JP6645061B2 - Photosensitive resin composition, photosensitive resin laminate, and photosensitive resin printing plate precursor - Google Patents

Description

  The present invention is a photosensitive resin composition that can be developed using a solution containing a lower alcohol, is capable of forming a high-definition relief image, and can provide an intaglio printing plate excellent in abrasion resistance, Provided are a photosensitive resin laminate and a photosensitive resin printing plate precursor.

  A photosensitive resin printing plate precursor using a photosensitive resin laminate having a layer formed of a photosensitive resin composition generally has a polymer soluble in the photosensitive resin layer, a monomer containing a photopolymerizable unsaturated group, and a photopolymerization initiator. Containing the agent as an essential component, by irradiating the photosensitive resin layer with ultraviolet light through a negative, positive original image film, by forming a portion that is soluble in the solvent and a portion that does not dissolve in the photosensitive resin layer , A relief image is formed and used as a printing plate.

  In tampo printing using an intaglio printing plate, ink is placed on the plate surface and scraped off with a metal doctor blade, or placed in a ring-shaped ink cup with a ceramic or special metal edge serving as a doctor blade. By filling the ink and scraping the plate surface with an ink cup, the ink is filled into the concave portions of the intaglio printing plate, the ink is transferred to a flexible pad surface such as silicone rubber, and the ink-attached surface of the pad is printed. This is a type of offset printing that prints by crimping on the body. The intaglio printing plate used for tampo printing requires abrasion resistance on the plate surface because the ink on the plate surface is scraped off by a doctor blade or an ink cup due to the printing method. As a photosensitive resin composition used in printing applications requiring such abrasion resistance, a photosensitive resin composition in which abrasive particles are blended has been proposed as disclosed in Patent Document 1.

JP-A-2-6957 JP-A-7-62229 JP 2007-63117 A JP 2010-265139 A International Publication No. 2012/161157 pamphlet

  However, when abrasive fine particles having a large average particle size are used in the photosensitive resin composition, the photosensitive resin composition becomes turbid. Therefore, when the photosensitive resin composition is irradiated with ultraviolet light and cured by light, the ultraviolet light in the photosensitive resin is scattered, making it difficult to form an intaglio printing plate having high-definition concave portions.

  The present invention has been made in view of the above circumstances, an intaglio printing plate capable of being developed using a solution containing a lower alcohol, capable of forming a high-definition relief image, and having excellent wear resistance. It is an object of the present invention to provide a photosensitive resin composition, a photosensitive resin laminate, and a photosensitive resin printing plate precursor that can obtain the following.

  In order to achieve the above object, the present invention relates to the following.

  (A) a polyamide having an aliphatic ring in the molecular main chain and / or a polyamide having a skeleton represented by the general formula (1), (B) inorganic fine particles having an average particle diameter of 1 to 50 nm, (C) ethylenic The present invention relates to a photosensitive resin composition containing a compound having a double bond and (D) a photopolymerization initiator.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin printing which can be developed using the solution containing a lower alcohol, can form a high-definition relief image, and can obtain the intaglio printing plate excellent in abrasion resistance An original plate can be provided.

  Hereinafter, embodiments of the present invention will be described.

  The (A) polyamide having an aliphatic ring in the molecular main chain and / or the polyamide having a skeleton represented by the general formula (1), which constitutes the photosensitive resin composition of the present invention, is used as the photosensitive resin composition. It has a function as a carrier resin for maintaining a form in a solid state. The polyamide (A) is used for imparting developability to a photosensitive resin layer with a solution containing a lower alcohol.

  Since the component (A) is insoluble in water, the printing plate obtained from the photosensitive resin composition containing the component (A) is not affected by water even when used in a high-humidity environment. Has wear resistance.

  The component (A) preferably has a number average molecular weight of 10,000 to 1,000,000. When it is 10,000 or more, the photosensitive resin composition has a function as a carrier resin for maintaining the form in a solid state, and when it is 1,000,000 or less, the photosensitive resin layer When the film is exposed to ultraviolet light like an image and selectively cured, and the uncured portion is removed by development, it can be quickly removed with a developer containing a lower alcohol. The lower alcohol refers to an alcohol having 5 or less carbon atoms in the molecule.

  The content of the component (A) in the photosensitive resin composition is preferably 20 to 80% by mass. When the content is 20% by mass or more, the composition can be in a solid state and the form can be maintained. When the content is 80% by mass or less, formation of a relief image becomes easy.

  The polyamide having an aliphatic ring in the molecular main chain of the component (A) can be obtained by co-condensation of a diamine and / or dicarboxylic acid having an aliphatic ring and a derivative thereof when polymerizing the polyamide. .

  As such a polyamide, for example, a polycondensate from ε-caprolactam, hexamethylenediammonium adipate and 4,4′-diaminodicyclohexylmethane adipate as shown in Patent Document 1 is known.

  These aliphatic ring-containing monomer components are present in an amount of 10 to 100 mol% based on the total amount of the polyamide components, that is, aminocarboxylic acid units (including lactams as raw materials), dicarboxylic acid units and diamine units. It is more preferably, and more preferably 10 to 80 mol%. When the content of these aliphatic ring-containing monomer components is 10 mol% or more, the solubility in lower alcohols when the photosensitive resin composition is used as a photosensitive resin layer is improved. As a result, when the photosensitive resin layer is imagewise exposed to ultraviolet light, selectively cured, and when the uncured portion is removed by development, it can be quickly removed with a developer containing a lower alcohol. Become. When it is at most 80 mol%, the chemical resistance as a crystalline polymer will be favorably maintained.

  On the other hand, the polyamide (A) having a skeleton represented by the general formula (1) is obtained by reacting hydrogen of an amide bond of the polyamide with formaldehyde and methanol, and N-methoxymethylating the amide bond. (For example, see Patent Document 2).

  Further, it is preferable that 10 to 50% of the hydrogen of the amide bond in the molecule is methoxymethylated. By setting the methoxymethylation to 10% or more, the solubility in lower alcohol is increased. Therefore, the photosensitive resin layer is exposed to ultraviolet light like an image, selectively cured, and the uncured portion is removed by development. In this case, it can be quickly removed with a developer containing a lower alcohol. Further, by setting the methoxymethylation to 50% or less, the abrasion resistance of the polymer can be maintained.

  As such a polyamide, for example, "Toresin" (registered trademark) having a number average molecular weight of 40,000 in which 30% of the amide bond of 6-nylon is modified into a skeleton represented by the above general formula (1) ) MF-30 (manufactured by Nagase ChemteX Corporation).

  It is also possible to use a mixture of a polyamide having an aliphatic ring in the molecular main chain and a polyamide having a skeleton represented by the general formula (1).

  The photosensitive resin composition of the present invention preferably uses fine particles having sufficient transparency to ultraviolet light to be exposed, and contains (B) inorganic particles having an average particle diameter of 1 to 50 nm.

  When the average particle diameter of the inorganic particles (B) is 1 nm or more, aggregation of the particles in the photosensitive resin can be suppressed, and when the average particle diameter is 50 nm or less, light of the photosensitive resin composition can be suppressed. Transparency can be ensured. By using such a component (B), a photosensitive resin composition capable of forming a high-definition relief image and having excellent abrasion resistance can be provided.

  The average particle diameter can be measured by the nitrogen adsorption method (BET method) of Patent Document 3 or the TME observation described in Patent Document 4.

  (B) Examples of the inorganic particles having an average particle diameter of 1 to 50 nm include, for example, fine particles of a simple metal, fine particles of an inorganic oxide, fine particles of an inorganic salt, and fine particles composed of an organic component and an inorganic component. Among these, silica fine particles having a refractive index relatively close to that of an organic component are preferred from the viewpoint of suppressing the scattering of ultraviolet light when the photosensitive resin composition is irradiated with light and cured by light. Among the silica fine particles, crystalline silica has carcinogenicity, and therefore, amorphous silica that can be safely handled is preferable.

  Among the amorphous silicas, the hydrolyzates of alkoxysilanes are preferable because they hardly aggregate.

  Further, colloidal silica, which is a hydrolyzate of alkoxysilane, is in a state of being dispersed in a dispersion medium, so that it is easy to mix with other components in the photosensitive resin composition when forming the photosensitive resin layer, and thereafter, Drying is preferable because a photosensitive resin layer uniformly dispersed can be formed.

  Further, among the colloidal silicas, colloidal silica dispersed in an organic solvent or a lower alcohol is more preferable because it can be easily mixed with the component (A).

  The photosensitive resin composition having such silica particles having low cohesiveness suppresses scattering of light irradiated during photocuring and has sufficient light transmittance, so that abrasion resistance and high-detail relief are provided. It is possible to obtain a printing plate compatible with image formation.

  The component (B) is preferably contained in the photosensitive resin composition in an amount of 3% by mass or more in order to impart abrasion resistance, and it is possible to suppress aggregation of particles. Is preferred.

  It is also possible to introduce an ethylenic double bond on the surface of the component (B) using a surface modifier.

  Examples of such a modifying agent include (3-acryloylpropyl) trimethoxysilane, methacryloylpropyltrimethoxysilane, methacryloylpropyltriethoxysilane, methacryloyloxymethyltriethoxysilane, and methacryloyloxymethyltrimethoxysilane. And the like, but not limited thereto.

  The photosensitive resin composition of the present invention contains (C) a compound having an ethylenic double bond.

  Specific examples of the compound (C) preferably used include the following, but are not limited thereto.

  For example, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, phenoxydiethylene glycol (meth) acrylate, 2- (meth) acryloy Roxyethyl phthalate, neopentyl glycol- (meth) acrylic acid-benzoate, (meth) acryloylmorpholine, styrene and its derivatives, vinylpyridine, N-vinyl-2-pyrrolidone, β- (meth) acryloyloxyethyl Hydrogen phthalate, N-phenylmaleimide and derivatives thereof, N- (meth) acryloxysuccinimide, 2-naphthyl (meth) acrylate, N-phenyl (meth) acrylamide, divinylethylene urea, Vinyl propylene urea, vinyl caprolactam, vinyl carbazole, bicyclopentenyl (meth) acrylate, 1-vinylimidazole, 2-methyl-1-vinylimidazole, (2-methyl-ethyldioxolan-4-yl) methyl acrylate, imide acrylate, (2-oxy-1,3-dioxolan-4-yl) methyl (meth) acrylate, 2- (oxydiimidazolidin-1-yl) ethyl (meth) acrylate, 2,2,6,6-tetramethyl- 4-piperidyl acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, Allyl (meth) acrylate, chloroethyl (meth) acrylate, chloropropyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene Glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, (meth) acrylamide, diacetone (meth) acrylamide, N, N'-methylenebis (meth) acrylamide, 2,2-dimethylaminoethyl (meth) acrylate, 2 , 2-Diethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide A compound having only one ethylenic double bond such as 2-hydroxyethyl (meth) acrylate, di (meth) acrylate of polyethylene glycol such as diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Compounds having an ethylenic double bond and active hydrogen such as unsaturated carboxylic acid and unsaturated alcohol in pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerol tri (meth) acrylate, ethylene glycol diglycidyl ether Is obtained by an addition reaction of an unsaturated epoxy compound such as polyvalent (meth) acrylate or glycidyl (meth) acrylate obtained by an addition reaction with a compound having active hydrogen such as a carboxylic acid or an amine. Polyvalent (meth) acrylate, methylenebis (meth) multivalent acrylamide (meth) acrylamide, polyvalent vinyl compounds such as divinylbenzene, a compound having two or more ethylenic double bonds, such as, and the like.

  Among these (C) compounds, those having one or more hydroxyl groups have good compatibility with the components (A) and (B) and have a uniform composition when blended with the photosensitive resin composition. Can be produced. Examples of such a compound (C) include 2-hydroxy-3-phenoxypropyl (meth) acrylate, [4- (hydroxymethyl) cyclohexyl] methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Propyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, β-hydroxy-β ′-(meth) acryloyloxyethyl phthalate, phenoxyethyl acrylate, nonylphenoxyethyl (Meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerol di (meth) acrylate and the like.

  Further, those having two or more hydroxyl groups can suppress the swelling of the intaglio printing plate due to the organic solvent of the ink used for tampo printing due to the hydrogen bond of the hydroxyl groups. Such compounds include, but are not limited to, glycerin mono (meth) acrylate and pentaerythritol mono (meth) acrylate.

  The content of the compound (C) is preferably 5 to 200 parts by mass based on 100 parts by mass of the component (A). When the amount is 5 parts by mass or more, when printing using the ink, the printing plate can be used without swelling, and when the amount is 200 parts by mass or less, molding of the photosensitive resin composition is facilitated, which is preferable. .

  The compound (C) preferably contains both an acryloyl group and a methacryloyl group, and the number of methacryloyl groups in the compound (C) is preferably larger than the number of acryloyl groups. In general, methacryloyl groups have a lower reaction rate than acryloyl groups. Therefore, when ultraviolet rays are irradiated through a positive film, the number of methacryloyl groups is large, so that the concave portion of the relief becomes deep. The adjustment of the depth becomes easier.

  Further, the photosensitive resin composition of the present invention contains (D) a photopolymerization initiator. As the photopolymerization initiator (D), any one can be used as long as it can polymerize a polymerizable carbon-carbon unsaturated group by light. Among them, those having a function of generating radicals by self-decomposition or hydrogen abstraction by light absorption are preferably used. For example, there are benzoin alkyl ethers, benzophenones, anthraquinones, benzyls, acetophenones, diacetyls and the like.

  (D) As a compounding quantity of a photoinitiator, the range of 0.1-20 mass parts is preferable with respect to 100 mass parts of (A) components. When the amount is 0.1 part by mass or more, the formability of the relief image is improved, and when the amount is 20 parts by mass or less, precipitation of the photopolymerization initiator can be suppressed.

  In the photosensitive resin composition of the present invention, compatibility, ethylene glycol, diethylene glycol, triethylene glycol, glycerin and its derivatives, trimethylolpropane and its derivatives, trimethylolethane and It is also possible to add polyhydric alcohols such as derivatives thereof, pentaerythritol and derivatives thereof. The content of these polyhydric alcohols is preferably 30% by mass or less based on the entire photosensitive resin composition. In particular, by improving the compatibility, turbidity of the resin composition and bleed-out of low molecular weight components can be suppressed.

  In order to increase the thermal stability of the photosensitive resin composition of the present invention, a conventionally known polymerization inhibitor can be added. Preferred polymerization inhibitors include phenols, hydroquinones, catechols, hydroxyamine derivatives and the like. It is preferable to use these compounds in the range of 0.001 to 5% by mass based on the entire photosensitive resin composition.

  Further, in the intaglio printing plate formed from the photosensitive resin printing plate precursor using the photosensitive resin composition of the present invention, in order to form a recess having a good shape, light scattering in the photosensitive resin layer is reduced. An ultraviolet absorber may be added for the purpose of suppression. As a preferred ultraviolet absorber, one or more benzotriazole-based, triazine-based, and benzophenone-based compounds can be used. In addition, it is preferable to use the compounding quantity of an ultraviolet absorber in the range of 0.001-5 mass% with respect to all the photosensitive resin compositions.

  Further, a dye, a pigment, a surfactant, an antifoaming agent, a fragrance, and the like can be added as other components to the photosensitive resin composition of the present invention.

  The photosensitive resin laminate of the present invention comprises an adhesive layer (G), a photosensitive resin layer (F) formed using the photosensitive resin composition of the present invention, and a protective layer on at least a support (E). Are stacked in this order. And the photosensitive resin printing plate precursor of the present invention is formed using the photosensitive resin laminate.

  As the support (E), a plastic sheet such as polyester, a synthetic rubber sheet such as styrene-butadiene rubber, or a metal plate such as steel, stainless steel, or aluminum can be used. To scrape with a metal doctor blade, or to put ink into a ring-shaped ceramic or special metal edged ink cup that serves as a doctor blade and scrape the plate surface with the ink cup. It is preferable to use a metal plate so that the support is not deformed by the force of scraping.

  The thickness of the support is not particularly limited, but is preferably in the range of 100 to 500 μm from the viewpoint of handleability. If it is 100 μm or more, deformation of the support is suppressed, and if it is 500 μm or less, handleability is improved.

  The support (E) is preferably subjected to an easy adhesion treatment for the purpose of improving the adhesion to the photosensitive resin layer (F). Examples of the method of the easy adhesion treatment include mechanical treatment such as sandblasting, physical treatment such as corona discharge, and chemical treatment such as coating, and the like. Is preferred.

  The photosensitive resin layer (F) is formed from the photosensitive resin composition of the present invention. The thickness of the photosensitive resin layer (F) is preferably 0.01 mm or more, more preferably 0.02 mm or more, from the viewpoint of having a sufficient relief depth and improving printability. On the other hand, the photosensitive resin layer is preferably 1 mm or less, more preferably 0.7 mm or less from the viewpoint of cost and resource saving.

  The photosensitive resin printing plate precursor of the present invention preferably has a cover film (H) as a protective layer on the photosensitive resin layer (F) from the viewpoint of surface protection and prevention of adhesion of foreign matter and the like. The photosensitive resin layer (F) may be in direct contact with the cover film (H), or may have one or more layers between the photosensitive resin layer (F) and the cover film (H). Good. As the layer between the photosensitive resin layer (F) and the cover film (H), for example, a release auxiliary layer provided for the purpose of preventing the surface of the photosensitive resin layer from sticking is exemplified.

  The material of the cover film (H) is not particularly limited, but a plastic sheet such as polyester or polyethylene is preferably used. The thickness of the cover film (H) is not particularly limited, but is preferably in the range of 10 to 150 μm from the viewpoint of handleability and cost. The cover film surface may be roughened for the purpose of improving the adhesion of the original film.

  Next, the photosensitive resin composition of the present invention and a method for producing a photosensitive resin printing original plate using the same will be described. For example, the components (A) and (B) are heated and dissolved in a mixed solvent containing alcohol as a main component, and then (C) a compound having an ethylenic double bond, (D) a photopolymerization initiator, and if necessary. Then, a plasticizer and other additives are added, and the mixture is stirred and sufficiently mixed to obtain a photosensitive resin composition solution.

  The photosensitive resin layer (F) composed of the photosensitive resin composition is obtained by casting the photosensitive resin composition solution obtained by the above-described method onto a support (E) having an adhesive layer (G) if necessary. It can be obtained by drying. Thereafter, the cover film (H) coated with the release auxiliary layer, if necessary, is brought into close contact with the photosensitive resin layer (F) to obtain a photosensitive resin printing plate precursor. Alternatively, a photosensitive resin printing plate precursor can also be obtained by preparing a photosensitive resin sheet by dry film formation and laminating the photosensitive sheet between the support (E) and the cover film (H) so as to sandwich the photosensitive sheet.

  When the photosensitive resin printing plate precursor has the release auxiliary layer (I), the method of forming the release auxiliary layer (I) is not particularly limited, but the component of the release auxiliary layer (I) is dissolved in a solvent because of the ease of forming a thin film. The method of applying the solution thus obtained on the cover film (H) and removing the solvent is particularly preferably performed. Examples of the method for removing the solvent include hot-air drying, far-infrared drying, and natural drying. The solvent for dissolving the component (I) is not particularly limited, but water, alcohol, or a mixture of water and alcohol is preferably used.

  Next, a printing plate formed using the photosensitive resin printing plate precursor of the present invention will be described. The printing plate of the present invention is obtained by exposing and developing the above-described photosensitive printing plate precursor of the present invention.

  When the photosensitive resin printing plate precursor has a cover film (H), the cover film (H) is peeled off, a positive original film is brought into close contact with the photosensitive resin layer (F), and the photosensitive resin layer (F) is irradiated with ultraviolet light to form a photosensitive resin layer (H). F) is light cured. Ultraviolet irradiation is performed using a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a carbon arc lamp, a chemical lamp, or the like, which can normally emit a wavelength of 300 to 400 nm.

  Next, a halftone screen film of 300 lines 90% is brought into close contact with the film and irradiated with ultraviolet rays so that the depth of the concave portion is adjusted to be appropriate.

  Next, the photosensitive printing plate precursor is immersed in a developing solution, and a relief image is formed on the substrate by a brush-type developing device that removes the uncured portion by rubbing with a brush. In addition to the brush type developing device, a spray type developing device can be used. As the developer, a solution containing a lower alcohol or a solution containing a surfactant can be used.

  The liquid temperature during development is preferably from 15 to 40C. After the formation of the relief image, the plate is dried at 50 to 70 ° C. for about 10 minutes and, if necessary, is subjected to actinic ray treatment in the air or in a vacuum to obtain an intaglio printing plate.

  The photosensitive resin composition of the present invention is most suitably used for a photosensitive resin printing plate precursor for intaglio printing, but is used as a lithographic printing, letterpress printing, stencil printing, or photoresist. Is also possible.

Hereinafter, the present invention will be described in detail with reference to Examples.
Component (A):
Polyamide having an aliphatic ring in the molecular main chain:
Polyamide 1 (manufactured by Toray) having a number average molecular weight of 85,000, in which ε-caprolactam, hexamethylene diammonium adipate and 4,4′-diaminodicyclohexyl methane adipate were polycondensed in almost the same amount, was used. .

Polyamide having a skeleton represented by the general formula (1):
"Toresin" (registered trademark) MF-30 having a number average molecular weight of 40,000 in which 30% of the amide bond of 6-nylon is modified to the skeleton represented by the general formula (1) (Nagase ChemteX Corporation) Was used.
Component (B):
The colloidal silica shown in Table 1 was used. The average particle size is measured and calculated by the apparatus and method described in paragraph 0054 of Patent Document 5. That is, after measuring the specific surface area S (m ² / g) of the dry powder of colloidal silica (using a specific surface area measuring device Monosorb MS-16 manufactured by Yuasa Ionics Co., Ltd.), the average particle diameter was calculated as D (nm) = It was calculated from the equation of 2720 / S.

<Preparation of support (E) having adhesive layer (G)>
66 parts by mass of "VINITOL" (registered trademark) # 284 (manufactured by Nagoya Yuka Co., Ltd.) and 2 parts by mass of hexamethylenetetramine (manufactured by Kanto Chemical Co., Ltd.) were mixed in a solvent of 16 parts by mass of dimethylformamide and 16 parts by mass of xylene. A solution prepared by mixing 90 parts by mass of “jER834” (manufactured by Mitsubishi Chemical Corporation) with a solvent of 30 parts by mass of dimethylformamide and 30 parts by mass of xylene was added to the solution to obtain a coating liquid 1 for the adhesive layer (G). .

  "Amilan" (registered trademark) CM833 (manufactured by Toray Industries, Inc.) 20 parts by mass, "CJPARL" (manufactured by Panasonic Corporation) 50 parts by mass of ethanol, 10 parts by mass of water, 10 parts by mass of dimethylformamide, and 50 parts by mass of benzyl alcohol In a mixed solvent at 70 ° C. for 2 hours to dissolve. Thereafter, 5 parts by mass of “jER834” (manufactured by Mitsubishi Chemical Corporation) and 0.3 parts by mass of dicyanodiamide (manufactured by Kanto Chemical Co., Ltd.) were added at 25 ° C. to obtain a coating liquid 2 for the adhesive layer (G). .

  The coating liquid 1 for the adhesive layer (G) is applied on a 250 μm-thick iron plate (manufactured by Nippon Steel & Sumitomo Metal Corporation) as a support (E) with a bar coater so as to have a thickness of 10 μm after drying. After heating in an oven at 180 ° C. for 3 minutes to remove the solvent, a coating liquid 2 for the adhesive layer (G) was applied thereon with a bar coater so that the dry film thickness became 10 μm, and then heated in an oven at 160 ° C. By heating for 3 minutes, a support (E) having an adhesive layer (G) was obtained.

<Preparation of cover film (H)>
In 100 μm thick “Lumirror” S10 (polyester film, manufactured by Toray Industries, Inc.), 10 parts by mass of “Ultramid 1C” (manufactured by BASF) is dissolved in a mixed solvent of 10 parts by mass of water and 90 parts by mass of ethanol. A coating liquid for a release auxiliary layer was obtained. The coating liquid for a release auxiliary layer thus obtained was applied to a dry film thickness of 1 μm, and dried at 100 ° C. for 25 seconds to obtain a cover film (H).

[Evaluation method]
Evaluation in each example and comparative example was performed by the following method.
The evaluation of the abrasion resistance was performed on the abrasion resistance and the ink resistance, and the evaluation of the high-resolution relief image was confirmed by the evaluation of the image reproducibility.

(1) Abrasion resistance Only the polyester film of the cover film (H) was peeled off from the photosensitive printing original plate having a size of 7 cm × 14 cm (the outermost surface of the photosensitive printing original plate after peeling was a release auxiliary layer having a dry film thickness of 1 μm). The film was adhered in vacuum and exposed with a chemical lamp FL20SBL-360 20 watt (manufactured by Mitsubishi Electric OSRAM Co., Ltd.) under the condition of a gray scale sensitivity of 13 ± 1 step (main exposure) to obtain a 7 cm × 14 cm photosensitive resin plate. The entire surface was light cured. Thereafter, the film was developed with ethanol / water at a liquid temperature of 25 ° C./80/20 for 1 minute using a brush-type developing device, dried at 60 ° C. for 10 minutes, and further subjected to a chemical lamp FL20SBL-360 20 watt (manufactured by Mitsubishi Electric OSRAM Co., Ltd.). ), Post-exposure was performed under the same conditions as in the main exposure to obtain a printing plate for evaluating abrasion resistance.

  The printing plate thus obtained was mounted on a hermetic 6-12 universal (manufactured by TAMPPRINT), squeegeeed 10,000 times using PAD-PLV-1 ink white (manufactured by Navitas) as the ink, and the printing plate was abraded. The depth was measured. If the worn depth is 10 μm or more, the recess filled with the ink during printing becomes shallow, causing printing trouble.

(2) Image reproducibility Only the polyester film of the cover film (H) was peeled off from the photosensitive printing original plate of 10 cm × 10 cm (the outermost surface of the photosensitive printing original plate after peeling was a peeling auxiliary layer having a dry film thickness of 1 μm), and the sensitivity was high. A gray scale negative film for measurement and a positive film for evaluation of image reproducibility (having a line with a width of 300 μm) were brought into close contact with each other in vacuum, and the gray scale sensitivity was 13 ± 1 with a chemical lamp FL20SBL-360 20 watt (manufactured by Mitsubishi Electric OSRAM Co., Ltd.). Exposure was carried out under the condition of step (main exposure). Thereafter, the film was developed with ethanol / water at a liquid temperature of 25 ° C./80/20 for 1 minute using a brush-type developing device, dried at 60 ° C. for 10 minutes, and further subjected to a chemical lamp FL20SBL-360 20 watt (manufactured by Mitsubishi Electric OSRAM Co., Ltd.). ), Post-exposure was performed under the same conditions as in the main exposure to obtain a printing plate for evaluating image reproducibility. The image reproducibility was evaluated by measuring the depth of the concave portion of the 300 μm wide line of the printing plate thus obtained. When the depth of the intaglio portion is 50 μm or less, it is difficult to adjust the depth of the concave portion by the halftone screen film.

(3) Ink resistance Only the polyester film of the cover film (H) was peeled off from the photosensitive printing original plate of 10 cm × 10 cm (the outermost surface of the photosensitive printing original plate after peeling was a peeling auxiliary layer having a dry film thickness of 1 μm). The film was adhered in vacuum and exposed with a chemical lamp FL20SBL-360 20 watt (manufactured by Mitsubishi Electric OSRAM Co., Ltd.) under the condition of a gray scale sensitivity of 13 ± 1 steps (main exposure) of a 10 cm × 10 cm photosensitive resin plate. The entire surface was light cured. Thereafter, the film was developed with ethanol / water at a liquid temperature of 25 ° C./80/20 for 1 minute using a brush-type developing device, dried at 60 ° C. for 10 minutes, and further subjected to a chemical lamp FL20SBL-360 20 watt (manufactured by Mitsubishi Electric OSRAM Co., Ltd.). ), Post-exposure was performed under the same conditions as the main exposure to obtain a printing plate for evaluating ink resistance.

  The printing plate thus obtained was cut into 1 cm × 1 cm, immersed in PAD-PLV-1 Ink White (manufactured by Navitas) at 50 ° C. for 24 hours, and evaluated for ink resistance. When the weight increase rate is 1% or more, the abrasion resistance is inferior because the plate swells with the ink during tampo printing.

Example 1
<Preparation of composition solution 1 for photosensitive resin composition 1>
In a three-necked flask equipped with a stirring spatula and a condenser, the component (A) shown in the column of Example 1 of Table 2 was added, and “Solmix” (registered trademark) H-11 (alcohol mixture, Japan After mixing a mixed solvent of 90 parts by mass of alcohol (manufactured by Alcohol Co., Ltd.) and 10 parts by mass of water, the mixture was heated at 80 ° C. for 2 hours with stirring to dissolve the component (A). After cooling to 40 ° C., other components were added and the mixture was stirred for 30 minutes to obtain a composition solution 1 for the photosensitive resin composition 1.

<Manufacture of photosensitive resin printing plate precursor 1>
The obtained composition solution 1 was cast on a support (E) having the adhesive layer (G), and dried at 60 ° C. for 2.5 hours. At this time, the thickness of the plate after drying (iron plate + photosensitive resin layer) was adjusted to be 0.2 mm. On the photosensitive resin layer (F) thus obtained, a mixed solvent of water / ethanol = 10/90 (weight ratio) is applied, a cover film (H) is pressed on the surface, and photosensitive resin printing is performed. An original plate 1 was obtained. Table 2 shows the results of evaluating the characteristics of the printing plate by the above method using the obtained photosensitive printing original plate 1.

Examples 2 to 8
A photosensitive resin sheet and a photosensitive printing original plate were prepared in the same manner as in Example 1 except that the composition of the photosensitive resin composition was changed as in Examples 2 to 8 in Table 2. Table 2 shows the evaluation results.

Comparative Examples 1-4
A photosensitive resin sheet and a photosensitive printing original plate were produced in the same manner as in Example 1 except that the composition of the photosensitive resin composition was changed as shown in Comparative Examples 1 to 4 in Table 2. Table 2 shows the evaluation results.

Claims (12)

An adhesive layer on at least a support, (A) a polyamide having an aliphatic ring in the molecular main chain and / or a polyamide having a skeleton represented by the general formula (1), and (B) an average particle diameter of 1 to 50 nm. A photosensitive resin layer and a protective layer comprising a photosensitive resin composition characterized by containing certain inorganic fine particles, (C) a compound having an ethylenic double bond, and (D) a photopolymerization initiator are sequentially laminated. A photosensitive resin laminate characterized by comprising:

2. The photosensitive resin laminate according to claim 1, wherein the polyamide (A) having an aliphatic ring in the molecular main chain has a 4,4′-diaminocyclomethane adipate skeleton. 3. The photosensitive resin laminate according to claim 1 or 2, wherein the inorganic fine particles (B) are amorphous silica. The photosensitive resin laminate according to claim 3, wherein the amorphous silica is a hydrolyzate of alkoxysilane. The photosensitive resin laminate according to claim 3 or 4, wherein the amorphous silica is colloidal silica. The photosensitive resin laminate according to claim 5, wherein the colloidal silica is colloidal silica dispersed in an organic solvent. The photosensitive resin laminate according to claim 6, wherein the organic solvent is a lower alcohol. The photosensitive resin laminate according to any one of claims 1 to 7, wherein the compound (C) having an ethylenic double bond has one or more hydroxyl groups in a molecule. The photosensitive resin laminate according to any one of claims 1 to 7, wherein the compound (C) having an ethylenic double bond has two or more hydroxyl groups in a molecule.
A photosensitive resin printing plate precursor used for intaglio printing or pad printing, comprising the photosensitive resin laminate according to any one of claims 1 to 9 . (A) a polyamide having an aliphatic ring in the molecular main chain and / or a polyamide having a skeleton represented by the general formula (1), (B) inorganic fine particles having an average particle diameter of 1 to 50 nm, (C) ethylenic A compound having a double bond, and (D) a polyamide containing a photopolymerization initiator and having (A) an aliphatic ring in a molecular main chain, having a 4,4′-diaminocyclomethane adipate skeleton. Photosensitive resin composition.

(A) a polyamide having an aliphatic ring in the molecular main chain and / or a polyamide having a skeleton represented by the general formula (1), (B) inorganic fine particles having an average particle diameter of 1 to 50 nm, (C) ethylenic A photosensitive resin composition comprising: a compound having a double bond; and (D) a compound having a photopolymerization initiator and (C) a compound having an ethylenic double bond has two or more hydroxyl groups in a molecule. object.