in dimensional stability is preferably used, and a metal such as steel, aluminum, copper, or nickel is used. The thickness of the support used here is preferably from 50 to 350 μm, preferably from 100 to 250 μm from the viewpoint of mechanical properties, shape stabilization, or handleability during printing plate making. Moreover, you may provide the adhesive agent generally used in order to improve the adhesion | attachment of a support body and the photosensitive resin layer as needed.

  Next, as a constituent material of the non-IR sensitive polymer resin layer in the present invention, polyamide, polyethylene, polypropylene, polyvinyl alcohol, polyacrylic acid, polyethylene oxide, amphoteric interpolymer, alkyl cellulose, cellulose-based polymer (particularly hydroxypropyl cellulose) , Hydroxyethyl cellulose, nitrocellulose), copolymers of ethylene and vinyl acetate, cellulose acetate butyrate, polybutyral, cyclic rubber and the like. These may be used alone or in combination of two or more. As the amphoteric interpolymer, those described in US Pat. No. 4,293,635 can be employed.

Among the materials exemplified above, the film thickness of the non-IR-sensitive polymer resin layer is preferably less than 0.1 to 2.0 μm, more preferably in consideration of development with water or an aqueous medium, generation of wrinkles, and the like. Is 0.5 to 1.5 μm, preferably 1.0 to 1.2 μm.
In the present invention, polyvinyl alcohol, modified polyvinyl alcohol, polyacrylic acid, and polyethylene oxide can be mentioned. Among them, the polymerization degree is 500 to 4000, preferably 1000 to 3000, and the saponification degree is 70% or more, preferably 80 to 99. %, More preferably 80-90% polyvinyl alcohol or modified polyvinyl alcohol is desirable. Here, the modified polyvinyl alcohol is a secondary reaction of a compound having reactivity with the hydroxyl group of polyvinyl alcohol (for example, a compound having a carboxyl group, a double bond, an aromatic ring, etc.), vinyl acetate and the like. A copolymer with a vinyl monomer is saponified to introduce a carboxyl group, a carbonyl group, a polyoxyalkylene group, an acetoacetyl group, a sulfone group, or a silanol group into the terminal or main chain.

In the present invention, the IR ablation layer does not substantially transmit ultraviolet rays (active light). That is, the optical density with respect to actinic rays is a value exceeding 2.5, and preferably a value exceeding 3.0.
In order to have the optical density, when only the IR absorbing metal layer is used as the IR ablation layer, the thickness is preferably 70 to 20000 mm, particularly preferably 100 to 8000 mm, and particularly preferably 300 to 5000 mm. If the thickness is less than 70 mm, the function as a mask after IR ablation is inferior because it is inferior, and if it exceeds 2000 mm, it is difficult to ablate (ablate) with IR for image formation. .

  On the other hand, when the IR ablation layer is composed of an IR absorbing metal layer and another IR absorbing material, the thickness of the IR absorbing metal layer is preferably 50 to 15000 mm, particularly preferably 70 to 8000 mm, and particularly preferably 100. ~ 5000cm. If the thickness is less than 50 mm, the function as a mask after IR ablation is inferior because it is inferior, and if it exceeds 15000 mm, it is difficult to ablate (ablate) with IR for image formation. .

  The photosensitive resin layer in the present invention is a layer of a composition containing at least a known soluble synthetic polymer compound including an elastomer binder, a photopolymerizable unsaturated compound (hereinafter also referred to as a crosslinking agent), and a photopolymerization initiator. is there. In addition, additives such as plasticizers, thermal polymerization inhibitors, dyes, pigments, UV absorbers, perfumes or antioxidants may be included.

  In the present invention, a known soluble synthetic polymer compound can be used as the soluble synthetic polymer compound. For example, polyether amide (for example, JP-A-55-79437), polyether ester amide (for example, JP-A-58-113537, etc.), tertiary nitrogen-containing polyamide (for example, JP-A-50-76055, etc.) , An ammonium salt type tertiary nitrogen atom-containing polyamide (for example, JP-A-53-36555), an addition polymer of an amide compound having at least one amide bond and an organic diisocyanate compound (for example, JP-A-58-140737) ), An addition polymer of a diamine having no amide bond and an organic diisocyanate compound (for example, JP-A-4-97154, etc.), among which a tertiary nitrogen atom-containing polyamide and an ammonium salt type tertiary nitrogen atom are included. Polyamide is preferred.

  In the case of an elastomer binder as the soluble synthetic polymer compound, a single polymer or a polymer mixture may be used. Further, it may be a hydrophobic polymer, a hydrophilic polymer, or a mixture of a hydrophobic polymer and a hydrophilic polymer. Hydrophobic polymers include butadiene rubber, isoprene rubber, 1,2-polybutadiene, styrene-butadiene rubber, chloroprene rubber, nitrile-butadiene rubber, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, butyl rubber, ethylene -Propylene rubber, chlorosulfonated polyethylene, butadiene- (meth) acrylic acid ester copolymer, acrylonitrile- (meth) acrylic acid ester copolymer, epichlorohydrin rubber, chlorinated polyethylene, silicone rubber and urethane rubber are suitable. These may be used alone or in combination of two or more.

  In addition, polybutadiene latex, natural rubber latex, styrene-butadiene copolymer latex, acrylonitrile-butadiene copolymer latex, polychloroprene latex, polyisoprene latex, polyurethane latex, methyl methacrylate-butadiene copolymer latex, vinyl pyridine Water-dispersed latex polymers such as polymer latex, butyl polymer latex, thiocol polymer latex, and acrylate polymer latex, and polymers obtained by copolymerizing these polymers with other components such as acrylic acid and methacrylic acid Can be mentioned. Among these, an aqueous dispersion latex polymer containing a butadiene skeleton or an isoprene skeleton in the molecular chain is preferably used from the viewpoint of hardness and rubber elasticity. Specifically, polybutadiene latex, styrene-butadiene copolymer latex, acrylonitrile-butadiene copolymer latex, methyl methacrylate-butadiene copolymer latex, and polyisoprene latex are preferable.

The hydrophilic polymer, -COOH, -COOM (M is monovalent, divalent, or trivalent metal ion or substituted or unsubstituted ammonium _{ion), - OH, -NH 2,} -SO 3 H, phosphoric acid Those having a hydrophilic group such as an ester group are preferred. Specifically, a polymer of (meth) acrylic acid or a salt thereof, a copolymer of (meth) acrylic acid or a salt thereof and an alkyl (meth) acrylate, ( Copolymer of meth) acrylic acid or a salt thereof and styrene, copolymer of (meth) acrylic acid or a salt thereof and vinyl acetate, copolymer of (meth) acrylic acid or a salt thereof and acrylonitrile, polyvinyl alcohol , Carboxymethylcellulose, polyacrylamide, hydroxyethylcellulose, polyethylene oxide, polyethyleneimine, − Polyurethane having a OOM group, polyureaurethane having -COOM group, include the polyamic acid and their salts or derivatives having a -COOM group. These may be used alone or in combination of two or more.

  When the soluble synthetic polymer compound is an elastomer binder, the photopolymerizable unsaturated compound preferably used is a conventional polymerizable ethylenic mono- or compound that can be used for the production of a polymerizable printing plate and is compatible with the elastomer binder. It is a polyunsaturated organic compound.

Examples of the photoinitiator include benzophenones, benzoins, acetophenones, benzyls, benzoin alkyl ethers, benzyl alkyl ketals, anthraquinones, thioxanthones, and the like.
The photosensitive resin layer in the present invention may contain additives such as a plasticizer, a thermal polymerization inhibitor, a dye, and an antioxidant in addition to the soluble synthetic polymer compound, the polymerizable compound, and the photoinitiator. .

  The photosensitive resin layer can be prepared so as to be soluble or dispersed in a water-soluble developer, a semi-water-soluble developer or an organic solvent-based developer by appropriately changing the material of each component. It is preferable that the film can be developed with the above. In the case of forming a photosensitive resin layer that can be developed with such water or an aqueous medium, specifically, EP-A 767407, JP-A-60-21451, JP-A-2-175702, JP-A-4-175, and the like. It is preferable to correspond to the photosensitive resin layer described in 3162, JP-A-2-305805, JP-A-3-228060, JP-A-10-339951, and the like.

  In the present invention, a cover film may be provided. The cover film is provided for protecting the IR ablation layer during storage and handling of the original plate, and is removed (peeled) before or after IR irradiation. The

The constituent materials of the cover film include polyethylene, polypropylene, polyethylene terephthalate, polyethylene-2,6-naphthalate, nylon 6, nylon 4, nylon 66, nylon 12, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, wholly aromatic. Polyamide, polyamideimide, polyimide, polyetherimide, polysulfone, polyphenylene sulfide, polyphenylene oxide and the like are suitable. Any of these may be used alone or in combination of two or more. In addition, a small amount of other organic polymers may be copolymerized or blended with them.
The cover film has a thickness of preferably 10 to 300 μm, particularly preferably 10 to 200 μm.

  Although it does not specifically limit as a method of creating the layer for IR ablation in the present invention, it is applied to a cover film provided with a blocking prevention layer in advance by forming a non-IR sensitive polymer resin layer if necessary by spray coating, etc. Subsequently, an IR-absorbing metal layer can be formed by vacuum deposition, sputtering, or the like.

In addition, as a method for producing the photosensitive resin laminate of the present invention (also referred to as a photosensitive printing original plate), generally, a photosensitive resin layer is formed on a support by coating, spray coating, or the like, or One laminate is prepared by peeling off the protective film from the commercially available photosensitive printing plate. Further, separately from this, the IR ablation laminate is formed, and these two laminates are used using a heat press machine or the like. It can be produced by laminating. The lamination conditions are such that the temperature is room temperature to 150 ° C., preferably 50 to 120 ° C., and the pressure is 20 to 200 kgf / cm ² , preferably 50 to 150 kgf / cm ² .

A printing plate is prepared from the photosensitive resin original plate as follows.
After the cover film is peeled off or left as it is, IR ablation is performed by irradiating the IR ablation layer with an IR laser to form a mask on the photosensitive resin layer. Examples of suitable IR lasers include ND / YAG laser (1064 nm) or diode laser (eg, 830 nm). Laser systems suitable for computer plate making technology are commercially available, for example, diode laser system OmniSetter® (Fa. Misomex; laser wavelength: 830 nm; working width: 1800 mm) or ND / YAG laser system Digilas® (Fa. Schepers). These include a rotating cylindrical drum holding a photosensitive printing original, an IR laser irradiation device, and a layout computer. Image information is transferred directly from the layout computer to the laser device.

  Next, after writing image information on the IR ablation layer as described above, this is used as a mask, and the photosensitive printing plate is irradiated with actinic radiation through the mask. This is advantageously done directly on the laser cylinder. Alternatively, the plate may be removed from the laser device and irradiated with a conventional flat irradiation unit. During the irradiation process, the photosensitive resin layer is polymerized in the area exposed in the mask formation process (ablation process), while in the IR ablation layer area that is still covered with the IR ablation layer that does not transmit the irradiation light, polymerization occurs. Does not happen. Irradiation with actinic rays can be performed by removing oxygen with a conventional vacuum frame, but it is advantageous to perform the irradiation in the presence of atmospheric oxygen.

The plate irradiated with actinic rays as described above is subjected to a development process. The development step can be carried out in a conventional development unit, and water, an organic solvent or a mixture thereof can be used depending on the properties of the plate. During development, the unpolymerized areas of the photosensitive resin layer and the remaining IR ablation layer are removed. It is also possible to first remove the IR ablation layer with one solvent or solvent mixture and develop the photosensitive resin layer with another developer. After the development process, the obtained printing plate is dried. The drying conditions of the plate are, for example, 45 to 80 ° C. and 5 minutes to 4 hours. Some post-treatment operations may be further performed after drying. For example, in order to make the printing plate non-adhesive, a germicidal lamp or treatment with Br ₂ can be performed.

  EXAMPLES Next, although this invention is demonstrated concretely using an Example, this invention is not limited to these Examples. In the examples, “parts” means “parts by weight”.

Example 1
2-methylpentamethylenediamine (MPDA) 2.0 parts, 1,4-bisaminopropylpiperazine (BAPP) 7.9 parts, polyethylene glycol hexamethylene diisocyanate reactant (HE-600) 45.2 parts and adipic acid 1 .7 parts were placed in 100 parts of methanol and a heated dissolution kettle with stirring, and after sufficient nitrogen substitution, the flask was sealed and gradually heated to 65.degree. After stirring for about 2 hours, 5.0 parts of N-ethyltoluenesulfonic acid amide, 0.03 part of 1,4-naphthoquinone and 0.1 part of hydroquinone monomethyl ether were added and dissolved by stirring for another 30 minutes. Thereafter, 2.5 parts of glycidyl methacrylate (GMA), 18 parts of water, 0.3 part of ammonium sulfite, 0.1 part of oxalic acid, 1.2 parts of adipic acid, 1.0 part of benzyldimethyl ketal as a photoinitiator, glycerin Further, 24.8 parts of dimethacrylate (Kyoeisha Chemical Co., Ltd. crosslinker light ester G101P) and Kyoeisha Chemical Co., Ltd. crosslinker trimethylolpropane polyglycidyl ether- (meth) acrylic acid adduct CHA 8.3 parts were further added and added. The mixture was dissolved with stirring for a minute. Next, the temperature was gradually raised to distill methanol and water, and the mixture was concentrated until the temperature in the kettle reached 110 ° C. At this stage, the flowable viscous photosensitive resin composition 1 is sandwiched between a metal support, a non-IR sensitive polymer resin layer having a film thickness of 1.2 μm, and a cover film having an IR ablation layer, and pressed to form a sheet. A photosensitive laminate 1 having a resin thickness of 675 μm was obtained. This photosensitive resin composition 1 was brushed with water at 25 ° C. for 2 minutes (hereinafter referred to as “washing out”), and was satisfactory with no residual resin.

Comparative Example 1
The photosensitive resin composition 1 obtained in Example 1 was sandwiched and pressed between a metal support, a non-IR sensitive polymer resin layer having a thickness of 2.4 μm, and a cover film having an IR ablation layer, and a sheet-like resin thickness of 675 μm. A photosensitive laminate 1 was obtained. This photosensitive resin laminate 1 was washed out for 2 minutes, but the unexposed part was also cured and could not be washed out.

Example 2
Hydrophobic polymer (α) as component (A): 8 parts by weight of acrylonitrile-butadiene latex (Nipol SX1503, nonvolatile content 42%, manufactured by Nippon Zeon Co., Ltd.), hydrophobic polymer (β): butadiene latex (Nipol LX111NF nonvolatile) Min 55% Nippon Zeon Co., Ltd.) 50 parts by weight, component (B) Oligobutadiene Acrylate (ABU-2S manufactured by Kyoeisha Chemical Co., Ltd.) 26 parts by weight, lauryl methacrylate (Light Ester L manufactured by Kyoeisha Chemical Co., Ltd.) ) 8 parts by weight, 8 parts by weight of dimethylol tricyclodecane diacrylate (C) 1 part by weight of photopolymerization initiator, 0.1 part by weight of hydroquinone monomethyl ether as a polymerization inhibitor, and nonionic interface as other additives After mixing 0.1 part by weight of activator with 15 parts by weight of toluene in a container, then 1 using a pressure kneader Kneaded at 5 ° C., followed by reducing the pressure to remove toluene and water to obtain a photosensitive resin composition 2.
A photosensitive laminate 2 was obtained and brushed with the obtained photosensitive resin composition 2 in the same manner as in Example 1, but it was satisfactory because there was no residual resin.

  As described above, the photosensitive resin laminate of the present invention having such a structure has no adverse effect on quality even if it has an IR-absorbing metal layer and a metal support, and has excellent image reproducibility. It can be widely used for various printing applications.

Claims (4)

  In a photosensitive resin laminate having at least a support, a photosensitive resin layer, a non-IR sensitive polymer resin layer, an IR ablation layer, and a cover film, the support is a metal, and the thickness of the non-IR sensitive polymer resin layer Is a water-developable photosensitive resin laminate, characterized by being less than 0.1 to 2.0 μm.   The photosensitive resin laminate according to claim 1, wherein the IR ablation layer is an IR absorbing metal layer.   The photosensitive resin laminate according to claim 1, wherein the IR ablation layer is an aluminum vapor deposition layer.   The photosensitive resin laminate according to claim 1, wherein the IR ablation layer is disposed in contact with the photosensitive resin layer.