JP2009090663A - Gravure simultaneously perfecting printer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gravure simultaneously perfecting printer equipped with a pair of gravure printing cylinders with cushioning properties, by making a direct simultaneous gravure perfecting printing possible to a rigid and brittle material to be printed, simultaneous perfecting printing of images different from each other on both the sides can be possible. <P>SOLUTION: In the gravure simultaneously perfecting printer to both the front and back sides of a sheet-like material to be printed, a conveying means for conveying and progressing the sheet-like material to be printed towards a definite direction, a pair of gravure printing cylinders, which is installed so as to be able to come into contact with the front surface and with the back surface of the progressing material to be printed and on the plate face of which gravure cells are provided, and doctor blades provided so as to be able to come into contact with the respective plate faces of the pair of gravure printing cylinders. By directly transferring the ink stored in the gravure cells to the front surface and the back surface of the sheet-like material to be printed, simultaneous gravure printing to the front surface and to the back surface of the sheet-like material to be printed is executed. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention provides simultaneous double-sided printing on a plate-shaped printing material, for example, simultaneous double-sided printing on a rough surface such as cardboard, or simultaneous double-sided printing of images on a compact disk, etc. The present invention relates to a gravure double-sided simultaneous printing apparatus provided with a pair of gravure printing cylinders having cushioning properties suitable for color printing of a matrix image for composition, and further, gravure printed matter, microlens, and wallpaper produced using the printing apparatus , Electromagnetic wave shield sheet, color filter, polarizing plate, condenser, electronic paper and the like.

  In gravure printing, for a gravure printing roll (gravure cylinder), a micro concave portion (gravure cell) corresponding to the plate making information is formed to produce a plate surface, and the gravure cell is filled with ink and transferred to a printing material. is there. In a general gravure plate-making roll, a copper plating layer (plate material) for forming a plate surface is provided on the surface of a plate base material such as aluminum or iron, and a number of minute concave portions are formed on the copper plating layer according to plate making information by etching. (Gravure cell) is formed, and then a hard chromium layer is formed by chromium plating for increasing the printing durability of the gravure plate making roll to form a surface-enhanced coating layer, and plate making (plate surface production) is completed.

  Conventionally, gravure offset printing or waterless offset printing has been adopted for color printing of matrix images for forming color filters on printing plates, especially glass for liquid crystal panels, or color printing of images on compact discs, etc. Gravure printing has not been adopted. The reason for this is that gravure printing has a cushioning property of the gravure printing cylinder, so that if the printing pressure is increased, the glass may be broken or a compact disk or the like may be distorted.

  Therefore, as shown in FIG. 7, this type of conventional printing apparatus 50 applies to a brittle plate-like printing material 56 such as a glass plate from a gravure plate cylinder 54 having a large number of gravure cells 52 formed on the surface thereof. Gravure offset printing has been employed in which printing is not performed directly, but printing is performed via a blanket roll 58 made of rubber, so that when printing pressure increases, the increase in printing pressure can be suppressed by deformation of the rubber. In FIG. 8, 60 is a doctor blade, and 62 is ink.

  For color printing on glass for liquid crystal panels, the thickness of the wet ink film immediately after transfer to the glass is set to a uniform 5-6 μm, and the dry ink film thickness is set to a uniform 1-1.5 μm. It is necessary to ensure uniform transmission and high transmittance. In addition, in order to print an image on a compact disk or the like, it is necessary to make the ink film thickness as thin as possible to the extent that the image can be obtained sharply. The reason is that the image printed on a compact disk or the like is printed with a bias with respect to the center, so the weight of the ink forming the image is the spindle that uses the fluid dynamic pressure bearing of the next generation compact disk device It is because it became clear that it became non-negligible as a cause of unbalanced rotation with high-speed rotation of a motor.

  In conventional gravure printing plates, it is necessary to form cells in the surface layer portion of copper plating so that the depth is 15 to 25 μm. Then, the film thickness of the wet ink is 15 to 25 μm. The ink film is too thick for color printing on glass or color printing of images on compact discs.

  In the conventional gravure printing plate, etching is performed so that the depth is 5 to 6 μm on the surface of the copper plating, and the cell cannot be formed by etching. The etching rate varies depending on the size of the cell. This is because it is not uniform. It is inevitable that the contour and bottom surface of the cell are uneven, and cells having different depths depending on the size are formed. In particular, even for a cell having a large shadow portion, even if the depth can be 5 to 6 μm, a cell having a small highlight portion has a high probability of irregularities on the contour and bottom surface, and the depth is 5 to 6 μm. I can hardly hope to do so.

  Therefore, in order to reliably obtain a gravure plate having a cell depth of 5 to 6 μm, a fairly accurate cell having a uniform depth can be formed by printing an image on glass, developing it, and etching with hydrofluoric acid. . However, this is not gravure printing but gravure offset printing in which printing is performed via a blanket roll.

  Thus, conventionally, gravure offset printing or waterless lithographic offset printing has been adopted for color printing on glass for liquid crystal panels or color printing on compact discs, etc., but gravure printing has not been adopted. It was.

  On the other hand, a conventional flexographic plate (resin relief plate) is developed by applying a mask film on a photocurable resin and exposing it with ultraviolet rays, or irradiating with a semiconductor thermal laser, a YAG laser or the like, or developing a photocurable resin. A plate of carbon black is applied, carbon black is burned off with a laser to form a positive image, and the first photocurable resin is baked and developed with ultraviolet rays to make a plate.

  However, the color filter for liquid crystal panels manufactured by the conventional printing method has low image sharpness, the edge of the line image is irregular, and the line image has irregularities. The quality is remarkably inferior to that of the above, and therefore, its use is widespread only for toys, and it is not used at all for high-end products such as computer displays and liquid crystal televisions with TFTs.

  The reason why the quality of the color filter for a liquid crystal panel manufactured by gravure offset printing is inferior is considered as follows. In gravure offset printing, a printing pressure is applied to some extent when ink is transferred from a blanket roll to a substrate such as glass. Since the printing pressure presses the ink, the contour of the ink spreads outward or is disturbed, which is one of the reasons why the line and space value used as an indicator of resolution or fineness cannot be reduced. In addition, when the transferred ink does not transfer from the plate to the blanket roll and from the blanket roll to the printed material such as glass with a probability of 100%, the ink is torn off and printed on the printed material such as glass. The ink film thickness is not uniform and the surface is uneven.

  No matter how high the precision of a gravure offset printing machine is pursued, it is necessary to apply printing pressure, and it is impossible to suppress fluctuations in printing pressure. Therefore, since it is essential that printing pressure is applied and the printing pressure fluctuates, it is very difficult to put it into practical use even if it is possible to transfer ink from the blanket roll to the liquid crystal panel glass with a probability of 100%. It is believed that there is.

  On the other hand, the conventional flexographic plate (resin relief plate) uses a photo-curing resin, so if a small dot is formed in a columnar shape, it easily breaks, and the brittleness of the cured resin cannot be eliminated. Could not make.

  By using a pair of gravure printing cylinders having cushioning properties, the present invention can simultaneously print different images on both sides by enabling direct double-sided simultaneous gravure printing without using a blanket roll on a hard and brittle substrate. In addition, printing efficiency can be doubled, and gravure double-sided simultaneous printing on rough surfaces, such as corrugated cardboard printing, can be performed satisfactorily, and matrix images for configuring color filters on liquid crystal panel glass can be printed in color, compact discs, etc. Another object of the present invention is to provide a gravure double-sided simultaneous printing apparatus provided with a gravure printing cylinder having cushioning properties suitable for color printing of images. Furthermore, an object of the present invention is to provide a gravure printed material, a microlens, a wallpaper, an electromagnetic wave shielding sheet, a color filter, a polarizing plate, a capacitor, electronic paper, and the like manufactured using the printing apparatus.

  In order to solve the above problems, the gravure double-sided simultaneous printing device of the present invention is a gravure double-sided simultaneous printing device for both the front and back surfaces of a plate-like printing material, and the plate-like printing material is conveyed in a certain direction. Conveying means, a pair of gravure printing cylinders that are installed so as to be in contact with the front and back surfaces of the material to be printed and have a gravure cell on the printing plate, and a plate surface of the pair of gravure printing drums A doctor blade provided in contact with each other, the ink supplied to the pair of gravure plate cylinders is stored in the gravure cell by the doctor blade, the pair of gravure plate cylinders are rotated and the plate-like By bringing the pair of gravure plate cylinders into contact with the front and back surfaces of the plate-like printing material in a state where the printing material is advanced in a certain direction, The ink stored in Rabiaseru is characterized in that to perform simultaneously gravure printing on the surface and the back surface of the plate-like printed material is transferred directly to the front and back surfaces of the plate-like printed material.

  The first aspect of the gravure plate cylinder having cushioning properties includes a plate base material provided with a cushion layer made of rubber or a resin having cushioning properties on the surface, and a photosensitive composition layer formed on the surface of the cushion layer. And a gravure cell formed on the surface of the photosensitive composition layer, and a reinforcing coating layer formed on the surface of the photosensitive composition layer on which the gravure cell is formed.

It is preferable that the photosensitive composition layer is formed using a negative photosensitive composition.
As a first aspect of the negative photosensitive composition, (A) a polymer having a carboxyl group and having an ethylenically unsaturated bond, (B) a near-infrared absorbing dye, and (C) at least one A monomer having an ethylenically unsaturated bond; (D) one or more amines selected from the group consisting of amino alcohols, amino alcohol derivatives and cyclic amines; (E) organoboron compounds; and (F) It is preferable to employ a composition containing a sulfonyl compound represented by the formula (1).

Wherein (1), Q represents an aryl group or a heterocyclic group, a halogen atom X ¹ to X ³ are each independently]

  The amino alcohol derivative is preferably a (meth) acrylic acid ester of amino alcohol. Moreover, it is preferable that the cyclic amine is a morpholino group-containing compound or a piperazine-based compound. In the present specification, acrylic and methacryl are collectively referred to as (meth) acrylic, and acrylate and methacrylate are collectively referred to as (meth) acrylate.

  The compound (F) represented by the formula (1) is preferably tribromomethylphenyl sulfone or 2-[(tribromomethyl) sulfonyl] pyridine.

  As a second aspect of the negative photosensitive composition, (A) a polymer having a carboxyl group and having an ethylenically unsaturated bond, (B) a near-infrared absorbing dye, (C) at least one A composition containing a monomer having an ethylenically unsaturated bond, (G) 2-mercaptobenzoxazole and / or 2-mercaptooxazole, and (H) a diphenyliodonium salt represented by the following formula (2) is adopted. Is preferred.

  It is preferable that the second aspect of the negative photosensitive composition further contains (I) a triazine compound represented by the following general formula (3).

[In the general formula (3), R ¹ is a vinyl group or a monovalent organic group containing a vinyl group]

  The (I) triazine compound is preferably 2,4-diamino-6-vinyl-s-triazine and / or 2,4-diamino-6-methacryloyloxyethyl-s-triazine.

  The first and second aspects of the negative photosensitive composition preferably further contain (J) a silane coupling agent.

  It is preferable that the first and second aspects of the negative photosensitive composition further contain (K) a polymerization inhibitor.

  The second aspect of the gravure plate cylinder having the cushioning property includes a plate base material provided with a cushion layer made of rubber or a resin having cushioning property on the surface, a gravure cell formed on the surface of the cushion layer, And a reinforcing coating layer formed on the surface of the cushion layer on which the gravure cell is formed.

  The third aspect of the gravure plate cylinder having cushioning properties is a plate base material provided with a cushion layer made of rubber or a resin having cushioning properties on the surface, a copper plating layer formed on the surface of the cushion layer, A gravure cell formed by etching on the copper plating layer and a reinforcing coating layer formed on the surface of the copper plating layer on which the gravure cell is formed are included.

  The fourth aspect of the gravure plate cylinder having the cushioning property is a plate base material provided with a cushion layer made of rubber or a resin having cushioning property on the surface, a copper plating layer formed on the surface of the cushion layer, A gravure cell formed by forming a gravure cell wall made of a metal plating layer on the surface of the copper plating layer, a copper plating layer on which the gravure cell is formed, and a reinforcing coating layer formed on the surface of the metal plating layer Including.

The printed matter of the present invention is manufactured using the printing apparatus of the present invention.
The printed matter is a printed matter that is gravure-printed by arranging a gravure ink composed of water-based ink, oil-based ink, or phase change ink so as to form a predetermined pattern by printing on the surface of the sheet to be printed. A printed material in which the gravure ink is printed using the printing apparatus is suitable.

  The microlens of the present invention is a microlens manufactured by arranging microlens forming ink on a surface of a sheet-like base material in a protruding shape at a predetermined interval by printing, and the printing apparatus of the present invention The ink for microlens formation is used for printing.

  The wallpaper of the present invention is a wallpaper produced by arranging the ink for wallpaper on the surface of the wallpaper substrate so as to form a predetermined pattern by printing, and the wallpaper ink using the printing apparatus of the present invention This is characterized in that printing is performed.

  The electromagnetic wave shielding sheet of the present invention is an electromagnetic wave shielding sheet produced by disposing a conductive paste on a surface of an electromagnetic wave shielding substrate so as to form an electromagnetic wave shielding layer having a predetermined pattern by printing, The conductive paste is printed using an apparatus.

  The color filter of the present invention is a color filter manufactured by arranging a color filter ink on a surface of a color filter substrate so as to form a color filter layer having a predetermined pattern by printing, and the printing apparatus of the present invention The color filter ink is used for printing.

  The polarizing plate of the present invention is a polarizing plate produced by arranging a polarizing ink on the surface of a polarizing plate substrate so as to form a polarizing layer having a predetermined pattern by printing, and using the printing apparatus of the present invention. The polarizing ink is printed.

  The ceramic capacitor of the present invention is a ceramic capacitor manufactured by arranging a conductive paste on a ceramic substrate so as to form an internal electrode by printing, and the conductive paste using the printing apparatus of the present invention. This is characterized in that printing is performed.

  The electronic paper of the present invention is an electronic paper manufactured by arranging a microencapsulated cell containing magnetic powder on a base film so as to form a predetermined pattern by applying it through a binder. The microencapsulated cell is applied using the printing apparatus of the present invention.

  According to the gravure printing apparatus equipped with the gravure printing cylinder having cushioning properties of the present invention, it is possible to simultaneously print different images on both sides by enabling direct double-sided simultaneous gravure printing without using a blanket roll on a hard substrate. It can be printed and the printing efficiency can be doubled. It is suitable for color printing a matrix image for constituting a color filter on glass for a liquid crystal panel, or for color printing an image on a compact disk, etc. Printing on rough surfaces such as cardboard printing can also be performed well. Furthermore, by using the printing apparatus of the present invention, in the production of printed matter, microlens, wallpaper, electromagnetic wave shield sheet, color filter, polarizing plate, capacitor, electronic paper, etc., fine transfer and fine transfer of ink materials and coating materials are possible. It becomes easy and it becomes possible to obtain a final product with excellent performance.

  In particular, the negative photosensitive composition of the first and second aspects described above that is preferably used for the production of the gravure plate cylinder of the apparatus of the present invention does not require burning and overcoat before exposure, and has excellent sensitivity, A gravure cell that has adhesion and storage stability and is formed using photolithography using this negative photosensitive composition has a sharp gravure cell shape that is practical and compatible with gravure printing. It has a remarkable effect.

  Embodiments of the present invention will be described below, but these embodiments are exemplarily shown, and it goes without saying that various modifications can be made without departing from the technical idea of the present invention.

FIG. 1 is a sectional explanatory view showing an example of an embodiment of a gravure double-sided simultaneous printing apparatus of the present invention.
In FIG. 1, 50A is a gravure double-sided simultaneous printing apparatus of the present invention, a conveying means 57 for conveying a plate-like printing material 56 such as a glass plate or cardboard in a fixed direction, and a surface 56a of the printing material 56 that advances. And a pair of gravure plate cylinders 10a and 10b having cushioning properties, which are disposed so as to be in contact with the back surface 56b and provided with gravure cells 14a and 14b on the plate surface. Reference numerals 60a and 60b denote doctor blades provided so as to be in contact with the plate surfaces of the pair of gravure plate cylinders 10a and 10b, respectively.

  With the above configuration, the inks 62a and 62b supplied to the pair of gravure plate cylinders 10a and 10b are stored in the gravure cells 14a and 14b by the doctor blades 60a and 60b, and the pair of gravure plate cylinders 10a and 10b are rotated. The gravure cell 14a is caused by bringing the pair of gravure plate cylinders 10a and 10b into contact with the front surface 56a and the back surface 56b of the plate-like printing material 56 in a state where the plate-like printing material is advanced in a certain direction. , 14b is directly transferred to the front surface 56a and the back surface 56b of the plate-shaped printing material 56 to simultaneously perform gravure printing on the front surface 56a and the back surface 56b of the plate-shaped printing material 56. is there.

  Thus, by using a gravure plate cylinder having cushioning properties as a pair of gravure plate cylinders 10a and 10b, it is hard and brittle as in the case of color printing a matrix image for forming a color filter on a glass for a liquid crystal panel. Printing on a glass plate or the like can be performed directly and efficiently without using a blanket roll as in the prior art, and printing on corrugated cardboard or the like having an uneven surface can also be effectively performed. In particular, in the apparatus of the present invention, by using a pair of gravure plate cylinders 10a and 10b, it is possible to perform direct double-sided simultaneous gravure printing on a hard and brittle substrate without using a blanket roll, thereby different images on both sides. Can be simultaneously printed and the printing efficiency can be doubled.

  The gravure printing cylinders 10a and 10b having cushioning properties are not limited to any particular one as long as the gravure printing drums have cushioning properties, and the following four modes can be adopted. Since the gravure plate cylinders 10a and 10b have the same structure, FIGS. 2 to 6 described below will be described with reference to only the gravure plate cylinder 10a, and the gravure cells 14a and 14b will be described as the gravure cell 14. To do.

  As shown in FIGS. 2 (e) and 3 (e), the first aspect of the gravure plate cylinder 10a having cushioning properties is a plate provided with a cushion layer 11b made of rubber or resin having cushioning properties on the surface. A base material 10, a photosensitive composition layer 12 formed on the surface of the cushion layer, a gravure cell 14 formed on the surface of the photosensitive composition layer 12, and a photosensitive composition in which the gravure cell 14 is formed. And a reinforcing coating layer 18 formed on the surface of the physical layer 12.

  FIG. 2 is an explanatory view schematically showing an example of the steps of the manufacturing method of the first aspect of the gravure plate cylinder 10a having cushioning properties used in the gravure double-sided simultaneous printing apparatus of the present invention, and (a) is a rubber or cushion. Cross-sectional view of a hollow roll (plate base material) having a cushion layer made of a resin having a property on its surface, (b) is a partially enlarged cross-section showing a state in which a negative photosensitive composition layer is formed on the surface of the cushion layer (C) is a partially enlarged sectional view showing a state where a mask is provided on the surface of the negative photosensitive composition layer, and (d) shows a state where a gravure cell is formed on the surface of the negative photosensitive composition layer. Partial enlarged sectional view, (e) is a partially enlarged sectional view showing a state in which a reinforcing coating layer is formed on the surface of the negative photosensitive composition layer. FIG. 3 is a view similar to FIG. 2 showing another example of the process of the first embodiment of the gravure plate having cushioning properties used in the gravure double-sided simultaneous printing apparatus of the present invention.

  First, a plate base material provided with a cushion layer made of rubber or a resin having cushioning properties on the surface is prepared. In FIG. 2 (a), reference numeral 10 denotes a plate base material, which is provided with a cushion layer 11b on the surface of a hollow roll 11a. The cushion layer 11b is made of rubber or a resin having cushioning properties, and a sheet-like material having a uniform thickness of about 1 mm to 10 cm and high surface smoothness is formed on the hollow roll 11a so as not to open a gap at the seam. Winding and bonding firmly, then precision cylindrical grinding and mirror polishing. The hollow roll 11a is preferably made of a metal such as aluminum or iron, or made of carbon fiber reinforced resin (CFRP).

  Next, a photosensitive composition layer 12 is formed on the surface of the cushion layer 11b [FIG. 2 (b)]. The film thickness of the photosensitive composition layer 12 is not particularly limited, and is determined according to the depth of the cell in relation to the purpose of use of the plate.

  For example, since the depth of the gravure cell may be 1 mm or more in corrugated cardboard printing or the like, the film thickness of the negative photosensitive composition layer 12 is made several mm thicker than that.

  For example, in order to color-print a matrix image for forming a color filter on a glass for a liquid crystal panel, it is necessary to form a gravure cell to a uniform depth of 5 to 6 μm in order to make the ink film thickness uniform. There is. Therefore, the photosensitive composition layer 12 is formed to have a thickness of 5 to 6 μm by coating, and cells are formed so that the cushion layer 11b is exposed. More preferably, the cushion layer 11b is formed of silicon rubber to enhance the transferability of the ink deposited in the cell to the glass for a liquid crystal panel.

  Since a compact disc or the like should have a very thin ink film thickness, the cell depth is set to several μm. The film thickness of the photosensitive composition layer 12 may be 1 to 2 mm, or may be a thin film of 5 to 6 μm. In short, it can be appropriately determined in relation to the ease of forming the photosensitive composition layer 12, cost, and development.

  The photosensitive composition layer is formed using a photosensitive composition. As the photosensitive composition, either a negative type or a positive type can be used, but it is preferable to use a negative photosensitive composition. There is no restriction | limiting in particular in the said negative photosensitive composition, Although a well-known negative photosensitive composition can be used, It is suitable to use the negative photosensitive composition of the 1st and 2nd aspect mentioned later. is there.

  As a first aspect of the negative photosensitive composition, (A) a polymer having a carboxyl group and having an ethylenically unsaturated bond, (B) a near-infrared absorbing dye, and (C) at least one ethylene A monomer having a polar unsaturated bond, (D) one or more amines selected from the group consisting of amino alcohols, amino alcohol derivatives and cyclic amines, (E) organoboron compounds, and (F) the following formula It is preferable to employ a composition containing the sulfonyl compound represented by (1).

Wherein (1), Q represents an aryl group or a heterocyclic group, a halogen atom X ¹ to X ³ are each independently]

  The polymer (A) is not particularly limited as long as it is a polymer having a carboxyl group and an ethylenically unsaturated bond. For example, a (co) polymer having an unsaturated compound having a carboxyl group as a monomer unit, A polymer obtained by reacting with a compound having an ethylenically unsaturated bond is preferably used. The polymer (A) preferably contains a carboxyl group so that the acid value is 30 to 500, particularly 200 to 250. The weight average molecular weight is preferably 1,500 to 100,000, more preferably around 6,000 to 50,000.

  As the unsaturated compound having a carboxyl group, (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, and derivatives thereof are preferable, and these can be used alone or in combination of two or more.

  The (co) polymer having an unsaturated compound having a carboxyl group as a monomer unit may be used in combination with another unsaturated compound other than the unsaturated compound having a carboxyl group as a monomer unit. As the other unsaturated compound, a compound having an unsaturated double bond is preferable, and styrene, α-methylstyrene, m or p-methoxystyrene, p-methylstyrene, p-hydroxystyrene, 3-hydroxymethyl-4. -Styrenic monomers such as hydroxy-styrene, and (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hydroxyethyl (meth) acrylate, etc. preferable. These can be used alone or in combination of two or more.

  Examples of the compound having an ethylenically unsaturated bond include unsaturated alcohols (for example, allyl alcohol, 2-buten-1--2-ol, furfuryl alcohol, oleyl alcohol, cinnamyl alcohol, 2-hydroxyethyl acrylate, Hydroxyethyl methacrylate, N-methylolacrylamide, etc.), alkyl (meth) acrylate (eg, methyl methacrylate, t-butyl methacrylate, etc.), epoxy compound having one oxirane ring and one ethylenically unsaturated bond (eg, glycidyl acrylate, Suitable examples include glycidyl methacrylate, allyl glycidyl ether, α-ethyl glycidyl acrylate, crotonyl glycidyl ether, itaconic acid monoalkyl monoglycidyl ester, and the like. And the like.

  Further, as the polymer (A), in order to further increase the concentration of the ethylenically unsaturated bond in the polymer having the ethylenically unsaturated bond introduced by the unsaturated alcohol, the above-described oxirane ring and ethylenically unsaturated bond are respectively You may use what reacted the epoxy compound which has one, and also enlarged the ethylenically unsaturated bond density | concentration.

  The content ratio of the polymer (A) in the first aspect of the negative photosensitive composition is not particularly limited, but is preferably 45 to 65% by weight based on the total solid content of the composition, 50 More preferred is -60% by weight. The polymer (A) may be used alone or in combination of two or more.

  Examples of the (B) near-infrared absorbing dye include organic or inorganic dyes having an absorption band in part or all of the infrared region having a wavelength of 700 to 1,100 nm, efficiently absorbing light in the wavelength region, In addition, a light-absorbing dye that absorbs almost no light in the ultraviolet region or is substantially insensitive even when absorbed is preferable, a compound represented by the following general formula (4) and a derivative thereof, and a polymethine type represented by the following formula (5) Compounds (for example, see JP-A No. 2001-64255 and WO 2005/049736) and the like are more preferably used.

[In General Formula (4), R ^{2 to} R ⁵ are each independently a hydrogen atom, an alkoxyl group, or a tertiary amino group, and include a methoxy group, —N (CH ₃ ) ₂ , or —N (C ₂ H _{5) 2} is preferred. X ^- is represents a counter anion, as the _{X C 4 H 9 -B (C} 6 H 5) 3, p-CH 3 C 6 H 4 SO 3, or _CF 3 SO ₃ and the like are preferable. ]

[In the general formula (5), R ⁶ represents a hydrogen atom, an alkyl group which may have a substituent or an alkoxy group which may have a substituent, and a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms. Is preferred. R ⁷ represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted alkoxy group, an alkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms in total, A sulfoalkyl group having 1 to 8 carbon atoms or a carboxyalkyl group having 2 to 9 carbon atoms is preferable. R ⁸ and R ⁹ each represent an alkyl group having 1 to 4 carbon atoms, preferably a methyl group, and R ⁸ and R ⁹ may be linked to each other to form a cyclic structure, and a cyclopentane ring or a cyclohexane ring It is preferable to form. Y ¹ represents a hydrogen atom, an alkoxy group which may have a substituent or an alkyl group which may have a substituent, a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms. Is preferred. Y ² represents a hydrogen atom, a halogen atom or a substituted alkyl group, and is preferably H, Cl, Br or a diphenylamino group. Z represents a charge neutralizing ion, and Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CF ₃ CO ₂ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , CH ₃ SO ₃ ⁻ or p-toluenesulfonate. , Na ⁺ , K ⁺ , and triethylammonium ion are preferable. ]

  As other light-absorbing dyes, for example, polymethine (—CH═) n is a heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, or the like as described in JP-A-11-231515. The so-called cyanine dyes in a broad sense bound to each other can be cited as representative examples. Specifically, for example, quinoline (so-called cyanine), indole (so-called indocyanine), benzothiazole (so-called) , Thiocyanine series), iminocyclohexadiene series (so-called polymethine series), pyrylium series, thiapyrylium series, squarylium series, croconium series, azurenium series, etc. Among them, quinoline series, indole series, benzothiazole series, iminocyclo Hexadiene, pyrylium, or thiapyrylium are preferred. In particular, phthalocyanine and cyanine are preferable.

  Although the content rate of the near-infrared absorption pigment | dye (B) in the 1st aspect of the said negative photosensitive composition is not specifically limited, It is 0.2 to 4.0 weight% with respect to the solid content total amount of a composition. It is preferable that it is 0.4 to 3.0% by weight. The near infrared absorbing dye (B) may be used alone or in combination of two or more.

  The monomer (C) having at least one ethylenically unsaturated bond is not particularly limited as long as it is a compound having at least one ethylenically unsaturated bond in the molecule. For example, methyl (meth) acrylate, Alkyl (meth) acrylates such as ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, furfuryl (Meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, mono (2- (meth) acryloyloxyethyl) acid phosphate , (Meth) acrylate having imide group or maleimide group such as dimethylaminoethyl (meth) acrylate quaternized product, N- (meth) acryloyloxyethyl hexahydrophthalimide, trimethylolpropane tri (meth) acrylate, trimethylolpropane Di (meth) acrylate, triethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, hexamethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tetra Methylolmethane tetra (meth) acrylate, resorcinol di (meth) acrylate, p, p'-dihydroxydiphenyl di (meth) acrylate, spiroglycol di (meth) ) Acrylate, cyclohexanedimethylol di (meth) acrylate, bisphenol A di (meth) acrylate, polypropylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, methylenebis (meth) acrylamide, urethane di (meth) acrylate Etc.

  The content ratio of the monomer (C) in the first aspect of the negative photosensitive composition is not particularly limited, but is preferably 25 to 46% by weight with respect to the total solid content of the composition, 30 to More preferably, it is 40% by weight. The monomer (C) may be used alone or in combination of two or more.

  As the amino alcohol in the (D) amine, an organic compound having an amino group and an alcoholic hydroxyl group in one molecule can be used, and examples thereof include N, N-dimethylethanolamine, N, N-diethyl. Preferable examples include ethanolamine, N, N-dibutylethanolamine, N-methylethanolamine, N-methyldiethanolamine and the like.

  As the derivative of the amino alcohol in the (D) amines, an ester or salt of an amino alcohol is preferable, and an amino alcohol such as dimethylaminoethyl (meth) acrylate or diethylaminoethyl (meth) acrylate and (meth) acrylic acid Esters are more preferred.

  The cyclic amine in the (D) amine is not particularly limited as long as it is a compound having an amine nitrogen inside and outside the ring, but morpholino such as morpholine, N-methylmorpholine, N-ethylmorpholine and morpholinoethyl methacrylate. A group-containing compound and a compound having a piperazine ring such as piperazine, hydroxyethylpiperazine and 2-methylpiperazine (piperazine-based compound) are preferable.

  Although the content rate of the said amines (D) in the 1st aspect of the said negative photosensitive composition is not specifically limited, It is 0.3 to 5.0 weight% with respect to the solid content total amount of a composition. And is more preferably 0.5 to 4.0% by weight. The amines (D) may be used alone or in combination of two or more.

  As said (E) organic boron compound, what has the structure of the ammonium salt of a quaternary boron anion, for example is preferable, and the compound which specifically has a structure shown by following General formula (6) is suitable.

[In the general formula (6), R ¹⁰ is a monovalent organic group, preferably an alkyl group, and more preferably an n-butyl group. R ^{11 to} R ¹³ are each independently a monovalent organic group, preferably an aryl group, and more preferably a phenyl group, a naphthyl group, or an alkylphenyl group. R ^{14 to} R ¹⁷ are each independently a monovalent organic group, preferably an alkyl group. ]

  Moreover, as the compound represented by the general formula (6), a compound represented by the following formula (7) is preferably used.

  The content ratio of the organoboron compound (E) in the first aspect of the negative photosensitive composition is not particularly limited, but is 0.3 to 4.0% by weight with respect to the total solid content of the composition. And is more preferably 0.5 to 3.0% by weight. The organoboron compound (E) may be used alone or in combination of two or more.

(F) In the sulfonyl compound represented by the formula (1), Q is an aryl group or a heterocyclic group, and the aryl group may be either a monocyclic aryl group or a polycyclic aryl group, and is substituted. Also good. Examples of the aryl group include a substituted or unsubstituted benzene ring and a substituted or unsubstituted naphthalene ring, and a phenylene group is preferable.
The heterocyclic group is a monocyclic or polycyclic heterocyclic group, preferably an aromatic heterocyclic group, and may be condensed with other aryl groups. Examples of the heterocyclic group include a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring, and a pyridine ring is more preferable.
Specifically, the sulfonyl compound (F) is more preferably tribromomethylphenyl sulfone or 2-[(tribromomethyl) sulfonyl] pyridine.

  The content ratio of the sulfonyl compound (F) in the first aspect of the negative photosensitive composition is not particularly limited, but is 0.1 to 5.0% by weight with respect to the total solid content of the composition. Is preferable, and it is further more preferable that it is 0.3 to 4.0 weight%. The said sulfonyl compound (F) may be used independently and may be used in combination of 2 or more type.

  The first aspect of the negative photosensitive composition preferably further comprises (J) a silane coupling agent. Adhesion can be improved by adding the (J) silane coupling agent. The (J) silane coupling agent is preferably an alkoxysilane compound having a reactive functional group, for example, an alkoxysilane compound having a vinyl group such as vinyltrichlorosilane, vinyltrimethoxysilane, or vinyltriethoxysilane, 2- Epoxy groups such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane Contained alkoxysilane compounds, alkoxysilane compounds having a styryl group such as p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropiyl Alkoxysilane compounds having a methacryloxy group such as methyldiethoxysilane and 3-methacryloxypropyltriethoxysilane, alkoxysilane compounds having an acryloxy group such as 3-acryloxypropyltrimethoxysilane, N-2 (aminoethyl) 3- Aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy Silane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N- (vinylbenzyl) -2-aminoethyl-3-amino Propyl Alkoxysilane compounds having an amino group such as hydrochloride of rmethoxysilane, alkoxysilane compounds having a ureido group such as 3-ureidopropyltriethoxysilane, and alkoxysilane compounds having a chloropropyl group such as 3-chloropropyltrimethoxysilane Alkoxysilane compounds having a mercapto group such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, alkoxysilane compounds having a sulfide group such as bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltri Examples include alkoxysilane compounds having an isocyanate group such as ethoxysilane, and alkoxysilane compounds having an imidazole group such as imidazolesilane. An alkoxysilane compound having a group is preferable because it can further improve the adhesion to a mirror surface substrate such as nickel or stainless steel.

  The content ratio of the silane coupling agent (J) in the first aspect of the negative photosensitive composition is not particularly limited, but is 0 to 3.0% by weight based on the total solid content of the composition. Is preferable, and it is still more preferable that it is 0.3 to 2.0 weight%. The said silane coupling agent (J) may be used independently and may be used in combination of 2 or more type.

  The negative photosensitive composition preferably further comprises (K) a polymerization inhibitor. The polymerization inhibitor may be any compound that can suppress the polymerization of the ethylenically unsaturated bond-containing group. For example, hydroquinone, 2,5-di-t-butylhydroquinone, 2,5-di-t-amyl Hydroquinone compounds such as hydroquinone and 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone; 4-methoxyphenol, 2,6-di-t-butyl-4-methylphenol, 4,4 '-Butylidenebis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol) Phenols such as: phenothiazine compounds such as phenothiazine and phenothiazine derivatives; dithiocarls such as copper dibutyldithiocarbamate Minates; nitroso compounds such as N-nitrosophenylhydroxylamine and N-nitrosophenylhydroxylamine aluminum salts; 2-mercaptobenzothiazole, 2-benzothiazolyl disulfide, zinc salt of 2-mercaptobenzothiazole, N- Cyclohexyl-2-benzothiazole sulfenamide, N, N-dicyclohexyl-2-benzothiazole sulfenamide, N-oxydiethylene-2-benzothiazole sulfenamide, Nt-butyl-2-benzothiazole sulfenamide Examples include thiazole compounds such as 2 (4-morpholinyldithio) benzothiazole, and thiazole compounds are more preferable.

  The content of the polymerization inhibitor (K) in the first aspect of the negative photosensitive composition is not particularly limited, but is 0.1 to 7% by weight based on the total solid content of the composition. Preferably, it is 0.1 to 5 weight%. The said polymerization inhibitor (K) may be used independently and may be used in combination of 2 or more type.

  Further, as a second aspect of the negative photosensitive composition used in the present invention, (A) a polymer having a carboxyl group and having an ethylenically unsaturated bond, (B) a near infrared absorbing dye, C) a monomer having at least one ethylenically unsaturated bond, (G) 2-mercaptobenzoxazole and / or 2-mercaptooxazole, and (H) a diphenyliodonium salt represented by the following formula (2): It is preferable to adopt the composition to be contained.

  In the second embodiment of the negative photosensitive composition, (A) a polymer having a carboxyl group and having an ethylenically unsaturated bond, (B) a near-infrared absorbing dye, and (C) at least one ethylenic compound The monomer having an unsaturated bond is the same component as in the negative photosensitive composition of the first aspect, and the specific examples and content ratios of these components are the same as those described above, so that the description thereof is omitted. To do.

  The component (G) is 2-mercaptobenzoxazole, 2-mercaptooxazole, or a combination of both, and is used as a chain transfer agent. The content ratio of the component (G) in the second aspect of the negative photosensitive composition is not particularly limited, but is preferably 0.5 to 20% by weight based on the total solid content of the composition, More preferably, it is 3 to 15% by weight.

  The component (H) is a diphenyliodonium salt represented by the formula (2) and is used as a photoinitiator. Although the content rate of the component (H) in the 2nd aspect of the said negative photosensitive composition is not specifically limited, It is 0.5-20.0 weight% with respect to the solid content total amount of a composition. It is preferably 4.0 to 15.0% by weight.

  The second aspect of the negative photosensitive composition preferably further comprises (I) a triazine compound represented by the following general formula (3).

In the general formula (3), R ¹ is a vinyl group or a monovalent organic group containing a vinyl group, preferably a vinyl group or a (meth) acryloyloxyalkyl group. Preferred examples of the (I) triazine compound include 2,4-diamino-6-vinyl-s-triazine and / or 2,4-diamino-6-methacryloyloxyethyl-s-triazine.

  The content ratio of component (I) in the second aspect of the negative photosensitive composition is not particularly limited, but is 0.1 to 5.0% by weight based on the total solid content of the composition. Preferably, it is 0.2 to 4.0 weight%. The (I) triazine compounds may be used alone or in combination of two or more.

  In the second aspect of the negative photosensitive composition, the negative photosensitive composition is selected from the group consisting of (D) amino alcohol, a derivative of amino alcohol, and a cyclic amine, which are components in the first aspect of the negative photosensitive composition. It is preferred to further contain one or more amines. Since specific examples and content ratios of the amines are the same as those described above, the description thereof will be omitted.

  In the second aspect of the negative photosensitive composition, it is preferable that the composition further contains (J) a silane coupling agent as in the case of the first aspect of the negative photosensitive composition. Since specific examples and content ratios of the silane coupling agent are the same as those described above, description thereof will be omitted.

  In the second aspect of the negative photosensitive composition, it is preferable that the composition further contains (K) a polymerization inhibitor as in the case of the first aspect of the negative photosensitive composition. Since specific examples and content ratios of the polymerization inhibitor are the same as those described above, the description thereof will be omitted.

  In addition to the above components, the negative photosensitive composition (including the first and second embodiments) may include a colorant such as a pigment or a dye, a sensitizer, a development accelerator, and an adhesion as necessary. Various additives such as a property modifier, a coating property improver, and a surface conditioner may be blended.

  The development accelerator is preferably added with a small amount of, for example, dicarboxylic acid, amines or glycols.

  The colorant is not particularly limited, but a triarylmethane dye is preferable. As the triarylmethane-based dye, conventionally known triarylmethane-based colored dyes can be widely used. Specifically, methyl violet, crystal violet, Victoria blue B, oil blue 613 (Orient Chemical Co., Ltd.) Product names) and derivatives thereof. These triarylmethane dyes can be used alone or in combination of two or more.

  By using a colored dye, there is an effect that when a pattern is formed by development, pinholes, dust and the like on the surface of the photosensitive film can be clearly recognized and the coating operation can be easily performed with a correction solution (opaque). The higher the concentration of the dye, the better it is easy to see. Since the semiconductor industry cannot make corrections, manufacturing is performed in a clean room. However, in the printing industry and electronic parts, corrections are made to regenerate failed products.

  The negative photosensitive composition is usually used as a solution (photosensitive solution) dissolved in a solvent. The ratio of the solvent used is usually in the range of about 1 to 20 times by weight with respect to the total solid content of the photosensitive composition.

  The solvent is not particularly limited as long as it has sufficient solubility with respect to the components used and gives good coating properties. Cellosolve solvent, propylene glycol solvent, ester solvent, alcohol solvent, ketone solvent Solvents and highly polar solvents can be used. Examples of the cellosolve solvent include methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, and ethyl cellosolve acetate. Examples of the propylene glycol solvent include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether and the like. . As ester solvents, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate Etc. Examples of the alcohol solvent include heptanol, hexanol, diacetone alcohol, furfuryl alcohol and the like. Examples of the highly polar solvent include ketone solvents such as cyclohexanone and methyl amyl ketone, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. In addition, acetic acid or a mixed solvent thereof, and those obtained by adding aromatic hydrocarbons to these may be used.

An example of a method for forming a negative photosensitive composition layer using the negative photosensitive composition as a photosensitive solution will be described below.
First, a photosensitive solution is applied to the surface of the cushion layer 11b [FIG. 2 (b)]. As a coating method, meniscus coating, fountain coating, dip coating, spin coating, roll coating, wire bar coating, air knife coating, blade coating, curtain coating, and the like can be used.
The film thickness of the coating film of the photosensitive solution may be appropriately set according to the desired film thickness of the photosensitive composition layer 12, but is preferably in the range of 1 to 10 μm, preferably 3 to 7 μm in terms of dry film thickness. Is more preferable. As for the thickness of the coating film, in order to eliminate pinholes, it is better that the film is thicker.

  Next, the applied photosensitive solution is dried to form a photosensitive composition layer 12 composed of a negative photosensitive film. The drying method is not particularly limited, but after applying the photosensitive solution to the cushion layer surface and drying it naturally, it rotates at a high speed, blows off the surface of the cushion layer, and the mass action due to centrifugal force in the photosensitive film and the surface vicinity are slightly It is preferable to reduce the residual solvent concentration to 6% or less by becoming a negative pressure state. The time required for this drying depends on the film thickness, but is about 15 minutes until touch drying, and about 15-20 minutes until the drying is completed. The negative photosensitive film formed by the negative photosensitive composition of the first and second aspects described above has the effect of exhibiting sufficient adhesion without performing a burning process (heating process) before exposure. Play.

A gravure cell 14 is formed on the surface of the formed photosensitive composition layer 12 by photolithography. The procedure of photolithography will be described below by taking as an example the case where a negative photosensitive composition is used as the photosensitive composition.
As shown in FIG. 2 (c), a mask 13 having a mask image as a gravure image is laminated on or closely adhered to the surface of the negative photosensitive composition layer 12, and light rays (ultraviolet rays or the like) 20 are required. Irradiation is performed for a period of time, a photoreaction is caused in a necessary portion of the negative photosensitive composition layer 12, and the exposed portion is insolubilized in the developer.

  The mask 13 is preferably formed by coating a black coating agent made of a carbon-containing polymer or a negative photochromic agent by coating. The negative photochromic agent is an organic photochromic molecule alone or a compatible solution of an organic photochromic molecule and a polymer that has ultraviolet shielding properties when colored and becomes transparent by laser irradiation, and is well baked by a semiconductor laser. Can save energy.

As a light source for image exposure of the photosensitive composition layer, a semiconductor laser or YAG laser that generates an infrared laser beam having a wavelength of 700 to 1,100 nm is preferable. For example, a semiconductor laser 20 having a wavelength of 830 nm and an intensity of 220 mJ / cm ² is used. Is preferred. In addition, a solid laser such as a ruby laser or an LED can be used. The light intensity of the laser light source is preferably 2.0 × 10 ⁶ mJ / s · cm ² or more, and more preferably 1.0 × 10 ⁷ mJ / s · cm ² or more.

  You may perform a burning process (heat processing) before image development with respect to the negative photosensitive composition layer after the said exposure. Adhesion can be further improved by performing the burning treatment. When performing the burning treatment, the treatment conditions are not particularly limited, but it is preferable to perform the heat treatment for a predetermined time using superheated steam. The temperature of the superheated steam is 100 ° C or higher, preferably more than 100 ° C and 300 ° C or lower, more preferably 105 ° C or higher and 200 ° C or lower. The heating time varies depending on the temperature of the superheated steam, but about 5 minutes to 1 hour is sufficient. Moreover, you may perform a burning process in multiple times.

  Subsequently, as shown in FIG. 2 (d), development is performed except for the mask 13, leaving the photo-reacted insolubilized exposed portion of the negative photosensitive composition layer 12 so that the cushion layer 11b is exposed to the unexposed portion. The gravure cell 14 is formed by dissolving in a developing solution.

Development is usually performed at a temperature of about 15 to 45 ° C., preferably 22 to 32 ° C., by immersion development, spray development, brush development, ultrasonic development and the like.
Examples of the developer used for the development include inorganic alkalis (for example, Na and K salts), organic alkalis (for example, TMAH (Tetra Methyl Ammonium Hydroxide), choline, triethanolamine, diethanolamine, monoethanolamine, and the like. A developer made of an inorganic or organic alkali such as For example, it is preferable to perform development at a temperature of 20 ° C. to 30 ° C. for about 60 to 90 seconds using a developer such as a triethanolamine 0.8% solution.

  The developed cushion layer surface is washed with spray water for about 20 seconds to 1 minute to completely remove unexposed portions. Through the steps described above, the insolubilized exposed portion 12a remains as a gravure cell wall, and a number of gravure cells 14 can be formed on the cushion layer surface. It is preferable that the depth of the gravure cell is 5 to 150 μm.

  In this embodiment, the gravure cell 14 is formed so that the cushion layer 11b is exposed on the photosensitive composition layer 12. However, as shown in FIG. 3 to be described later, the gravure cell 14 is not exposed so that the cushion layer 11b is not exposed. Can also be formed.

  In the first embodiment of the gravure plate cylinder 10a, as shown in FIG. 2 (e), a reinforcing coating layer 18 is formed on the surface of the photosensitive composition layer 12 on which the gravure cell 14 is formed. As a result, a gravure printing roll (gravure plate, gravure plate cylinder) is completed.

As the reinforcing coating layer 18, a DLC layer, a silicon dioxide film, or a chromium plating layer can be applied.
The DLC layer is preferably formed by CVD or sputtering. The thickness of the DLC layer may be 0.1 to 10 μm.
The chrome plating layer can be formed by a conventional method. The thickness of the chromium plating layer is preferably about 0.1 to 10 μm.

  The silicon dioxide film is preferably formed using a perhydropolysilazane solution. As a method of forming a silicon dioxide film using the perhydropolysilazane solution, a coating film forming step of forming a coating film having a predetermined thickness by applying a perhydropolysilazane solution to the surface of the photosensitive composition layer; It is preferable to include a step of heat-treating the coated perhydropolysilazane coating film with superheated steam under predetermined conditions to form a silicon dioxide film having a predetermined hardness on the surface of the photosensitive composition layer.

  As the solvent for dissolving perhydropolysilazane, known solvents may be used. For example, benzene, toluene, xylene, ether, THF, methylene chloride, carbon tetrachloride, anisole, decalin, cyclohexene, methylcyclohexane, sorbeso, decahydronaphthalene. , Methyl tertiary butyl ether, diisobutyl ether, ethylcyclohexane, limonene, hexane, octane, nonane, decane, C8-C11 alkane mixture, C18-C11 aromatic hydrocarbon mixture, C8 or higher aromatic hydrocarbon in an amount of 5 wt% or more 25 Aliphatic / alicyclic hydrocarbon mixtures containing not more than% by weight, dibutyl ether and the like can be used.

  The perhydropolysilazane solution prepared by dissolving in the above-mentioned various solvents can be converted into silicon dioxide by heating with superheated steam, but the reaction rate is increased, the reaction time is shortened, the reaction temperature is decreased, and formed. It is preferable to use a catalyst for the purpose of improving the adhesion of the silicon dioxide film. These catalysts are also known. For example, amines and palladium are used. Specifically, organic amines such as primary to tertiary straight chain in which 1-3 alkyl groups of C1-5 are arranged. Aliphatic amines, primary to tertiary aromatic amines having 1 to 3 phenyl groups arranged, pyridine or cyclic aliphatic amines in which an alkyl group such as methyl or ethyl group is substituted with a nucleus. More preferable examples include diethylamine, triethylamine, monobutylamine, monopropylamine, dipropylamine and the like. These catalysts may be added in advance to the perhydropolysilazane solution, or may be contained in a vaporized state in the treatment atmosphere during the heat treatment with superheated steam.

  As a method for forming the coating layer of the perhydropolysilazane solution, the perhydropolysilazane solution may be applied by a spray coating method or an inkjet method.

  Subsequently, a heat treatment with superheated steam is performed on the perhydropolysilazane coating layer to form a silicon dioxide coating. The temperature of the superheated steam is 100 to 300 ° C. However, when the material of the hollow roll is aluminum, heating exceeding 200 ° C. causes deterioration of the hollow roll. 200 ° C. is preferred.

  The heat treatment is more preferably a multi-stage heat treatment including a primary heat treatment and a secondary heat treatment, and the conditions of the primary heat treatment are 100 ° C. to 170 ° C., 1 minute to 30 minutes, and Adopting a configuration in which the conditions of the secondary heat treatment are 140 ° C. to 200 ° C., 1 minute to 30 minutes, and the temperature of the secondary heat treatment is set higher than the temperature of the primary heat treatment. Is preferred. Furthermore, the temperature of the second heat treatment is preferably set to 5 ° C. or more, preferably 10 ° C. or more higher than the temperature of the first heat treatment.

  By further providing a step of washing the surface of the silicon dioxide film formed by the heat treatment with cold water or hot water, the hardness of the obtained silicon dioxide film can be further improved.

  The thickness of the silicon dioxide film is 0.1 to 5 μm, preferably 0.1 to 3 μm, and more preferably 0.1 to 1 μm.

  FIG. 3 is a view similar to FIG. 2 showing another example of the process of the first embodiment of the gravure plate cylinder having cushioning properties used in the gravure double-sided simultaneous printing apparatus of the present invention. In the process shown in FIG. 2, the example in which the gravure cell 14 is formed so that the cushion layer 11b is exposed on the photosensitive composition layer 12 is shown, but the cushion layer 11b is exposed as shown in FIG. The gravure cell 14 can also be formed so as not to occur. In FIG. 3, the configuration and operation of the other steps are the same as those in FIG. In this case, the unexposed portion is dissolved in the developer so as not to expose the cushion layer 11b to form the gravure cell 14. Therefore, after forming the gravure cell, the entire surface is irradiated with light (such as ultraviolet rays) to form a photosensitive composition. The part of the physical layer 12 that has not undergone photoreaction needs to be photoreacted to be stabilized.

  As shown in FIG. 4G, the second aspect of the gravure plate cylinder 10a having cushioning properties is a plate base material 10 provided with a cushion layer 11b made of rubber or resin having cushioning properties on the surface, and the cushion. The gravure cell 14 formed on the surface of the layer 11b and the reinforcing coating layer 18 formed on the surface of the cushion layer 11b on which the gravure cell 14 is formed are included.

  FIG. 4 is an explanatory view schematically showing an example of the process of the production method of the second embodiment of the gravure plate cylinder having cushioning properties used in the gravure double-sided simultaneous printing apparatus of the present invention, wherein (a) is rubber or cushioning properties. FIG. 5B is an overall cross-sectional view of a hollow roll (plate base material) having a cushion layer made of a resin having a surface formed thereon, and FIG. 5B is a partially enlarged cross-sectional view showing a state in which a negative photosensitive composition layer is formed on the surface of the cushion layer. (C) is a partially enlarged cross-sectional view showing a state where a mask is provided on the surface of the negative photosensitive composition layer, and (d) is a case where an exposed portion is insolubilized exposed portion by a developer by exposure, and an unexposed portion is formed by the developer. The partial expanded sectional view which shows the state melt | dissolved and removed to the cushion layer surface, (e) is the partial expanded sectional view which shows the state which formed the gravure cell in the cushion layer by etching, (f) is an insolubilized exposure part. Partially enlarged sectional view showing a state in which separated removed, (g) is a partially enlarged sectional view showing a state of forming a reinforcing coating layer on the surface of the cushion layer.

  First, in the same manner as described above, a plate base material 10 having a cushion layer 11b made of rubber or a resin having cushioning properties provided on the surface is prepared [FIG. 4 (a)].

  Next, a gravure cell is formed on the surface of the cushion layer 11b. The method for forming the gravure cell on the surface of the cushion layer is not particularly limited, but it is preferable to form the gravure cell on the surface of the cushion layer by a lithography method using a photosensitive composition. As the photosensitive composition, any of a positive type and a negative type can be used. However, it is preferable to use a negative type photosensitive composition, and the negative type photosensitive properties of the first and second aspects described above. It is more preferable to use a composition.

A method for forming a gravure cell on the cushion layer 11b using the negative photosensitive composition will be described below.
In the same manner as described above, a negative photosensitive composition layer 12 made of a negative photosensitive composition is formed on the surface of the cushion layer 11b [FIG. 4B]. Subsequently, in the same manner as described above, the negative photosensitive composition layer 12 is exposed to light (ultraviolet rays or the like) 20 through the mask 13 [FIG. 4 (c)]. The mask on the exposed negative photosensitive composition layer 12 is removed and developed as described above. This development process dissolves and removes the unexposed portions, leaving only the insolubilized exposed portions 12a that have undergone photoreaction. The developed cushion layer surface is washed with spray water for about 20 seconds to 1 minute to completely remove the unexposed portion, and the surface of the cushion layer 11b corresponding to the unexposed portion is exposed [FIG. 4 (d). ].

Subsequently, the exposed surface of the cushion layer is etched by an etching means such as an organic solvent or plasma etching to form a recess (gravure cell) having a predetermined depth [FIG. 4 (e)].
In addition to toluene and xylene, organic solvents as the above etching means include ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and butyl acetate, hydrocarbons such as n-hexane, cyclohexane and methylcyclohexane, methanol And alcohol solvents such as ethanol.

  Next, the insolubilized exposed portion 12a is peeled and removed [FIG. 4 (f)]. Although there is no restriction | limiting in particular as a peeling removal method, It is preferable to use alkaline aqueous solution (The density | concentration may be about 5 wt%), such as KOH aqueous solution and NaOH aqueous solution.

  In the second aspect of the gravure plate cylinder, the reinforcing coating layer 18 is formed on the surface of the cushion layer 11b having the concave portion (gravure cell) 14 formed on the surface in the same manner as described above [FIG. 4 (g)]. As a result, a gravure printing roll (gravure version) is completed.

  As shown in FIG. 5 (i), the third aspect of the gravure printing cylinder having cushioning properties is the plate base material 10 provided with a cushion layer 11b made of rubber or cushioning resin on the surface, The copper plating layer 15 formed on the surface of the cushion layer 11b, the gravure cell 14 formed by etching on the copper plating layer 15, and the reinforcing coating layer 18 formed on the surface of the copper plating layer on which the gravure cell is formed. Is included.

  FIG. 5 is an explanatory view schematically showing an example of the process of the third embodiment of the method for producing a gravure plate cylinder having cushioning properties used in the gravure double-sided simultaneous printing apparatus of the present invention, wherein (a) is rubber or cushioning properties. The whole sectional view of the hollow roll (plate base material) which formed the cushion layer which consists of resin which has a surface on the surface, (b) is the partial expanded sectional view showing the state where the copper plating layer was formed in the surface of the cushion layer, (c) Is a partially enlarged sectional view showing a state in which a negative photosensitive composition layer is formed on the surface of the copper plating layer, and (d) is a partially enlarged sectional view showing a state in which a mask is provided on the surface of the negative photosensitive composition layer. (E) is a partially enlarged cross-sectional view showing a state in which an exposed portion is insolubilized exposed to a developer by exposure and an unexposed portion is dissolved and removed to the copper plating layer surface by the developer, and (f) is an etching on the surface of the copper plating layer. (G) is a partially enlarged cross-sectional view showing a state where the insolubilized exposed part is peeled and removed, and (h) is a base layer (for example, on the surface of the copper plating layer). (C) is a partially enlarged sectional view showing a state in which a chrome plating layer is formed, and (i) is a partially enlarged sectional view showing a state in which a reinforcing coating layer is formed on the surface of the chrome plating layer.

  First, in the same manner as described above, a plate base material 10 having a cushion layer 11b made of rubber or a resin having cushioning properties provided on the surface is prepared [FIG. 5 (a)].

  Next, a copper plating layer 15 is formed on the surface of the cushion layer 11b [FIG. 6 (b)]. There is no restriction | limiting in particular in the formation method of the said copper plating layer, A well-known copper plating method is employable. Although there is no restriction | limiting in particular in the film thickness of a copper plating layer, It is preferable that it is 50-200 micrometers.

  Next, a gravure cell 14 is formed on the surface of the copper plating layer 15 by etching. An etching method for forming a gravure cell on the surface of the copper plating layer 15 is not particularly limited, but it is preferable to form a gravure cell on the surface of the copper plating layer by a lithography method using a photosensitive composition. As the photosensitive composition, any of a positive type and a negative type can be used, but it is preferable to use a negative type photosensitive composition, and the negative type photosensitive properties of the first and second aspects described above. It is more preferable to use a composition.

A method for forming a gravure cell on the copper plating layer 15 using the negative photosensitive composition will be described below.
Similarly to the above, the photosensitive composition layer 12 made of a negative photosensitive composition is formed on the surface of the copper plating layer 15 [FIG. 5 (c)]. Subsequently, in the same manner as described above, the photosensitive composition layer 12 is exposed to light (ultraviolet rays or the like) 20 through the mask 13 and exposed to light, and the exposed portion is set as an insolubilized exposed portion [FIG. 5 (d)]. The mask on the exposed photosensitive composition layer 12 is removed and developed in the same manner as described above, and the unexposed portion is dissolved and removed up to the copper plating layer 15. This development process dissolves and removes the unexposed portions, leaving only the insolubilized exposed portions 12a that have undergone photoreaction. The surface of the developed copper plating layer is washed with spray water for about 20 seconds to 1 minute to completely remove the unexposed portion and expose the surface of the copper plating layer 15 corresponding to the unexposed portion [FIG. e)].

Subsequently, the surface of the exposed copper plating layer is etched to form a recess (gravure cell) 14. [FIG. 5 (f)].
Next, the insolubilized exposed portion 12a is peeled off as described above. The gravure cell 14 is formed by removing the insolubilized exposed portion 12a [FIG. 5 (g)].

  In the third aspect of the gravure plate cylinder, the reinforcing coating layer 18 is formed on the surface of the copper plating layer 13 having the gravure cell 14 formed on the surface in the same manner as described above (FIG. 5 (i)). As a result, a gravure printing roll (gravure version) is completed. In addition, in order to improve the adhesiveness of the copper plating layer 13 and the reinforcement coating layer 18, it is preferable to form the base layer 16 between the copper plating layer 13 and the reinforcement coating layer 18 [FIG.5 (h)]. As the underlayer 16, a chrome plating layer is suitable.

  As shown in FIG. 6 (h), the fourth aspect of the gravure plate cylinder 10a having cushioning properties is a plate base material 10 provided with a cushion layer 11b made of rubber or resin having cushioning properties on the surface, A copper plating layer 15 formed on the surface of the cushion layer 11b, a gravure cell 14 formed by forming a gravure cell wall body made of a metal plating layer 16 on the surface of the copper plating layer 15, and the gravure cell 14 And a reinforced coating layer 18 formed on the surface of the metal plating layer 16.

  FIG. 6 is an explanatory view schematically showing an example of the process of the fourth embodiment of the method for producing a gravure plate cylinder having cushioning properties used in the gravure double-sided simultaneous printing apparatus of the present invention, wherein (a) is rubber or cushioning properties. The whole sectional view of the hollow roll (plate base material) which formed the cushion layer which consists of resin which has a surface on the surface, (b) is the partial expanded sectional view showing the state where the copper plating layer was formed in the surface of the cushion layer, (c) Is a partially enlarged sectional view showing a state in which a negative photosensitive composition layer is formed on the surface of the copper plating layer, and (d) is a partially enlarged sectional view showing a state in which a mask is provided on the surface of the negative photosensitive composition layer. (E) is a partially enlarged cross-sectional view showing a state in which an exposed portion is insolubilized exposed portion with respect to a developer by exposure and an unexposed portion is dissolved and removed to the copper plating layer surface by the developer to form a non-gravure cell portion, (f) Metal mesh FIG. 4G is a partially enlarged cross-sectional view showing a state in which a metal plating layer is formed on a non-gravure cell portion, and FIG. 4G is a partial enlarged cross-sectional view showing a state in which a gravure cell is formed by peeling and removing the insolubilized exposed portion to expose a copper plating layer (H) is a partial expanded sectional view which shows the state which formed the reinforcement coating layer on the surface of a copper plating layer and a metal plating layer.

  First, in the same manner as described above, a plate base material 10 provided with a cushion layer 11b made of rubber or a resin having cushioning properties on the surface is prepared [FIG. 6 (a)]. Next, as described above, a copper plating layer 15 is formed on the surface of the cushion layer 11b [FIG. 6 (b)].

  In the fourth aspect of the gravure plate cylinder 10a, a gravure cell having a gravure cell wall of a metal plating layer is formed on the surface of the copper plating layer 13 by lithography without using etching. Specifically, after forming the photosensitive composition layer on the surface of the copper plating layer, leaving the gravure cell forming portion of the photosensitive composition layer, removing the photosensitive composition layer of the non-gravure cell forming portion. Then, a non-gravure cell recess is formed on the surface of the photosensitive composition layer. Thereafter, after forming a metal plating layer in the non-gravure cell recess, the photosensitive composition layer in the gravure cell formation portion is removed to form a gravure cell recess.

  The photosensitive composition layer is formed using a photosensitive composition. As the photosensitive composition, either a negative type or a positive type can be used, but it is preferable to use a negative type photosensitive composition, and the negative type photosensitive composition of the first and second aspects described above. It is more preferable to use

A method for forming a gravure cell using a negative photosensitive composition will be described below.
Similarly to the above, a photosensitive composition layer 12 made of a negative photosensitive composition is formed on the surface of the copper plating layer 15 [FIG. 6 (c)]. Subsequently, in the same manner as described above, the photosensitive composition layer 12 is exposed to light (ultraviolet rays or the like) 20 through the mask 13 and exposed to light, and the exposed portion is set as an insolubilized exposed portion [FIG. 6 (d)]. The mask on the exposed photosensitive composition layer 12 is removed and developed in the same manner as described above, and the unexposed portion is dissolved and removed up to the copper plating layer 15. By this development processing, the unexposed part is dissolved and removed to form a concave non-gravure cell part 12b, and only the insolubilized exposed part 12a subjected to photoreaction is left. The surface of the developed copper plating layer 15 is washed with spray water for about 20 seconds to 1 minute to completely remove the unexposed portion and expose the surface of the copper plating layer 15 corresponding to the unexposed portion 12b [FIG. 6 (e)].

Subsequently, the surface of the exposed copper plating layer, that is, the concave non-gravure cell portion 12b is subjected to metal plating to form a metal plating layer 16 [FIG. 6 (f)]. Suitable metal plating includes nickel plating, chromium plating, copper plating and the like.
Next, the insolubilized exposed portion 12a is peeled off as described above. The gravure cell 14 is formed by removing the insolubilized exposed portion 12a [FIG. 6 (g)].

  In the fourth aspect of the gravure plate cylinder, the reinforced coating layer 18 is formed on the surfaces of the copper plating layer 15 and the metal plating layer 16 on which the gravure cell 14 is formed [FIG. 6 (h)]. . As a result, a gravure printing roll (gravure version) is completed.

  The present invention will be described more specifically with reference to the following examples. However, it is needless to say that these examples are shown by way of illustration and should not be construed in a limited manner.

(Production Examples 1-6)
A negative photosensitive composition was prepared with the compounding substances and blending ratios (parts by weight) shown in Table 1, and used as a test photosensitive solution.

Each component in Table 1 is as follows.
Polymer A1: Polymer having a structure represented by the following formula (8) [acid value (mgKOH / g) = 55]

(In the formula (8), R ²¹ represents a methyl group or an ethyl group, l is 20 to 50, m is 15 to 25, and n is 5 to 25.)

  Polymer A2: a polymer having a structure represented by the following formula (9) (acid value 65)

[In the formula (9), R ²² is hydrogen or a group represented by the following formula (10), and the equivalent ratio of the hydrogen atom in R ²² in the polymer to the group represented by the following formula (10) is 0.00. 6: 0.4. m is 37-40. ]

  Near-infrared absorbing dye B1: IR-T (made by Showa Denko KK, compound having a structure represented by the following formula (11))

Near-infrared absorbing dye B2: YKR-2100 (manufactured by Yamamoto Kasei Co., Ltd., near-infrared absorbing dye)
Monomer C1: DPE-6A (dipentaerythritol hexaacrylate)
Amines D1: Dimethylaminoethyl acrylate Amines D2: N, N-dimethylethanolamine Amines D3: Morpholine Amines D4: Piperazine hexahydrate Organic boron compounds E1: P3B (made by Showa Denko K.K. 12) a compound having the structure

Organoboron compound E2: CGI909 (Ciba Specialty Chemicals Co., Ltd., compound represented by formula (7))
Sulfonyl Compound F1: α, α, α-Tribromomethylphenylsulfone Sulfonyl Compound F2: 2-[(Tribromomethyl) sulfonyl] pyridine Silane coupling agent J1: Imidazolesilane [manufactured by Nikko Materials Co., Ltd.]
Polymerization inhibitor K1: Cuperon (manufactured by Wako Pure Chemical Industries, Ltd., trade name Q-1300)
Polymerization inhibitor K2: 2-mercaptobenzothiazole Coloring pigment: Oil blue 613 (manufactured by Orient Chemical Co., Ltd., Color Index (CI) No. 42595)
Surface conditioner: BYK-378 (3% solution, manufactured by Big Chemie, polyether-modified dimethylpolysiloxane)
PM: Propylene glycol monomethyl ether MeOH: Methanol IPA: Isopropyl alcohol MEK: Methyl ethyl ketone

(Production Examples 7 to 9)
A negative photosensitive composition was prepared with the compounding substances and blending ratios (parts by weight) shown in Table 2, and used as a test photosensitive solution.

Each component in Table 2 is as follows.
Polymer A3: a polymer having a structure represented by the following formula (13) [acid value (mgKOH / g) = 97, molecular weight Mw = 17000, Mn = 9200]

[In Formula ^{(13), R 23} represents a methyl or ethyl group, m is 15 to 60, n is 40 to 85. ]

Irgacure (Irgacure is a registered trademark of Ciba Specialty Chemicals Holdings Inc.) 250: a photoinitiator manufactured by Ciba Japan, a compound represented by the formula (2).
Triazine compound I1: Curezole (Cureazole is a registered trademark of Shikoku Kasei Kogyo Co., Ltd.) VT (2,4-diamino-6-vinyl-s-triazine, manufactured by Shikoku Kasei Kogyo Co., Ltd.)
Triazine Compound I2: Cureazole (Cureazole is a registered trademark of Shikoku Chemicals Co., Ltd.) MAVT (manufactured by Shikoku Chemicals Co., Ltd., 2,4-diamino-6-methacryloyloxyethyl-s-triazine)
Polymerization inhibitor K3: MNT (4-methoxynaphthol)
The near-infrared absorbing dye B2, the monomer C1, the coloring dye, the surface conditioner, PM, MeOH, IPA, and MEK are the same as in Table 1.

(Production Example 10)
A negative photosensitive composition was prepared with the compounding substances and blending ratios (parts by weight) shown in Table 3, and used as a test photosensitive solution.

  Each component in Table 3 is the same as Table 1.

(Example 1)
In order to produce the gravure plate cylinder (gravure plate making roll) shown in FIG. 2 using the test photosensitive solution obtained in Production Example 1, the following experiment was conducted.
First, a synthetic rubber sheet having a thickness of 5 cm is wound around the surface of an iron hollow roll having a circumference of 600 mm and a surface length of 1100 mm, and is firmly bonded, and then the surface is uniformly polished by cylindrical grinding and mirror polishing using a polishing machine. And a plate-making roll having a cushion layer was formed.

  The plate making roll is chucked at both ends with a fountain coating device (a device in which a dehumidifying device and a humidifying device are attached so that the humidity can be controlled as desired). p. Rotate at m and wipe thoroughly with a wiping cloth. The fountain coating apparatus is suitable for leveling while the solvent in the negative photosensitive composition evaporates during coating and the ratio of the solvent gradually rotates.

  After that, the pipe from which the test photosensitive solution is sprinkled from the upper end is positioned so as to have a gap of about 500 μm at one end of the plate making roll, and the test photosensitive solution is swelled by an amount necessary for coating, and the pipe is made to plate making. The test photosensitive solution was moved from one end of the roll to the other end and uniformly applied in a thickness of 5 μm by a spiral scan method, and 25 r. p. After continuing the rotation at m, it became touch dry (the state without the stickiness of the coating film) and stopped rotating.

  After waiting for 5 minutes and observing the dripping, it was not possible to observe that dripping occurred with the naked eye. When the film thickness was measured, there was no difference between the lower surface portion and the upper surface portion of the roll. Thus, it was confirmed that the dried photosensitive film could be set in a state without dripping.

  Subsequently, the plate making roll was set to 100 r. p. After rotating at m for 20 minutes and stopping, the residual solvent concentration in the photosensitive film was measured and found to be 2%.

  A gravure cell was formed on the surface of the photosensitive film by photolithography. That is, the plate-making roll is attached to an exposure apparatus (manufactured by Sink Laboratories) equipped with a high-power semiconductor laser head of Creositex, and a mask having a mask image which is a gravure image is laminated on the surface of the photosensitive film, A negative image is printed by irradiating the plate-making roll with a laser in the infrared wavelength region, and then the plate-making roll is attached to a developing device except for the mask and rotated to raise the developing tank for development. The photo-reacted insolubilized exposed portion was left and the unexposed portion was dissolved in a developer so that the cushion layer was exposed to form a gravure cell having a depth of 5 μm, and then washed with water. The developer used was 0.8% triethanolamine (24 ° C.).

  A gravure printing roll (gravure cylinder) was completed by forming a diamond-like carbon (DLC) film having a thickness of 1 μm on the upper surface of the cushion layer of the plate-making roll on which the gravure cell was formed by sputtering.

  Subsequently, cyan ink (Zahn cup viscosity 18 seconds, water-based ink Super Lampy Pure Indigo 800PR-5, manufactured by Sakata Inks Co., Ltd.) was applied to the obtained gravure cylinder, and OPP (Oriented Polypropylene Film: biaxially stretched polypropylene film) ) Was used to perform a printing test (printing speed: 120 m / min). The obtained printed matter had no plate fog and could be printed up to a length of 50,000 m. The accuracy of the pattern did not change. Since the gradation from the highlight portion to the shadow portion of this gravure plate is not different from that of the conventional gravure plate produced according to a conventional method, it is determined that there is no problem in ink transferability. Moreover, when the printing test was done with respect to the glass plate, it confirmed that favorable printing could be performed without a glass plate breaking.

(Examples 2-9)
A gravure cylinder in which a gravure cell was formed was manufactured in the same procedure as in Example 1 except that the test photosensitive solution obtained in Production Examples 2 to 9 was used as the test photosensitive solution. When a printing test was performed using this gravure cylinder, good printing performance was shown as in Example 1.

(Example 10)
As a test sensitizing solution, the test sensitizing solution obtained in Production Example 10 was used, and an experiment was performed in the same manner as in Example 1 except that the burning treatment was performed before exposure. As a result, a large number of recesses could be formed. However, compared with Examples 1-9, there was unevenness | corrugation in a recessed part and the uneven | corrugated shaped precision was inferior.

(Example 11)
The same plate-making roll as in Example 1 was produced, and the following experiment was conducted to produce the gravure plate cylinder (gravure plate-making roll) shown in FIG. 4 using the test photosensitive solution obtained in Production Example 1. The same procedure as in Example 1 was performed until the photosensitive solution was applied and dried.

  Subsequently, the plate-making roll is attached to an exposure apparatus (manufactured by Sink Laboratories, Inc.) equipped with a high-power semiconductor laser head of Creositex, and a mask having a mask image as a gravure image is laminated on the surface of the photosensitive film. The plate-making roll is irradiated with a laser in the infrared wavelength region to print a negative image, and then the plate-making roll is attached to the developing device except for the mask and rotated to raise the developing tank for development and photosensitivity. The insolubilized exposed part of the film that had been photoreacted was left, and the unexposed part was dissolved in the developer so that the cushion layer was exposed, and then washed with water. The developer used was 0.8% triethanolamine (24 ° C.).

  The plate-making roll that had been developed and left the insolubilized exposed portion was washed with spray water for about 20 seconds to 1 minute to completely remove the unexposed portion. Subsequently, the cushion layer surface of the plate-making roll leaving the insolubilized exposed portion (resist) was etched. This etching was performed using toluene. The depth of the recess (gravure cell) was 5 μm. After completion of the etching, the insolubilized exposed portion (resist) was peeled off with an aqueous NaOH solution. Finally, the surface of the plate making roll from which the insolubilized exposed portion (resist) was removed was washed with water. A concave part (gravure cell) having a beautiful edge depth of 5 μm could be formed on the surface of the cushion layer of the plate-making roll obtained.

  A gravure printing roll (gravure cylinder) was completed by forming a diamond-like carbon (DLC) film having a thickness of 1 μm on the upper surface of the cushion layer of the plate-making roll on which the gravure cell was formed by sputtering.

  Subsequently, when a printing test was performed using the obtained gravure cylinder, good printing performance was shown as in Example 1.

Example 12
The same plate-making roll as in Example 1 was produced, and the following experiment was conducted to produce the gravure plate cylinder (gravure plate-making roll) shown in FIG. 5 using the test photosensitive solution obtained in Production Example 1.

  This plate making roll is mounted on a plating tank, the anode chamber is brought close to the plate making roll up to 20 mm by an automatic slide device by a computer system, the plating solution is overflowed, and the plate making roll is completely submerged, and 18A / dm2,6. An 80 μm copper plating layer was formed at 0V. The plating time was 20 minutes, and the surface of the plating was free of spots and pits, and a uniform copper plating layer was obtained. The same procedure as in Example 1 was performed until the photosensitive solution was applied to the plate-making roll on which the copper plating layer was formed and dried.

  Subsequently, the plate-making roll is attached to an exposure apparatus (manufactured by Sink Laboratory Co., Ltd.) equipped with a high-power semiconductor laser head manufactured by Creositex, and a mask having a mask image as a gravure image is laminated on the surface of the photosensitive film. The plate-making roll is irradiated with a laser in the infrared wavelength region to print a negative image, and then the plate-making roll is attached to the developing device except for the mask and rotated to raise the developing tank for development and photosensitivity. The insolubilized exposed portion that was photoreacted on the film was left, and the unexposed portion was dissolved in the developer so that the copper plating layer was exposed, and then washed with water. The developer used was 0.8% triethanolamine (24 ° C.).

  The plate-making roll that had been developed and left the insolubilized exposed portion was washed with spray water for about 20 seconds to 1 minute to completely remove the unexposed portion. Next, the copper plating layer was dry-etched by plasma etching to engrave an image from the gravure cell, and then the insolubilized exposed portion (resist) was peeled off with a 5% KOH aqueous solution. Finally, the surface of the plate making roll from which the insolubilized exposed portion (resist) was removed was washed with water. A concave portion (gravure cell) having a beautiful depth of 5 μm could be formed on the surface of the copper plating layer of the plate making roll obtained.

  A foundation layer (chromium plating layer) having a thickness of 1 μm was formed on the upper surface of the copper plating layer of the plate-making roll on which the gravure cell was formed.

  A diamond-like carbon (DLC) film having a thickness of 1 μm was formed on the upper surface of the chromium plating layer by sputtering to complete a gravure printing roll (gravure cylinder).

  Subsequently, when a printing test was performed using the obtained gravure cylinder, good printing performance was shown as in Example 1.

(Example 13)
The same plate-making roll as in Example 1 was produced, and the following experiment was conducted to produce the gravure plate cylinder (gravure plate-making roll) shown in FIG. 6 using the test photosensitive solution obtained in Production Example 1. A copper plating layer was formed on the plate making roll in the same manner as in Example 8, and then the same procedure as in Example 1 was performed until the photosensitive solution was applied and dried on the plate making roll on which the copper plating layer was formed.

  Subsequently, the plate-making roll is attached to an exposure apparatus (manufactured by Sink Laboratory Co., Ltd.) equipped with a high-power semiconductor laser head manufactured by Creositex, and a mask having a mask image as a gravure image is laminated on the surface of the photosensitive film. The plate-making roll is irradiated with a laser in the infrared wavelength region to print a negative image, and then the plate-making roll is attached to the developing device except for the mask and rotated to raise the developing tank for development and photosensitivity. The insolubilized exposed portion that was photoreacted on the film was left, and the unexposed portion was dissolved in the developer so that the copper plating layer was exposed, and then washed with water. The developer used was 0.8% triethanolamine (24 ° C.).

  The plate-making roll that had been developed and left the insolubilized exposed portion was washed with spray water for about 20 seconds to 1 minute to completely remove the unexposed portion. Next, the plate-making roll leaving the insolubilized exposed portion (resist) was subjected to Ni plating treatment to form a Ni plating layer in the recess from which the unexposed portion was removed. This Ni plating treatment was performed at 8 to 10 V for 10 minutes to form a Ni plating layer having a thickness of 5 μm, which is the height of the recess from which the unexposed portions were removed. After the completion of the Ni plating treatment, the insolubilized exposed portion (resist) was peeled and removed with a 5% KOH aqueous solution to form a recess (gravure cell). Finally, the surface of the plate making roll from which the insolubilized exposed portion (resist) was removed was washed with water. A concave portion (gravure cell) having a beautiful depth of 5 μm at the edge, in which the wall of the gravure cell was a Ni plating layer, could be formed on the surface of the copper plating layer of the plate making roll obtained.

  A diamond-like carbon (DLC) film having a thickness of 1 μm was formed on the upper surfaces of the copper plating layer and the Ni plating layer of the plate-making roll on which the gravure cell was formed by sputtering to complete a gravure printing roll (gravure cylinder). .

  Subsequently, when a printing test was performed using the obtained gravure cylinder, good printing performance was shown as in Example 1.

(Example 14)
A gravure platemaking roll was produced in the same manner as in Example 13 except that a Cr plating layer was formed in a recess from which an unexposed portion was removed by Cr plating instead of a Ni plating layer. As in Example 13, good printing results were obtained.

(Example 15)
A gravure platemaking roll was produced in the same manner as in Example 13 except that a Cu plating layer was formed in a recess from which an unexposed portion was removed by Cu plating instead of a Ni plating layer. As in Example 13, good printing results were obtained.

(Example 16)
A gravure cell was formed in the same procedure as in Example 1, and a silicon dioxide film was formed on the upper surface of the cushion layer of the plate-making roll on which this gravure cell was formed as follows. A 20% dibutyl ether solution of perhydropolysilazane (product name: AQUAMICA (registered trademark of AZ Electronic Materials Co., Ltd.) NL120A, manufactured by AZ Electronic Materials Co., Ltd.) is applied to the surface of the photosensitive composition layer. HVLP spray application was performed. The coating film thickness uniformly applied on the surface of the photosensitive composition layer was 0.8 μm. The cylinder coated with perhydropolysilazane was subjected to two-stage heat treatment (140 ° C. 5 minutes + 170 ° C. 5 minutes) using superheated steam to form a silicon dioxide film. This film had an extremely high film hardness that was not damaged by a cutter knife. In this way, a gravure cylinder having cushioning properties was completed. When a printing test was performed using this gravure cylinder, good printing performance was shown as in Example 1.

(Example 17)
A gravure cylinder was produced in the same procedure as in Example 1 except that a chromium plating layer was formed by a conventional method instead of the DLC layer (including the W layer and the WC layer) as the reinforcing coating layer. When a printing test was performed using this gravure cylinder, good printing performance was shown as in Example 1.

(Example 18)
A gravure printing roll was produced in the same manner as in Example 1 except that a 0.1 μm Al layer and a 1 μm DLC layer were formed by plasma CVD instead of forming a DLC film by sputtering. It was confirmed that the results were obtained.

  In the above-described embodiments and examples, examples in which the above-described negative photosensitive composition is used as a preferred example of the photosensitive composition (photosensitive solution) have been described. However, a positive type is used unless departing from the technical idea of the present invention. It is needless to say that a photosensitive composition can be used, and negative photosensitive compositions other than those exemplified can be used. In the present invention, a DLC film (by a sputtering method or a CVD method), a silicon dioxide film (using a perhydropolysilazane solution), and a conventional chromium plating layer can be used as the reinforcing coating layer for the gravure plate cylinder. In the above embodiment, it is shown that any reinforced coating layer can be applied to the gravure plate cylinder (gravure plate making roll) of Example 1, but also about the gravure plate cylinder (gravure plate making roll) obtained by other examples. Confirmed that it is applicable.

It is sectional explanatory drawing which shows an example of embodiment of the gravure double-sided simultaneous printing apparatus of this invention. It is explanatory drawing which shows typically an example of the process of the manufacturing method of the 1st aspect of the gravure printing cylinder which has a cushioning property used for the gravure double-sided simultaneous printing apparatus of this invention, (a) is resin which has rubber | gum or cushioning property (B) is a partially enlarged sectional view showing a state in which a negative photosensitive composition layer is formed on the surface of the cushion layer, (c) ) Is a partially enlarged sectional view showing a state in which a mask is provided on the surface of the negative photosensitive composition layer, and (d) is a partially enlarged sectional view showing a state in which a gravure cell is formed on the surface of the negative photosensitive composition layer. (E) is a partial expanded sectional view which shows the state which formed the reinforcement | strengthening coating layer on the surface of the negative photosensitive composition layer. It is drawing similar to FIG. 2 which shows the other example of the process of the manufacturing method of the 1st aspect of the gravure printing cylinder which has a cushioning property used for the gravure double-sided simultaneous printing apparatus of this invention. It is explanatory drawing which shows typically an example of the process of the manufacturing method of the 2nd aspect of the gravure printing cylinder which has a cushioning property used for the gravure double-sided simultaneous printing apparatus of this invention, (a) is resin which has rubber | gum or cushioning property (B) is a partially enlarged sectional view showing a state in which a negative photosensitive composition layer is formed on the surface of the cushion layer, (c) ) Is a partial enlarged cross-sectional view showing a state where a mask is provided on the surface of the negative photosensitive composition layer. (D) is a case where an exposed portion is insolubilized exposed portion by a developer by exposure and an unexposed portion is exposed to the cushion layer surface by the developer. Partial enlarged cross-sectional view showing a state after dissolution and removal, (e) is a partial enlarged cross-sectional view showing a state in which a gravure cell is formed on the cushion layer by etching, and (f) is a separation removal of the insolubilized exposed portion. Partially enlarged sectional view showing a state, which is a partially enlarged cross-sectional view showing a (g) is a state of forming a reinforcing coating layer on the surface of the cushion layer. It is explanatory drawing which shows typically an example of the process of the manufacturing method of the 3rd aspect of the gravure printing cylinder which has a cushioning property used for the gravure double-sided simultaneous printing apparatus of this invention, (a) is resin which has rubber | gum or cushioning property A sectional view of the whole of a hollow roll (plate base material) having a cushion layer formed on the surface, (b) is a partially enlarged sectional view showing a state in which a copper plating layer is formed on the surface of the cushion layer, and (c) is a copper plating. The partial expanded sectional view which shows the state which formed the negative photosensitive composition layer in the surface of the layer, (d) is the partial expanded sectional view which shows the state which provided the mask in the surface of the negative photosensitive composition layer, (e ) Is a partially enlarged cross-sectional view showing a state in which an exposed portion is insolubilized exposed portion with a developer by exposure and an unexposed portion is dissolved and removed by the developer to the surface of the copper plating layer, and (f) is a recess ( (G) is a partially enlarged sectional view showing a state in which the insolubilized exposed portion is peeled and removed, and (h) is a base layer (for example, a chromium plating layer) on the surface of the copper plating layer. ) Is a partially enlarged cross-sectional view showing a state in which a reinforced coating layer is formed on the surface of the chromium plating layer. It is explanatory drawing which shows typically an example of the process of the manufacturing method of the 4th aspect of the gravure printing cylinder which has a cushioning property used for the gravure double-sided simultaneous printing apparatus of this invention, (a) is resin which has rubber | gum or cushioning properties A sectional view of the whole of a hollow roll (plate base material) having a cushion layer formed on the surface, (b) is a partially enlarged sectional view showing a state in which a copper plating layer is formed on the surface of the cushion layer, and (c) is a copper plating. The partial expanded sectional view which shows the state which formed the negative photosensitive composition layer in the surface of the layer, (d) is the partial expanded sectional view which shows the state which provided the mask in the surface of the negative photosensitive composition layer, (e ) Is a partially enlarged sectional view showing a state in which an exposed portion is insolubilized exposed portion by a developer and an unexposed portion is dissolved and removed to the copper plating layer surface by a developer to form a non-gravure cell portion, and (f) is a metal plating. Yo Partial enlarged sectional view showing a state in which a metal plating layer is formed on a non-gravure cell part, (g) is a partial enlarged sectional view showing a state in which a gravure cell is formed by peeling and removing an insolubilized exposed part to expose a copper plating layer (H) is a partial expanded sectional view which shows the state which formed the reinforcement coating layer on the surface of a copper plating layer and a metal plating layer. It is sectional drawing which shows the structural example of the conventional gravure offset printing apparatus.

Explanation of symbols

  10: Plate base material, 10a, 10b: Gravure plate (gravure plate cylinder, gravure plate roll), 11a: Hollow roll, 11b: Cushion layer, 12: Photosensitive composition layer, 12a: Insolubilized exposed portion, 13: Mask, 14, 14a, 14b: gravure cell, 15: copper plating layer, 16: chrome plating layer, 18: reinforced coating layer, 20: light, 50: conventional gravure offset printing apparatus, 50A, 50B: gravure printing apparatus of the present invention 52: gravure cell, 54: gravure printing cylinder, 56: plate-shaped printing material, 58: blanket roll, 60, 60a, 60b: doctor blade, 62, 62a, 62b: ink, 64: impression cylinder.

Claims (25)

A gravure double-sided simultaneous printing device for both the front and back surfaces of a plate-shaped printing material,
Transport means for transporting the plate-shaped printing material in a certain direction;
A pair of gravure printing cylinders having cushioning properties that are installed so as to be able to come into contact with the front and back surfaces of the material to be printed and have gravure cells on the printing plate;
A doctor blade provided so as to be in contact with the plate surface of the pair of gravure plate cylinders,
Including
The ink supplied to the pair of gravure plate cylinders is stored in the gravure cell by the doctor blade, and the pair of gravure plate cylinders is rotated and the pair of gravure printing materials is advanced in a certain direction. The gravure plate cylinder is brought into contact with the front and back surfaces of the plate-like printing material, so that the ink stored in the gravure cell is directly transferred to the front and back surfaces of the plate-like printing material and the plate-like printing material A gravure double-sided simultaneous printing apparatus, wherein gravure printing is performed simultaneously on the front and back surfaces of a material. The gravure plate cylinder having the cushioning property,
A plate base material provided with a cushion layer made of rubber or a resin having cushioning properties on the surface;
A photosensitive composition layer formed on the surface of the cushion layer;
A gravure cell formed on the surface of the photosensitive composition layer;
A reinforcing coating layer formed on the surface of the photosensitive composition layer on which the gravure cell is formed;
The gravure double-sided simultaneous printing apparatus according to claim 1, further comprising: The photosensitive composition layer is formed using a negative photosensitive composition,
The negative photosensitive composition is
(A) a polymer having a carboxyl group and having an ethylenically unsaturated bond;
(B) a near infrared absorbing dye,
(C) a monomer having at least one ethylenically unsaturated bond;
(D) one or more amines selected from the group consisting of amino alcohols, amino alcohol derivatives and cyclic amines;
(E) an organoboron compound;
(F) a sulfonyl compound represented by the following formula (1);
The gravure double-sided simultaneous printing apparatus according to claim 2, further comprising:

Wherein (1), Q represents an aryl group or a heterocyclic group, a halogen atom X ¹ to X ³ are each independently]   4. The gravure double-sided simultaneous printing apparatus according to claim 3, wherein the amino alcohol derivative is a (meth) acrylic acid ester of amino alcohol.   The gravure duplex printing apparatus according to claim 3, wherein the cyclic amine is a morpholino group-containing compound or a piperazine compound.   6. The compound (F) represented by the formula (1) is tribromomethylphenyl sulfone or 2-[(tribromomethyl) sulfonyl] pyridine. Gravure duplex printing device. The photosensitive composition layer is formed using a negative photosensitive composition,
The negative photosensitive composition is
(A) a polymer having a carboxyl group and having an ethylenically unsaturated bond;
(B) a near infrared absorbing dye,
(C) a monomer having at least one ethylenically unsaturated bond;
(G) 2-mercaptobenzoxazole and / or 2-mercaptooxazole;
(H) a diphenyliodonium salt represented by the following formula (2);
The gravure double-sided simultaneous printing apparatus according to claim 2, further comprising:

The gravure double-sided simultaneous printing apparatus according to claim 7, wherein the negative photosensitive composition further comprises (I) a triazine compound represented by the following general formula (3).

[In the general formula (3), R ¹ is a vinyl group or a monovalent organic group containing a vinyl group]   9. The (I) triazine compound is 2,4-diamino-6-vinyl-s-triazine and / or 2,4-diamino-6-methacryloyloxyethyl-s-triazine. Gravure double-sided simultaneous printing device.   The gravure double-sided simultaneous printing apparatus according to any one of claims 3 to 9, wherein the negative photosensitive composition further contains (J) a silane coupling agent.   The gravure double-sided simultaneous printing apparatus according to any one of claims 3 to 10, wherein the negative photosensitive composition further contains (K) a polymerization inhibitor. The gravure plate cylinder having the cushioning property,
A plate base material provided with a cushion layer made of rubber or a resin having cushioning properties on the surface;
A gravure cell formed on the surface of the cushion layer;
A reinforcing coating layer formed on the surface of the cushion layer forming the gravure cell;
The gravure double-sided simultaneous printing apparatus according to claim 1, further comprising: The gravure plate cylinder having the cushioning property,
A plate base material provided with a cushion layer made of rubber or a resin having cushioning properties on the surface;
A copper plating layer formed on the surface of the cushion layer;
A gravure cell formed by etching on the copper plating layer;
A reinforced coating layer formed on the surface of the copper plating layer on which the gravure cell is formed;
The gravure double-sided simultaneous printing apparatus according to claim 1, further comprising: The gravure plate cylinder having the cushioning property,
A plate base material provided with a cushion layer made of rubber or a resin having cushioning properties on the surface;
A copper plating layer formed on the surface of the cushion layer;
A gravure cell formed by forming a gravure cell wall comprising a metal plating layer on the surface of the copper plating layer;
A reinforced coating layer formed on the surface of the copper plating layer and the metal plating layer on which the gravure cell is formed;
The gravure double-sided simultaneous printing apparatus according to claim 1, further comprising:   The gravure double-side printing apparatus according to any one of claims 2 to 14, wherein the reinforcing coating layer is a DLC layer, a silicon dioxide film, or a chromium plating layer.   The gravure double-sided simultaneous printing apparatus according to claim 15, wherein the silicon dioxide film is formed using a perhydropolysilazane solution.   A printed matter produced using the printing apparatus according to any one of claims 1 to 16.   A printed matter that is gravure-printed by arranging a gravure ink composed of water-based ink, oil-based ink, or phase change ink on a surface of a printing material sheet so as to form a predetermined pattern by printing. The printed matter according to claim 17, wherein the gravure ink is printed using the printing apparatus according to claim 1.   It is a microlens manufactured by arrange | positioning the ink for microlens formation on the surface of a sheet-like base material by printing at predetermined intervals, Comprising: The printing of any one of Claims 1-16 A microlens, wherein the microlens forming ink is printed using an apparatus.   It is the wallpaper manufactured by arrange | positioning so that a predetermined pattern may be formed by printing the wallpaper ink on the surface of a wallpaper base material, Comprising: Using the printing apparatus of any one of Claims 1-16, A wallpaper characterized by printing ink for wallpaper.   The electromagnetic wave shielding sheet manufactured by arrange | positioning so that the electromagnetic wave shielding layer of a predetermined pattern may be formed by printing an electrically conductive paste on the surface of an electromagnetic wave shielding base material, Comprising: The electromagnetic wave shielding sheet of any one of Claims 1-16 An electromagnetic wave shielding sheet, wherein the conductive paste is printed using a printing apparatus.   The color filter manufactured by arrange | positioning so that a color filter layer of a predetermined pattern may be formed by printing color filter ink on the surface of a color filter base material, Comprising: Printing of any one of Claims 1-16 A color filter, wherein the color filter ink is printed using an apparatus.   It is a polarizing plate manufactured by arrange | positioning so that a polarizing layer of a predetermined pattern may be formed by printing a polarizing ink on the surface of a polarizing plate base material, Comprising: The printing apparatus of any one of Claims 1-16 A polarizing plate, wherein the polarizing ink is used for printing.   A ceramic capacitor manufactured by arranging a conductive paste on a ceramic substrate so as to form an internal electrode by printing, wherein the conductive paste is formed using the printing apparatus according to any one of claims 1 to 16. Ceramic capacitor, characterized in that a functional paste is printed.   Electronic paper manufactured by disposing a microencapsulated cell containing magnetic powder on a base film so as to form a predetermined pattern by applying it through a binder, An electronic paper, wherein the microencapsulated cell is applied using the printing apparatus according to any one of the preceding claims.

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