TW202013074A - Resin intaglio printing plate, method for manufacturing same, and printing method - Google Patents

Abstract

The present invention addresses the problem of providing a resin intaglio printing plate that enables attaining a printed matter having good linearity at the edge of an image portion, and a method for manufacturing the resin intaglio printing plate. This resin intaglio printing plate has an image portion including dots formed on the surface of the printing plate, wherein the minimum distance between the edge of the image portion and a dot closest to the edge of the image portion is 20-300 [mu]m.

Description

Resin gravure printing plate, its manufacturing method and printing method

The present invention relates to a resin gravure printing plate.

Pad printing using a gravure printing plate is to place the ink on the plate and remove it with a metal doctor blade, or put the ink into a ceramic or special ring-shaped ceramic that acts as a doctor blade In the ink cup with metal edges, the ink cup is used to remove the plate surface, so that the ink is filled in the concave portion of the gravure printing plate, and the ink is transferred to a soft cushion surface such as silicone rubber, and the A type of lithography in which the ink adhesion surface of the pad is pressure-contacted with the object to be printed. In addition, gravure printing plates can also be used for gravure printing. (For example, Patent Document 1).

In general, the depth and shape of the concave portion of the gravure printing plate system have a significant influence on the appearance of the printed matter. The depth of the concave part is generally adjusted by attaching a positive original film to the original plate of the photosensitive resin printing plate and irradiating it with ultraviolet rays, then sticking to the halftone screen film and irradiating ultraviolet rays, and forming a dot in the concave part and using The depth of the recess becomes adjusted in an appropriate manner.

[Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 5-165200

However, if the depth of the concave portion is adjusted by the method of using the halftone screen, the halftone of the halftone screen will overlap at the end of the image portion of the original film under a certain probability, resulting in the end of the image portion. The bad situation where the linearity of the part deteriorates.

Therefore, an object of the present invention is to provide a resin gravure printing plate and a method for producing a resin gravure printing plate that can obtain a printed matter having excellent linearity at the end of an image portion.

The present invention is a resin gravure printing plate which forms a resin gravure printing plate having an image portion of a dot on the surface of a plate material, wherein the end of the image portion and the dot located closest to the end of the image portion are the smallest The distance is 20 μm or more and 300 μm or less.

In addition, the present invention is a method of manufacturing a resin gravure printing plate, which is a method of manufacturing a resin gravure printing plate by sequentially performing an exposure step and a development step on a photosensitive resin printing plate precursor, wherein the exposure step includes the following steps: This is performed using an original film having an original image part and a dot inside the original image part.

In addition, the present invention is a printing method which uses a resin gravure printing plate having an image portion having dots formed on the surface of a plate for printing, and is characterized by having a distance from the end of the image portion A step of forming dots in an area other than an area of 20 μm or less; a filling step of filling the recording material in the image portion; a first transfer step of transferring the recording material filled in the image portion to the transfer body; and The second transfer step of transferring the recording material transferred to the transfer body to the printed matter to form a printed matter.

By using the resin gravure printing plate of the present invention, it is possible to provide a printed matter having excellent linearity at the end of the image portion.

1‧‧‧ outlets

2‧‧‧ Tangent

3‧‧‧Non-Image Department

4‧‧‧Image Department

5‧‧‧The end of the original image part

6‧‧‧The largest cut point

7‧‧‧ Non-image part of printed matter

8‧‧‧Images of printed matter

9‧‧‧ auxiliary line

d‧‧‧Minimum distance between the end of the image and the dot

S‧‧‧Amplitude

P‧‧‧Contact

Q‧‧‧Point on the end of the image

FIG. 1 is a schematic diagram showing the minimum distance between the end of the image portion and the halftone dot located closest to the end of the image portion.

FIG. 2 is a photograph of the end of the image portion of the printed matter.

[Form for carrying out the invention]

Hereinafter, embodiments of the present invention will be described.

In the present invention, the end portion of the image portion refers to a portion formed on the outermost side of the image portion of the resin gravure printing plate. Specifically, as shown in FIG. 1, it is the boundary between the image portion 4 and the non-image portion 3.

In the resin gravure printing plate of the present invention, it is necessary that the minimum distance between the end of the image portion and the dot located closest to the end of the image portion is 20 μm or more and 300 μm or less. The minimum distance is measured using a digital microscope "VHX-2000" (manufactured by Keyence Co., Ltd.) using an optical microscope under the conditions of a lens Z250 and a magnification of 250 times. The halftone dot located closest to the end of the image part, that is, the halftone dot closest to the boundary line between the image part 4 and the non-image part 3 refers to the halftone dot reflected on the screen during measurement with an optical microscope In the halftone dot, the distance between the end of the image portion (the boundary between the image portion 4 and the non-image portion 3) and the halftone dot is the smallest. Here, the minimum distance between the end of the image part and the halftone dot is the distance d of the straight line PQ connecting the point P on the circumference of the halftone dot 1 shown in FIG. 1 and the point Q of the end of the image part. Specifically, by pulling out the tangent 2 of the point P on the circumference of the dot 1, the angle between the straight line PQ and the tangent to the point P becomes 90°, and the angle between the straight line PQ and the end of the image portion becomes 90° The distance of the straight line PQ is obtained.

That is, in the present invention, no dots exist in the area within 20 m from the end of the image portion, and there are always dots in the area within 300 m or more from the end of the image portion. In addition, the distance to the adjacent (ie, closest) dot is preferably 60 μm to 170 μm.

The minimum distance d between the end of the image portion and the halftone dot located closest to the end of the image portion is preferably 20 μm or more and more preferably 30 μm from the viewpoint of improving the linearity of the end of the image portion Above, even more preferably 40 μm or more. In addition, from the viewpoint of changing the depth of the image portion and adjusting the amount of ink during printing, the minimum distance d is preferably 300 μm or less, more preferably 150 μm or less, and still more preferably 80 μm or less.

The dots present in the image portion have a diameter of preferably 5.0 μm or more, and more preferably 10 μm or more from the viewpoint that the depth of the image portion can be changed and the amount of ink during printing can be adjusted. From the viewpoint of improving the linearity at the end of the image portion, the diameter of the halftone dot is preferably 50 μm or less, and more preferably 40 μm or less.

In addition, the height difference between the surface of the printing plate provided in the image portion of the resin gravure printing plate and the deepest portion of the concave portion existing between the dots among the concave portions provided on the printing plate surface is preferably 10 to 40 μm. Here, the deepest part is defined as the deepest part in the part that does not include the image end in the image part. With a thickness of 10 μm or more, the transfer amount of the ink becomes a sufficient density, and a printed matter with good linearity without blurring can be obtained at the time of printing. With a thickness of 40 μm or less, the deterioration of the linearity due to the bleeding of the printed matter can be prevented. The height difference between the surface of the printing plate and the deepest part of the recessed part was measured using a laser microscope "VK-X250" (manufactured by Keyence) at a magnification of 20 times. The height difference can be adjusted by the ultraviolet irradiation time, the dot diameter of the positive film, and the dot area ratio.

The binder polymer contained in the photosensitive resin composition constituting the resin gravure printing plate of the present invention is preferably (A) a polyamide having an aliphatic ring from the molecular main chain, and having the general formula ( 1) At least one polyamide selected from the group consisting of the polyamides having a skeleton and a methylene chain having 8 or more carbon atoms (hereinafter, referred to as "polyamide (A)" ) Has a function as a carrier resin for maintaining the form in a solid state. In addition, the polyamide (A) is used for imparting developability to a photosensitive resin layer by a solution containing a lower alcohol. In addition, other polymers can be used in combination as a binder polymer.

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

The number average molecular weight of the polyamide (A) is preferably 10,000 to 1,000,000. By being 10,000 or more, it functions as a carrier resin for keeping the photosensitive resin composition in a solid state, and by being 1,000,000 or less, the photosensitive resin layer can be exposed like an image under ultraviolet light. When it is selectively hardened and the unhardened portion is removed by development, it is quickly removed with a developing solution containing lower alcohol. The lower alcohol refers to an alcohol having 5 or less carbon atoms in the molecule. The number average molecular weight of the polyamide (A) may be more preferably 2,000 or more, still more preferably 30,000 or more, and further preferably 1,000,000 or less, and still more preferably 200,000 or less. In the present specification, the number average molecular weight of the polyamide (A) can be set to the number average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

The content of the polyamide (A) is preferably 20 to 80% by mass including the photosensitive resin composition. By containing 20 mass% or more, the photosensitive resin composition at the time of solvent removal can be made into a solid state, and can maintain a form. In addition, by containing 80% by mass or less, the formation of a relief image becomes easy. The content of the polyamide (A) may be more preferably 20% by mass or more, and still more preferably 30% by mass or more. In addition, the content of the polyamide (A) may be more preferably 80% by mass or less, and even more preferably 70% by mass or less.

In the polyamide (A), the polyamine having an aliphatic ring in the main chain of the molecule can be obtained by polymerizing the polyamine with diamine and/or dicarboxylic acid having an aliphatic ring and derivatives thereof Obtained by co-condensation. Examples of the aliphatic ring include alicyclic compounds such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane. Polyamide (A)-based molecular backbones have these alicyclic compounds with divalent residues. Among them, a residue of cyclohexane is preferred, and for example, a polyamide (A) having a 4,4'-diaminodicyclohexylmethane adipic acid skeleton residue is preferred.

As such a polyamide, for example, a polycondensate containing at least 4,4'-diaminodicyclohexylmethane adipate is known. In addition, co-condensates of 4,4'-diaminodicyclohexylmethane adipate, ε-caprolactam, and hexamethylene diammonium adipate as shown in Patent Document 1 are known. . The monomer component containing these aliphatic rings is a total of 100 moles relative to the total polyamine constituent components, that is, the amino carboxylic acid unit (in the case of containing internal amide as a raw material), the dicarboxylic acid unit and the diamine unit. Ear%, preferably 10 to 100 mol%, more preferably 10 to 80 mol%. When the content of the monomer component containing these aliphatic rings is 10 mol% or more, the solubility in the lower alcohol when the photosensitive resin composition is used as the photosensitive resin layer is improved. As a result, the photosensitive resin layer can be exposed like an image with ultraviolet light to selectively harden it, and when the unhardened portion is removed by development, it can be quickly removed with a developer containing a lower alcohol. If it is 80 mol% or less, the chemical resistance as a crystalline polymer can be maintained well.

In addition, other examples of the polyamide (A) may or may not have an aliphatic ring in the molecular main chain, and have a skeleton represented by the following general formula (1).

Polyamide (A) having a skeleton represented by the aforementioned general formula (1) can react the N-methoxymethyl of the amide bond by reacting the hydrogen of the amide bond of the polyamide with formaldehyde and methanol Obtained by basification.

In addition, the hydrogen of the amide bond in the molecule is preferably methoxymethylated at 10 to 50%. By setting the methoxymethylation to 10% or more, the solubility caused by the lower alcohol becomes high, so that the photosensitive resin layer can be selectively cured by exposing the photosensitive resin layer like an image with ultraviolet light, When the unhardened portion is removed by development, it is quickly removed with a developer solution containing lower alcohol. In addition, by setting the methoxymethylation to 50% or less, the wear resistance of the polymer can be maintained. The methoxymethylation of the hydrogen of the amide bond may be more preferably 10% or more, and still more preferably 20% or more. In addition, the methoxymethylation may be more preferably 80% or less, and still more preferably 70% or less. In addition, the methoxymethylation rate of the hydrogen of the amide bond can be controlled by the addition amount of the acetamide and methanol, the reaction temperature, and the reaction time.

As such a polyamide, for example, "Tresin" (registration) in which the number average molecular weight of the skeleton represented by the general formula (1) is 40,000 in which 30% of the amide bond of 6-nylon is modified Trademark) MF-30 (manufactured by Nagase Chemtex Corporation).

In addition, as the polyamide (A), a polyamide having an aliphatic ring in the molecular main chain and a polyamide having a skeleton represented by the general formula (1) may be used as a mixture.

In addition, as another example of the polyamide (A), a polyamide having a methylene chain having 8 or more carbon atoms can be mentioned. For example, what is called a copolymer nylon which copolymerizes the monomer which has a methylene chain of 8 or more carbons, such as nylon 6, nylon 66, and nylon 610, nylon 11, nylon 12, etc., can also be used. By containing 15 to 60% by weight of a monomer having a methylene chain with a carbon number of 8 or more based on the weight ratio of the monomer in the polyamide, it can be dissolved in a lower alcohol. In addition, it is preferable to dissolve in a lower alcohol when the carbon number of the methylene chain is 8 or more, and it is preferable because it is economically advantageous when the carbon number is 12 or less. Examples of such a polyamide having a methylene chain having 8 or more carbon atoms include "Amilan" (registered trademark) CM8000 (Toray Co., Ltd.) which copolymerizes nylon 6/66/610/12. system).

In addition, as the polyamidoamine (A), in the polyamidoamine having a methylene chain having 8 or more carbon atoms, the polyamidoamine having an aliphatic ring in the main chain of the mixed molecule and/or having the general formula ( 1) The polyamide represented by the skeleton is used.

Specific examples of the compound containing (B) an ethylenic double bond used as the photosensitive resin composition include those having only one ethylenic double bond as described in International Publication No. 2018/-123773 Compound (B-1), or a polyvalent (meth)acrylate obtained by addition reaction of an ethylenic double bond and a compound having active hydrogen, addition of an unsaturated epoxy compound and a compound having active hydrogen Compound (B-2) having two or more ethylenic double bonds such as polyvalent (meth)acrylate, polyvalent (meth)acrylamide, and polyvalent vinyl compound obtained by the reaction, but not limited to Etc. The photosensitive resin composition contains a compound having an ethylenic double bond.

Specific examples of the compound (B) containing an ethylenic double bond that can be preferably used include the following, but it is not limited thereto.

啉、苯乙烯及其衍生物、乙烯基吡啶、N-乙烯基-2-吡咯酮、鄰苯二甲酸-β-(甲基)丙烯醯氧基乙基氫酯、N-苯基馬來醯亞胺及其衍生物、N-(甲基)丙烯酸氧基琥珀醯亞胺、(甲基)丙烯酸-2-萘酯、N-苯基(甲基)丙烯醯胺、二乙烯基伸乙基脲、二乙烯基伸丙基脲、乙烯基己內醯胺、乙烯基咔唑、(甲基)丙烯酸二環戊烯酯、1-乙烯基咪唑、2-甲基-1-乙烯基咪唑、丙烯酸(2-甲基-乙基二氧雜環戊烷-4-基)甲酯、醯亞胺丙烯酸酯、(甲基)丙烯酸(2-氧基-1,3-二氧雜環戊烷-4-基)甲酯、(甲基)丙烯酸-2-(氧基二咪唑啶-1-基)乙酯、丙烯酸-2,2,6,6-四甲基-4-哌啶酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸氯乙酯、(甲基)丙烯酸氯丙酯、(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯、(甲基)丙烯酸丁氧基乙酯、乙氧基二乙二醇(甲基)丙烯酸酯、甲氧基三乙二醇(甲基)丙烯酸酯、甲氧基二丙二醇(甲基)丙烯酸酯、(甲基)丙烯醯胺、二丙酮(甲基)丙烯醯胺、N,N’-亞甲基雙(甲基)丙烯醯胺、(甲基)丙烯酸-2,2-二甲基胺基乙酯、(甲基)丙烯酸-2,2-二乙基胺基乙酯、N,N-二甲基胺基乙基(甲基)丙烯醯胺、N,N-二甲基胺基丙基(甲基)丙烯醯胺、(甲基)丙烯酸-2-羥基乙酯等的只具有1個乙烯性雙鍵的化合物；使如二乙二醇二(甲基)丙烯酸酯的聚乙二醇的二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、 新戊四醇四(甲基)丙烯酸酯、丙三醇三(甲基)丙烯酸酯、乙二醇二縮水甘油醚與不飽和羧酸、不飽和醇等的具有乙烯性雙鍵和活性氫的化合物進行加成反應所得到的多價(甲基)丙烯酸酯、使(甲基)丙烯酸縮水甘油酯等的不飽和環氧化合物與如羧酸、胺的具有活性氫的化合物進行加成反應所得到的多價(甲基)丙烯酸酯、亞甲基雙(甲基)丙烯醯胺等的多價(甲基)丙烯醯胺、二乙烯基苯等的多價乙烯基化合物等的具有2個以上乙烯性雙鍵的化合物等。 Examples include: benzyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofuran methyl (meth)acrylate, 2-(meth)acryloxyethyl hexahydrophthalic acid , Phenoxydiethylene glycol (meth)acrylate, 2-(meth)acryloyloxyethyl phthalate, neopentyl glycol-(meth)acrylic acid-benzoate, (meth Base) acryl

Porphyrin, styrene and its derivatives, vinylpyridine, N-vinyl-2-pyrrolidone, phthalic acid-β-(meth)acryloyloxyethyl hydrogen ester, N-phenylmaleimide Imines and their derivatives, N-(meth)acrylic acid oxysuccinimide, 2-naphthyl (meth)acrylate, N-phenyl(meth)acrylamide, divinyl urea , Divinyl propyl urea, vinyl caprolactam, vinyl carbazole, dicyclopentenyl (meth)acrylate, 1-vinylimidazole, 2-methyl-1-vinylimidazole, acrylic acid ( 2-methyl-ethyldioxolane-4-yl) methyl ester, amide imine acrylate, (meth)acrylic acid (2-oxy-1,3-dioxolane-4 -Yl)methyl ester, (meth)acrylic acid-2-(oxydiimidazolidin-1-yl)ethyl ester, acrylic acid-2,2,6,6-tetramethyl-4-piperidinyl ester, (meth Base) methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Ester, lauryl (meth)acrylate, stearyl (meth)acrylate, chloroethyl (meth)acrylate, chloropropyl (meth)acrylate, methoxyethyl (meth)acrylate, (meth) Group) ethoxyethyl acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxy Dipropylene glycol (meth)acrylate, (meth)acrylamide, diacetone (meth)acrylamide, N,N'-methylenebis(meth)acrylamide, (meth)acrylic acid -2,2-dimethylaminoethyl, (meth)acrylic acid-2,2-diethylaminoethyl, N,N-dimethylaminoethyl(meth)acrylamide, Compounds such as N,N-dimethylaminopropyl (meth)acrylamide, 2-hydroxyethyl (meth)acrylate that have only one ethylene double bond; such as diethylene glycol di (Meth)acrylate polyethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, neopentaerythritol tri(meth)acrylate, neopentaerythritol tetra (Meth) acrylate, glycerol tri (meth) acrylate, ethylene glycol diglycidyl ether and unsaturated carboxylic acid, unsaturated alcohol and other compounds having an ethylene double bond and active hydrogen addition reaction The resulting polyvalent (meth)acrylate, polyvalent (meth)acrylic acid, and other unsaturated epoxy compounds such as glycerol (meth)acrylate, and compounds such as carboxylic acids, amines with active hydrogen addition reaction of the resulting polyvalent ( Polyvalent (meth)acrylamide such as meth)acrylate, methylenebis(meth)acrylamide, polyvalent vinyl compounds such as divinylbenzene, etc. have two or more ethylenic double bonds Compounds etc.

Among these ethylenic double bond-containing compounds, those having at least one hydroxyl group are preferred. Such a compound has good compatibility with polyamide (A). In addition, the dispersibility of inorganic fine particles (D) in the pH range of extraction water of 5.5 to 8.5 also becomes good. When blended with photosensitive resin In the case of a composition, a uniform composition can be produced. Examples of such (B) compounds containing an ethylenic double bond include: (meth)acrylic acid-2-hydroxy-3-phenoxypropyl ester, (meth)acrylic acid[4-(hydroxymethyl) ring Hexyl]methyl ester, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-chloro(meth)acrylic acid -2-hydroxypropyl ester, phthalic acid-β-hydroxy-β'-(meth)acryloxyethyl, (meth)acrylic acid-3-chloro-2-hydroxypropyl ester, glycerol (Meth) acrylate, etc.

Furthermore, it is more preferable that the (B) compound having two or more hydroxyl groups contains an ethylenic double bond. Such a compound can suppress the swelling of the resin gravure printing plate caused by the organic solvent of the ink used for pad printing through the hydrogen bond of the hydroxyl group. Examples of such compounds include glycerol mono(meth)acrylate and neopentyltetraol mono(meth)acrylate, but these are not limited to these examples.

The content of these (B) compounds containing an ethylenic double bond is preferably 5 to 200 parts by mass relative to 100 parts by mass of the polyamide (A). If it is 5 parts by mass or more, the printing plate can be used without swelling when printing with ink. If it is 200 parts by mass or less, the photosensitive resin composition can be easily formed, which is preferable. (B) The compound containing an ethylenic double bond can be contained in more preferably 10 parts by mass or more, and still more preferably 20 parts by mass or more, based on 100 parts by mass of the polyamide (A). In addition, the content of the compound containing (B) an ethylenic double bond may be more preferably 150 parts by mass or less, and still more preferably 100 parts by mass or less.

(B) The compound containing an ethylenic double bond preferably contains both acryl and methacryl, preferably (B) the number of methacryl groups in the compound containing an ethylenic double bond More than propylene acetyl group. Generally speaking, the reaction speed of the methacryloyl group is slower than that of the acryloyl group. Therefore, in the case of ultraviolet irradiation through a positive-type film, if the number of methacryl groups is large, the concave portion of the relief becomes deep, so close to the 300-line 90% and other halftone screen film, irradiating ultraviolet rays by With the screen mesh formed, the depth of the concave portion can be easily adjusted.

All (C) photopolymerization initiators used as the photosensitive resin composition can be used if they can polymerize a polymerizable carbon-carbon unsaturated group by light. Among them, those having a function of generating free radicals by self-decomposition and dehydrogenation due to light absorption can be preferably used. Examples of the (C) photopolymerization initiator include benzoin alkyl ethers, benzophenones, anthraquinones, benzyls, acetophenones, and diethyl acetyls.

The blending amount of the (C) photopolymerization initiator is preferably in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the polyamide (A). If it is 0.1 parts by mass or more, the formability of the relief image is improved, and if it is 20 parts by mass or less, the precipitation of the photopolymerization initiator can be suppressed. (C) The blending amount of the photopolymerization initiator may be more preferably 0.5 parts by mass or more, and still more preferably 1 part by mass or more. In addition, the blending amount of the (C) photopolymerization initiator may be more preferably 10 parts by mass or less, and still more preferably 8 parts by mass or less.

In addition, the photosensitive resin gravure printing plate of the present invention is excellent in abrasion resistance and improves the ink removability of the plate surface when squeegee is performed with a blade of a pad printing machine For the purpose, inorganic fine particles (D) may be blended into the photosensitive resin composition. Examples of preferable inorganic fine particles include inorganic fine particles having an average particle diameter of 0.5 μm or more and 4 μm or less and a sphericity of 0.90 or more.

Inorganic fine particles (D), with an average particle size of 0.5 μm or more, can ensure the abrasion resistance when the pad printing machine is bladed (blade), and 4 μm or less, can be dialed with the pad of the pad printing machine Ink off the surface of the plate. The average particle diameter of the inorganic fine particles (D) may be preferably 0.8 μm or more, and more preferably 1.0 μm or more. In addition, the average particle diameter may be preferably 4.0 μm or less, and more preferably 3.0 μm or less. In addition, since the sphericality of the inorganic fine particles (D) is 0.90 or more, preferably 0.90 to 1.0, the surface roughness of the printing plate becomes smaller, so that it is possible to achieve better ink repellency. In addition, in the present invention, the average particle diameter of the inorganic fine particles (D) is the median diameter measured by the laser diffraction scattering method. In addition, the so-called sphericity refers to the observation of the shape of 50 inorganic fine particles (D) using a scanning electron microscope, and the ratio of the shortest diameter to the longest diameter of each inorganic fine particle is obtained, and the ratio of 50 averages .

Examples of such inorganic fine particles (D) include metal single inorganic fine particles, inorganic oxide particles, inorganic salt inorganic fine particles, inorganic fine particles composed of organic components and inorganic components, and the like. Among them, from the viewpoint of suppressing the scattering of ultraviolet rays when the photosensitive resin composition is irradiated with light to cure it, it is preferably polymerized with (A) of the organic component contained in the photosensitive resin composition Acetamide, (B) a compound having an ethylenic double bond, (C) a silica particle having a refractive index close to that of a photopolymerization initiator and a surfactant. In addition, from the viewpoint of safe disposal, amorphous silicon dioxide is more preferable. On the other hand, in order to improve the abrasion resistance when the plate is removed by the blade, alumina with a larger Vickers hardness than silica particles can be used, or silica particles and alumina can be mixed and used .

The method for producing such amorphous silica and alumina having a sphericity of 0.90 or more is not particularly limited, but it is known such as Japanese Patent Laid-Open No. 58-145613 and Japanese Patent Laid-Open No. 2006-36915 As shown in the Japanese Patent Publication, a method of melting silicon dioxide particles or aluminum oxide particles in a flame; as shown in Japanese Patent Laid-Open No. 2006-36915, by the VMC (Vaperized Metal Combustion) method, burning silicon powder or metal aluminum Manufacturing methods, etc.

The inorganic fine particles (D) preferably have a specific surface area of 10 m ² /g or less. If it is 10 m ² /g or less, the leveling of the photosensitive resin composition is good, and the formation of a flat plate surface becomes easy. The specific surface area of the inorganic fine particles (D) may be more preferably 9 m ² /g or less, and still more preferably 8 m ² /g or less. In this specification, the specific surface area of the inorganic fine particles (D) can be measured based on the method described in JIS Z8830:2013.

On the other hand, the maximum particle diameter of the inorganic fine particles (D) is preferably 20.0 μm or less. In the case where the maximum particle size is 20.0 μm or less, the ink residue when scraping with the blade of the pad printer can be reduced. The maximum particle diameter of the inorganic fine particles (D) is more preferably 10.0 μm or less. In addition, the maximum particle size is set by passing it through a sieve corresponding to the size of the inorganic fine particles.

In addition, the inorganic fine particles (D) preferably contain the pH of the extraction water in the range of 5.5 to 8.5. With this range, the dispersibility of other components used in the present invention is good, and the aggregation of inorganic fine particles is suppressed. More preferably, the pH of the extraction water is in the range of 6.0 to 8.0. In addition, in the production of the photosensitive resin composition used in the resin gravure printing plate original plate or the printing plate original plate, even if the inorganic fine particles (D) are precipitated and aggregated during storage, the electrostatic attraction is small, and then they are stirred again. The dispersion system is easy and has excellent handling properties. The pH of the extraction water of the inorganic fine particles (D) is a mixture of 10% by mass of inorganic fine particle powder in distilled water, and the upper clarified water after stirring for 30 minutes can be measured with a pH meter. In addition, the pH of the inorganic fine particles can be adjusted by causing an activity inhibitor to act on the active hydroxyl group of the inorganic fine particles. As an example of the activity inhibitor, one or more selected from organic phosphine compounds, thioether compounds, thiol compounds, ketone compounds, and amide compounds may be used, but it is not limited thereto. In addition, these active inhibitors can be mixed with inorganic fine particles (D) and heated at a temperature of 90 to 180°C for 4 to 24 hours before use.

When such inorganic fine particles (D) are used, when blending with a compound having an ethylenic double bond in polyamides (A) and (B), aggregation and reagglomeration of the inorganic fine particles (D) are suppressed and it is possible Use the blade of the pad printer to remove the ink on the surface of the plate.

In order to impart abrasion resistance, the inorganic fine particles (D) are preferably contained in the photosensitive resin composition at 3% by mass or more, and in order to enable the formation of the photosensitive resin layer, it is preferably 70% by mass or less. The content of the inorganic fine particles (D) may be more preferably 8% by mass or more and 60% by mass or less, and still more preferably 10% by mass or more and 30% by mass or less.

A surface modifier can also be used to introduce the ethylenic double bond to the surface of the inorganic fine particles (D). As such a modifier, for example, (3-propenyl propyl) trimethoxy silane, methacryl propyl trimethoxy silane, methacryl propyl triethoxy silane , Methacryloyloxymethyltriethoxysilane, methacryloyloxymethyltrimethoxysilane, etc., but not limited thereto. By modifying the surface of the ethylenic double bond to the inorganic fine particles (D), the dispersibility becomes good when mixed with the polyamide (A), (B) compound having an ethylenic double bond, and aggregation and reaggregation can be suppressed.

It is also possible to add ethylene glycol, diethylene glycol, triethylene glycol, glycerin and its derivatives, trimethylolpropane and its derivatives, trimethylolethane and tris in the photosensitive resin composition Its derivatives, neopentaerythritol and its derivatives and other polyols are used as compatibility aids for improving compatibility and flexibility. These polyols are preferably added in an amount of 30% by mass or less relative to the entire photosensitive resin composition. In particular, by improving compatibility, it is possible to suppress turbidity of the resin composition and bleeding of low-molecular-weight components.

系、二苯甲酮系的化合物，此等可以使用1種以上。又，紫外線吸收劑的摻合量係相對於全部感光性樹脂組成物，較佳為在0.001~5質量%的範圍使用。 In addition, in the resin gravure printing plate formed from the photosensitive resin printing plate precursor using the photosensitive resin composition, in order to form a well-shaped concave portion, for the purpose of suppressing the scattering of light in the photosensitive resin layer, it may be Blended with UV absorbers. As preferred ultraviolet absorbers, benzotriazole-based, tri-

One or more types of compounds based on benzophenone and benzophenone can be used. In addition, the blending amount of the ultraviolet absorber is preferably used in the range of 0.001 to 5% by mass based on the entire photosensitive resin composition.

In addition, in order to increase the thermal stability of the photosensitive resin composition, a conventionally known (E) polymerization inhibitor can be added. Examples of preferred (E) polymerization inhibitors include phenols, hydroquinones, catechols, and nitrosoamine derivatives. These blending amounts are preferably used in the range of 0.001 to 5 with respect to the entire photosensitive resin composition.

In addition, organic solvents, dyes, pigments, surfactants, defoamers, perfumes, and the like can be added to the photosensitive resin composition as other components.

Next, the photosensitive resin laminate will be described.

The photosensitive resin lamination system sequentially laminates at least the support (F) with an adhesive layer (G), a layer formed of a photosensitive resin composition, and a protective layer. Then, a photosensitive resin printing plate precursor is formed using this photosensitive resin laminate. That is, the photosensitive resin printing plate precursor is formed by sequentially laminating an adhesive layer (G), a photosensitive resin layer (H) formed of a photosensitive resin composition, and a protective layer on at least the support (F).

As the support (F), 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. Put it on the plate and remove it with a metal scraper, or put the ink into the ink cup with a ring-shaped ceramic or special metal edge that acts as a scraper and remove the plate with the ink cup. Therefore, it is preferable to use, for example, a metal plate that is not deformed by the force at the time of pulling out.

The shape of the support (F) can be a plate, a roller, or the like, but it is preferably appropriately selected according to the printing method.

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

The support (F) is preferably for easy adhesion treatment for the purpose of improving the adhesion with the photosensitive resin layer (H). As a method of easy adhesion treatment, mechanical treatments such as sand blasting, physical treatments such as corona discharge, chemical treatments such as coating, etc. can be exemplified, but from the viewpoint of adhesion, it is preferably by coating To set up the next layer (G).

The adhesive layer (G) is not particularly limited as long as it improves the adhesion between the support (F) and the photosensitive resin layer (H). The adhesive layer (G) preferably contains at least a part of the constituent units contained in the photosensitive resin layer (H), and the adhesiveness is further improved. As such a common structural unit, a polymer compound soluble in a solution containing a lower alcohol can be exemplified. In addition, as the soluble polymer compound, a polyamide resin containing a unit of ε-caprolactam can be preferably mentioned.

The photosensitive resin layer (H) is formed of the above-mentioned photosensitive resin composition. The thickness of the photosensitive resin layer (H) is preferably 0.01 mm or more, and more preferably 0.02 mm or more from the viewpoint of having a sufficient relief depth to improve suitable printability. On the other hand, the thickness of the photosensitive resin layer (H) is preferably 1 mm or less, and more preferably 0.7 mm or less from the viewpoint of cost and resource saving.

The photosensitive resin printing plate original plate preferably has a cover film (I) as a protective layer on the photosensitive resin layer (H) from the viewpoint of protecting the surface and preventing the adhesion of foreign materials and the like. The photosensitive resin layer (H) may be in direct contact with the cover film (I), or may have one layer or a plurality of layers between the photosensitive resin layer (H) and the cover film (I). As a layer between the photosensitive resin layer (H) and the cover film (I), for example, a peeling auxiliary layer (J) provided for the purpose of preventing adhesion on the surface of the photosensitive resin layer can be mentioned.

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

Next, a method of manufacturing a photosensitive resin gravure printing plate precursor will be described. For example, after heating and dissolving polyamide (A) in a mixed solvent containing alcohol as a main component, (B) a compound containing an ethylenic double bond, (C) a photopolymerization initiator, and inorganic fine particles as needed, The plasticizer and other additives are stirred and mixed thoroughly to obtain a photosensitive resin composition solution.

The photosensitive resin layer (H) containing the photosensitive resin composition can be cast on the support (F) having the adhesive layer (G) by casting the photosensitive resin composition solution obtained by the above method , Dried to get. After that, the photosensitive resin printing plate original can be obtained by closely adhering the cover film (I) to which the peeling auxiliary layer (J) is arbitrarily applied to the photosensitive resin layer (H). In addition, a photosensitive resin sheet can also be obtained by laminating a photosensitive resin sheet by dry film formation and sandwiching the photosensitive sheet between a support (F) and a cover film (I) to obtain a photosensitive resin printing plate original. In addition, a photosensitive resin composition not containing inorganic fine particles (D) may be provided between the adhesive layer (G) and the photosensitive resin layer (H).

In the case where the photosensitive resin printing plate precursor has a peeling auxiliary layer (J), the method for forming the peeling auxiliary layer (J) is not particularly limited, but from the viewpoint of the ease of forming a thin film, the following method can be performed particularly well : A solution in which the component of the peeling auxiliary layer (J) has been dissolved in the solvent is applied on the cover film (I) to remove the solvent. Examples of the method for removing the solvent include hot air drying, far infrared drying, and natural drying. The solvent dissolving the component of the peeling auxiliary layer (J) is not particularly limited, but water, alcohol, or a mixture of water and alcohol can be preferably used.

Next, a method of manufacturing the resin gravure printing plate of the present invention used for a photosensitive resin printing plate original plate will be described. The printing plate of the present invention can be obtained by sequentially exposing and developing a photosensitive resin printing plate original plate. Then, the exposure step includes the step of using an original film having an original image portion and a halftone dot inside the original image portion. The original film having the original image portion and the dots inside the original image portion can be obtained by the following method. First, read the original image into an image processing software, such as "Adobe Illustrator" (made by Adobe Systems). Next, select the original image part, set the offset value from -0.020mm to -0.30mm from the path of the object tab, and chrome the original image part. After that, by setting the color density of the rimmed portion to K100% and the color density of the original portion other than the rimmed portion to K100%, the original portion and the original image can be obtained. Original film of the dot inside the part. Hereinafter, an example of this manufacturing method will be described, but the manufacturing method of the resin gravure printing plate of the present invention is not limited to this.

First, the front end of the original part in the positive original film used is trimmed. In addition, the original image portion refers to an area corresponding to the image portion of the intaglio printing plate. Flanging is effective for halftone dots arranged so as to avoid the end of the image part. By forming a halftone screen of the original image part other than the edged part, a gravure printing plate corresponding to the end of the original image part The linearity of the image part is improved. From the viewpoint of improving the linearity of the end portion of the image portion in the printed material, the width of the border portion of the original image portion is preferably 20 μm or more, more preferably 30 μm or more, and still more preferably 40 μm or more. In addition, from the viewpoint of changing the depth of the image portion and adjusting the amount of ink during printing, it is preferably 300 μm or less, more preferably 150 μm or less, and still more preferably 80 μm or less.

Next, a halftone screen is formed outside the edging portion of the original image portion to produce an original film portion. Halftone screen integrated positive film. In addition, it is sufficient if the halftone dot system is included at least inside the original image portion.

It is preferable that the dots existing in the original image portion be 3% or more and 20% or less when the area of the original image portion is 100%. The so-called dot area ratio refers to the area ratio of dots existing in the original image portion, and the area ratio is expressed by the ratio of the hollow area to the area of the original image portion. In the original image film, there are hollow dots in the original image portion of the black matrix. The dot area ratio can be selected at any 10 points on the original part of the positive film. For the selected point, a positive color filter is used and a Macbeth transmission densitometer "TR-927" (manufactured by Kollmorgen Instruments Corps.) is used. Determination. In the present invention, the average value of the aforementioned 10-point measurement results is defined as the halftone dot area ratio. The dot area ratio is preferably 3 from the viewpoint of eliminating uneven ink removal caused by the blade falling into the concave portion when the excess ink existing on the surface of the resin gravure printing plate is removed with a doctor blade or the like % Or more, more preferably 5% or more. From the viewpoint of deepening the depth of the resin gravure printing plate and adjusting the amount of ink during printing, it is preferably 20% or less, and more preferably 15% or less.

After that, when the photosensitive resin printing plate original plate is provided with the cover film (I), it is peeled off, the aforementioned integrated positive film is closely attached to the photosensitive resin layer (H), and ultraviolet rays are irradiated to form a gravure printing plate The image part can also adjust the depth of the concave part by forming a halftone dot. In addition, by trimming the end of the original image part, the dots falling on the end of the image part disappear, so there is no unintended cutout at the end of the image part in the print, the image part of the print The linearity of the end is improved. Ultraviolet irradiation can usually be performed using high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halogen lamps, xenon lamps, carbon arc lamps, chemical lamps, etc. that can irradiate wavelengths of 300 to 400 nm.

Next, the photosensitive resin printing plate precursor is immersed in a developing solution, and a relief device is formed on the substrate by a brush-type developing device that removes the unhardened portion by brushing. In addition to the brush type developing device, a spray type developing device may be used. As the developing solution, a solution containing a lower alcohol or a surfactant may be further used.

In addition, the liquid temperature during development is preferably 15 to 40°C. After the relief statue is formed, it can be dried at 50-70°C for about 10 minutes. If necessary, active light treatment in the atmosphere or vacuum can be used as a post-exposure step to obtain a resin gravure printing plate.

In addition, the photosensitive resin composition is most suitable for use in resin gravure printing, particularly a photosensitive resin printing plate precursor for pad printing, but it can also be used for lithography, relief printing, stencil printing, and photoresist.

In addition, a resin gravure printing plate whose support is a plastic film is lighter in weight and easier to handle than a resin gravure printing plate using a metal as a support. As a method of fixing such a resin gravure printing plate whose support is a plastic film to a pad printing machine, there is a method of attaching a double-sided tape to the support of the resin gravure printing plate, and fixing one side of the double-sided tape to the plate of the pad printing machine Method, but compared with the use of magnets to fix the support containing metal, especially iron resin gravure printing plate to the plate, because it is firmly attached to the support, the installation and removal of the resin gravure printing plate From the viewpoint of reposting work (exchange work) (reproducibility), time may be difficult to use.

In addition, in pad printing, the ink on the surface of the printing plate is removed by a blade. However, if a resin gravure printing plate with a plastic film as the support is used, the support deforms when the ink is removed by the blade, and it may not perform well. The situation of printing.

Therefore, in the case of pad printing, when using a resin gravure printing plate whose support is a plastic film, it is preferably used for easy exchange (excellent reproducibility). It is also a member (plate, structural body) which is difficult to deform at the time of the support.

Such a board preferably has an adhesive layer on at least one side of the substrate. The adhesive layer is preferably located in the outermost layer.

As the base material, any one of metal, plastic, wood, glass, ceramic, etc. can be used. The metal is preferably iron or aluminum, and the plastic is preferably polyester. Among them, the iron system is particularly suitable for use when the magnet is used in the plate stage of the pad printing machine.

The thickness of the substrate is preferably 200 μm or more and 1 cm or less. With a mechanical strength of 200 μm or more, it can perform well: put the ink on the plate and pull it away with a metal scraper, or put the ink into a ceramic or special metal with a ring that acts as a scraper In the ink cup on the edge, use the ink cup to remove the layout. That is, it is possible to suppress the deformation of the support when the ink is removed by the blade. In addition, since the base material is 1 cm or less, it is preferable from the viewpoint of mounting to a printing machine and cost.

The adhesive layer is a layer having self-adhesiveness. For example, the adhesive layer described in JP-A-2014-122285 can be used, but it is not limited thereto.

The thickness of the adhesive layer is preferably 1 to 100 μm, and more preferably 5 to 75 μm. By setting it to 1 μm or more, sufficient adhesion to the adherend can be ensured, and by setting it to 100 μm or less, the processing when forming the adhesive layer becomes easy.

This plate is fixed to the support of the resin intaglio printing plate through the adhesive layer of the plate. The adhesion force between the adhesive layer and the support body of the resin gravure printing plate to be adhered is preferably in the range of 0.015N to 0.1N/25mm. With 0.015N/25mm or more, it can be carried out well: place the ink on the surface of the resin gravure printing plate, remove it with a metal scraper, or put the ink into a ceramic with a ring that functions as a scraper Or in the ink cup with a special metal edge and use the ink cup to remove the layout. That is, it is possible to suppress the deformation of the support when the ink is removed by the blade. In addition, from the viewpoint of the re-sticking operation (reproducibility), it is preferably 0.1 N/25 mm or less.

Next, as a method for forming the adhesive layer on the substrate, as a first example, a method of applying the components of the adhesive layer on the substrate; as a second example, preparing a film with an adhesive layer formed on the film The method on the side opposite to the side on which the adhesive layer is formed is to apply an adhesive, and to adhere to the substrate through the adhesive; the third example is to use an adhesive layer formed on one side of the film, on the other side A film in which an adhesive layer that can be adhered to the substrate is formed, and a method of bonding the film to the substrate through the adhesive layer, etc., but is not limited thereto.

In addition, the size of such a board is preferably a size that can be mounted on a printing plate.

By using such a plate, even if a resin gravure printing plate whose support is a plastic film is used, it can be easily exchanged (excellent reproducibility). In addition, it can suppress the support when the ink is removed by the blade Deformed.

This type of board is used when printing is produced using pad printing. The method of manufacturing a printed matter using pad printing using such a board preferably includes the following steps in sequence.

Step 1) Step of fixing the support body of the resin gravure printing plate to the board through the adhesive layer of the board to obtain a structure.

Step 2) The step of attaching the structure to the pad printer.

By using the method described above, even if a resin gravure printing plate whose support is a plastic film is used, it can be easily exchanged (excellent reproducibility). In addition, it can suppress the support when the ink is removed by the blade Deformed. As a result, the printability of pad printing can be improved.

In addition, in the present invention, it is possible to use a bonding layer that penetrates the plate to fix (integrate) the resin gravure printing plate to the structure on the plate.

That is, the structure is a structure having a resin layer including a concave portion, a support, an adhesive layer, and a substrate in order.

Such a structure can be used when manufacturing printed matter by pad printing. The method of manufacturing a printed matter using pad printing using such a structure preferably includes the step of mounting the structure on a pad printer.

By using such a structure and method, even if a resin gravure printing plate whose support is a plastic film is used, it can be easily exchanged (excellent reproducibility). In addition, it can also suppress Deformation of the support. As a result, the printability of pad printing can be improved.

In addition, the technology described in the specification of Japanese Patent Application No. 2017-120049 can be applied to the board, the structure, and the method of using them.

The object that can be printed using the resin gravure printing plate of the present invention is not particularly limited, and examples thereof include paper, plastic, cloth, glass, metal, and ceramics. Among them, the resin gravure printing plate of the present invention is preferably used for printing of so-called non-absorbent originals that do not absorb ink, especially plastics, glass, metals, ceramics, etc. For example, The application of directly printing electrode circuits, etc. on plastic, glass, metal, ceramic. The electrode circuit requires high linearity in order to keep lines even in a fine pattern. By using the present invention, it is possible to provide a printed matter that is excellent in linearity at the end of the image portion and is not broken.

[Example]

Hereinafter, the present invention will be described in detail with examples.

<Fabrication of Support (F) with Adhesive Layer (G)>

To the solvent of 16 parts by mass of dimethylformamide and 16 parts by mass of xylene, 66 parts by mass of "Binitol" (registered trademark) #284 (made by Nagoya Oil Chemical Co., Ltd.) and hexamethylenetetramine were mixed (Made by Kanto Chemical Co., Ltd.) 2 parts by mass of a solution, mixed with 30 parts by mass of dimethylformamide and 30 parts by mass of xylene and mixed with bisphenol A "jER" (registered trademark) 834 (Mitsubishi Chemical (Manufactured by a company) 90 parts by mass of a solution to obtain a coating liquid 1 for an adhesive layer (G).

At 70° C., mix “Amilan” (registered trademark) CM833 (Toray (share) in a mixed solvent of 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. )) 20 parts by mass, "CJPARL" (manufactured by Automotive & Industrial Systems) 10 parts by mass for 2 hours and dissolved. Thereafter, at 25° C., 5 parts by mass of bisphenol A “jER” (registered trademark) 834 (manufactured by Mitsubishi Chemical Corporation) and 0.3 parts by mass of dicyanodiamide (manufactured by Kanto Chemical Corporation) were added to obtain Next, the coating liquid 2 for the layer (G).

Using a bar coater, apply the coating liquid 1 of the adhesive layer (G) to a 250 μm-thick iron plate (made by Nippon Steel & Sumitomo Co., Ltd.) with a thickness of 10 μm after drying so that the thickness of the film becomes 10 μm. After heating in a 180°C oven for 3 minutes to remove the solvent, the adhesive layer (G) was coated with the coating liquid 2 on the bar coater so that the dry film thickness became 10 μm, and heated in a 160°C oven 3 In minutes, a support (F) having an adhesive layer (G) was obtained.

<Cover Film (I)>

As the cover film (I), "Lumirror" (registered trademark) S10 (polyester film, manufactured by Toray Co., Ltd.) with a thickness of 100 μm was used.

<Original version of photosensitive resin printing plate>

The following shows the materials used in the original plate of the photosensitive resin printing plate.

Polyamide (A):

Polyamides with aliphatic rings in the molecular backbone:

Using ε-caprolactam, hexamethylene diammonium adipate, and 4,4'-diaminodicyclohexylmethane adipate, almost the same amount of polycondensation, the number average molecular weight is 85,000. Acetamide 1 (manufactured by Toray Co., Ltd.) 80 parts by mass.

(B) Compounds containing ethylenic double bonds

Compound having an ethylenic double bond containing one hydroxyl group

. 20 parts by mass of glycerin dimethacrylate (LIGHT-ESTER G101P manufactured by Kyoeisha Chemical Co., Ltd.)

. 60 parts by mass of 2-hydroxypropyl methacrylate (Kyoeisha Chemical Co., Ltd. LIGHT-ESTER HOP)

(C) Photopolymerization initiator

. 2,2-dimethoxy-1,1-diphenylethane-1-one ("IRGACURE" (registered trademark) 651 manufactured by BASF) 3 parts by mass

Other ingredients

. Inorganic fine particles (D): SC-2500SQ (made by Admatechs Co., Ltd., spherical silica, sphericity 0.95, average particle diameter 0.5 μm) 20 parts by mass

. Polymerization inhibitor: N-(ammoniumoxy)-N-nitrosophenylamine (Kanto Chemical Co., Ltd. Cupferron) 0.01 parts by mass

. Ultraviolet absorber: 2,4-di-tertiary butyl-6-(5-chloro-2H-1,2,3-benzotriazol-2-yl)phenol ("TINUVIN" (registered trademark manufactured by BASF Corporation ) 326) 0.01 parts by mass.

In a three-necked flask equipped with a scraper for stirring and a cooling tube, after mixing 180 parts by mass of the mixed solvent of polyamidoamine (A) and water/ethanol = 10/90 (weight ratio), the mixture was stirred at 80°C Heat for 2 hours to dissolve the polyamide (A). After cooling to 40°C, the aforementioned (B), (C) and other components are added and mixed, and further dispersed using a continuous media disperser (NANO GRAIN MILL, manufactured by Asada Iron Works Co., Ltd.) to obtain a photosensitive resin composition Thing. Using a bar coater, the obtained photosensitive resin composition was applied to the support (F) having the aforementioned 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 0.5 mm. A mixed solvent of water/ethanol=10/90 (weight ratio) is applied on the photosensitive resin layer (H) obtained in this way, and the cover film (I) is pressed onto the surface to obtain a photosensitive resin printing plate original .

<positive film>

The black carbon film TK100 (manufactured by Takano Machinery Co., Ltd.) is mounted on the outer surface of the drum-type plate mounter "CDI SPARK" equipped with an optical fiber laser having an infrared light emitting area so that the base material contacts the drum. Esco.Graphics Co., Ltd.), under the conditions of laser power of 9kW and drum rotation speed of 400rpm, draw the test patterns corresponding to the image parts and dots shown in Table 1 to produce positive films 1-10. In addition, the height difference between the surface of the resin gravure printing plate and the deepest part of the recesses existing between the dots among the recesses provided on the printing plate surface is adjusted by changing the dot diameter of the positive film.

[Evaluation method]

The evaluation in each example and comparative example was performed by the following method.

(1) The difference in height between the surface of the resin gravure printing plate and the deepest part of the recess between the dots among the recesses provided on the printing plate surface

Using a laser microscope "VK-X250" (manufactured by Keyence), the difference in height between the surface of the resin gravure printing plate and the deepest part of the recess provided on the surface between the dots was observed at a magnification of 20 times. The average value of the measurement results of the dots is the difference in height between the surface of the printing plate and the deepest part of the recess between the dots.

(2) Linearity of the end of the image part

The resin gravure printing plate is mounted on hermetic 6-12 universal (manufactured by TAMPOPRINT), the ink uses PAD-PLV-1 ink white (manufactured by Navitas), after scraping the ink once, it is transferred to a pad, and the PET film is carried out print. Using a digital microscope "VHX-2000" (manufactured by Keyence), the end of the image portion of the obtained printed matter was observed under the conditions of lens Z250 and magnification of 250 times, and the end of the printed matter shown in FIG. 2 was measured The amplitude s of the shape. The amplitude s refers to the portion cut from the original image portion end 5 to the largest notch point 6 in the portion formed by the cut portion that is generated at the image portion end of the printed matter and does not exist in the original film. depth. In Fig. 2, line 9 is an auxiliary line for confirming that point 6 is the maximum depth. When measuring with a digital microscope, the amplitude with the largest depth among the amplitudes reflected on the screen is defined as the amplitude s.

As an evaluation criterion, when the amplitude s is 30 μm or more, the linearity is poor, and the shape of the end portion of the printed matter is jagged to cause a printing failure. Therefore, it is judged as a failure. If the amplitude is less than 30 μm, it is judged as passing, if it is within 20 μm, it is judged as good, and if it is within 10 μm, it is judged as excellent.

Example 1

Only the polyester film covering the film (I) was peeled from the photosensitive resin printing plate original plate of 7 cm×14 cm (the outermost surface of the photosensitive resin printing plate original plate after peeling was a peeling auxiliary layer with a dry film thickness of 1 μm). Table 1 The positive type film 1 is vacuum-attached, with a chemical lamp FL20SBL-360 20 watts (manufactured by Mitsubishi Electric Osram Co., Ltd.), and exposed to a gray scale sensitivity of 13±1 steps (main exposure), The entire surface of the 7 cm×14 cm photosensitive resin layer was light-cured. After that, it was developed with a brush-type developing device for 1 minute in an ethanol aqueous solution (ethanol/water = 80/20) at a liquid temperature of 25°C, dried at 60°C for 10 minutes, and then further treated with a chemical lamp FL20SBL-360 20W (Mitsubishi Motor Osram Co., Ltd.), post exposure under the same conditions as the main exposure, to obtain a resin gravure printing plate. In the resin gravure printing plate of Example 1, the image and the dot system are formed so as to have the minimum distance described in Table 1. The evaluation results of Example 1 are shown in Table 2.

Example 2~7

Except that the positive film of the plate-making member was changed as described in Table 1, the resin gravure printing plates of Examples 2 to 7 were produced in the same manner as in Example 1. The evaluation results are shown in Table 2.

Comparative Examples 1 and 2

Except for changing the positive film of the plate-making member as described in Table 1, the photosensitive resin printing plate original plate and the resin gravure printing plates of Comparative Examples 1 and 2 were produced in the same manner as in Example 1. The evaluation results are shown in Table 2.

Comparative Example 3

Vacuum the positive film described in Table 2 with a chemical lamp FL20SBL-360 20 watts (manufactured by Mitsubishi Electric Osram Co., Ltd.), and perform exposure (main exposure) at a gray scale sensitivity of 13±1 steps. The entire surface of the photosensitive resin layer of 7 cm×14 cm is photocured. Next, a 300-line 90% halftone dot screen film was closely attached to screen exposure. After that, it was developed with a brush-type developing device for 1 minute in an ethanol aqueous solution (ethanol/water = 80/20) at a liquid temperature of 25°C, dried at 60°C for 10 minutes, and then further treated with a chemical lamp FL20SBL-360 20W (Mitsubishi Motor Osram Co., Ltd.) was subjected to post-exposure under the same conditions as the main exposure to obtain the resin gravure printing plate of Comparative Example 3. The evaluation results are shown in Table 2.

[Table 1]

[Table 2]

1‧‧‧ outlets

2‧‧‧ Tangent

3‧‧‧Non-Image Department

4‧‧‧Image Department

d‧‧‧Minimum distance between the end of the image and the dot

P‧‧‧Contact

Q‧‧‧Point on the end of the image

Claims (13)

A resin gravure printing plate, which is a resin gravure printing plate having an image portion having dots on the surface of a plate material, wherein the minimum distance between the end of the image portion and the dot located near the end of the image portion is 20 μm Above 300μm. The resin gravure printing plate of claim 1, wherein the diameter of the dot is 5.0 μm or more and 50 μm or less. The resin gravure printing plate according to claim 1 or 2, wherein the difference in height between the surface of the resin gravure printing plate and the deepest part of the concave portion existing between the dots among the concave portions provided on the printing plate surface is 10 to 40 μm. The resin gravure printing plate according to any one of claims 1 to 3, wherein the resin gravure printing plate has a photosensitive resin composition containing at least a binder polymer, an ethylenically unsaturated compound, and a photopolymerization initiator The photosensitive resin laminate of the formed photosensitive resin layer. The resin gravure printing plate as claimed in claim 4, wherein the binder polymer is a polyamide having a 4,4'-diaminodicyclohexylmethane adipate skeleton. The resin gravure printing plate according to any one of claims 1 to 5, wherein the resin gravure printing plate has a photosensitive resin layer containing inorganic fine particles having an average particle diameter of 0.5 μm or more and 4.0 μm or less. The resin gravure printing plate of claim 6, wherein the inorganic fine particle system has a sphericity of 0.90 or more. The resin gravure printing plate according to any one of claims 6 or 7, wherein the inorganic fine particles are amorphous silica. The resin gravure printing plate according to any one of claims 6 to 8, wherein in the photosensitive resin layer, when the mass of the photosensitive resin layer is set to 100% by mass, 3% by mass or more and 30% by mass or less are included The inorganic fine particles. The resin gravure printing plate according to any one of claims 1 to 9 is used for pad printing. The resin gravure printing plate according to any one of claims 1 to 10, which is for non-absorbent original printing. A method of manufacturing a resin gravure printing plate, which is a method of manufacturing a resin gravure printing plate by sequentially performing an exposure step and a development step on a photosensitive resin printing plate original plate, wherein the exposure step includes the following steps: using an original image portion This is done with the original film of the dot inside the original image part. A printing method that uses a resin gravure printing plate that forms an image portion with dots on the surface of a plate to perform printing, and is characterized by having an area at a distance of 20 μm or less from the end of the image portion The steps of forming dots in areas other than this; the filling step of filling the recording material in the image portion; the first transfer step of transferring the recording material filled in the image portion to the transfer body; and the transfer The recording material of the transfer body is transferred to the object to be printed to form a second transfer step of the printed object.

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