JP2009093170A - Photogravure plate having cushion property and method of manufacturing it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a printing plate, especially a photogravure plate having cushion property, enabling direct gravure printing without a blanket roll to a hard material to be printed by cushion property, favorably performing gravure printing to a rough surface such as corrugated board printing, color printing a matrix image for forming a color filter to glass for a liquid crystal panel glass, or preferable for color printing an image on a compact disk. <P>SOLUTION: This photogravure plate includes: a cushion layer made of resin rubber or cushion property; a negative photosensitive composition layer formed on the surface of the cushion layer; and a gravure cell formed on the surface of the negative photosensitive composition layer, wherein the negative photosensitive composition layer is formed of a negative photosensitive composition, and the negative photosensitive composition contains a predetermined composition. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention provides cushioning properties suitable for printing on a rough surface such as cardboard, printing an image on a compact disk, etc., or color printing a matrix image for constituting a color filter on a glass for a liquid crystal panel. In particular, the present invention relates to a gravure printed material, a microlens, a wallpaper, an electromagnetic wave shield sheet, a color filter, a polarizing plate, a capacitor, electronic paper, and the like manufactured using the gravure plate.

  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 is that gravure printing does not have cushioning properties, so if the printing pressure increases, it may break the glass or distort the compact disc, etc., so by printing through a blanket roll made of rubber, This is because when the printing pressure increases, gravure offset printing that can suppress an increase in printing pressure due to deformation of rubber is appropriate.

  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.

Therefore, the applicant of the present application forms a photosensitive composition layer on a cushion layer made of rubber or a resin having cushioning properties, and stacks or overlaps a mask having a gravure image on the surface of the photosensitive composition layer, and irradiates with ultraviolet rays. A method for producing a gravure plate having cushioning properties, in which a mask is removed and development is performed to form a gravure cell in the photosensitive composition layer, and then a DLC film is formed (Patent Document 1). However, in this proposal, since the gravure cell is formed using the existing photosensitive composition layer, the shape of a practical gravure cell that can be used for gravure printing has not yet been formed. Is the current situation.
JP 2000-199949 A

  The applicant of the present application has recently developed a new type of negative photosensitive composition that has not been conventionally used, and has been researching various application fields using this new negative photosensitive composition. As a result of applied research on a gravure plate having the property, a gravure plate having a new cushioning property has been completed. Since the present invention has a printing plate, in particular, cushioning properties, direct gravure printing without using a blanket roll can be performed on a hard substrate, and gravure printing on a rough surface such as cardboard printing can be performed well. And providing a gravure plate having cushioning properties suitable for color printing a matrix image for forming a color filter on glass for a liquid crystal panel or color printing an image on a compact disk and the like, and a method for producing the same. Furthermore, it is an object to provide a gravure printed matter, a microlens, a wallpaper, an electromagnetic wave shielding sheet, a color filter, a polarizing plate, a condenser, electronic paper and the like manufactured using the gravure plate.

  In order to solve the above problems, a first aspect of a gravure plate having cushioning properties according to the present invention includes a plate base material provided with a cushion layer made of rubber or a resin having cushioning properties on the surface, and the surface of the cushion layer. A negative photosensitive composition layer formed on the surface of the negative photosensitive composition layer and a gravure cell formed on the surface of the negative photosensitive composition layer. The negative photosensitive composition comprises (A) a polymer having a carboxyl group and an ethylenically unsaturated bond, (B) a near infrared absorbing dye, and (C) at least one ethylenically unsaturated compound. A monomer having a 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 (1) Indicated by Characterized in that it contains a sulfonyl compound, a.

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.

  The second aspect of the gravure plate having cushioning properties of the present invention includes a plate base material provided with a cushion layer made of rubber or a resin having cushioning properties on the surface, and a negative photosensitive material formed on the surface of the cushion layer. And a gravure cell formed on the surface of the negative photosensitive composition layer, the negative photosensitive composition layer comprising a negative photosensitive composition, the negative photosensitive composition (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, and (G 2) 2-mercaptobenzoxazole and / or 2-mercaptooxazole, and (H) a diphenyliodonium salt represented by the following formula (2).

  In the second aspect of the gravure plate of the present invention, it is preferable that 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.

  In the first and second embodiments of the gravure plate of the present invention, it is preferable that the negative photosensitive composition further contains (J) a silane coupling agent.

  In the first and second embodiments of the gravure plate of the present invention, it is preferable that the negative photosensitive composition further contains (K) a polymerization inhibitor. As the polymerization inhibitor (K), a thiazole compound is preferably used.

  The first and second aspects of the gravure plate having cushioning properties of the present invention preferably further include a reinforcing coating layer formed on the surface of the negative photosensitive composition layer on which the gravure cell is formed. As the reinforcing coating layer, a DLC (diamond-like carbon) layer, a silicon dioxide film or a chromium plating layer can be used. The silicon dioxide film is preferably formed using a perhydropolysilazane solution.

  A gravure cell may be formed on the surface of the photosensitive composition layer so that the cushion layer is not exposed, or a gravure cell may be formed on the surface of the photosensitive composition layer so that the cushion layer is exposed. It can also be formed.

  The first aspect of the method for producing a gravure plate having cushioning properties of the present invention is a method for producing the above-described first aspect of the gravure plate of the present invention, wherein the cushion layer is made of rubber or a resin having cushioning properties. Forming a negative photosensitive composition layer on the surface of the film, and forming a gravure cell on the surface of the negative photosensitive composition layer, wherein the negative photosensitive composition layer is a negative photosensitive film. The negative photosensitive composition comprises (A) a polymer having a carboxyl group and 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) Characterized in that it contains and a sulfonyl compound represented by the serial 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 second aspect of the method for producing a gravure plate having cushioning properties of the present invention is a method for producing the above-described second aspect of the gravure plate of the present invention, wherein the cushion layer is made of rubber or a resin having cushioning properties. Forming a negative photosensitive composition layer on the surface of the film, and forming a gravure cell on the surface of the negative photosensitive composition layer, wherein the negative photosensitive composition layer is a negative photosensitive film. The negative photosensitive composition comprises (A) a polymer having a carboxyl group and an ethylenically unsaturated bond, (B) a near-infrared absorbing dye, and (C) at least one 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). Characterized in that it.

  In the first and second embodiments of the method for producing a gravure plate having cushioning properties of the present invention, the method for forming a gravure cell on the surface of the negative photosensitive composition layer is as follows. A step of applying a negative photosensitive composition to the cushion layer surface, a step of drying the applied negative photosensitive composition film, a step of exposing the dried negative photosensitive composition film, and the exposure And developing the negative photosensitive composition film so as to dissolve and remove the unexposed portion to leave the exposed portion. The unexposed portion thus dissolved and removed becomes a gravure cell, and the remaining exposed portion becomes a gravure cell wall. Part.

  The first and second aspects of the method for producing a gravure plate having cushioning properties according to the present invention further includes a step of forming a reinforcing coating layer that covers the surface of the negative photosensitive composition layer on which the gravure cell is formed. It is preferable to include. As the reinforcing coating layer, as described above, a DLC layer, a silicon dioxide film, or a chromium plating layer can be used.

The printed matter of the present invention is manufactured using the gravure plate having cushioning properties according to the first and second aspects of the present invention described above.
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 matter in which the gravure ink is printed using a gravure plate 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 gravure plate 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 gravure plate 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, and the gravure of the present invention The conductive paste is printed using a plate.

  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 of a predetermined pattern by printing, and the gravure plate 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 placing a polarizing ink on the surface of a polarizing plate substrate so as to form a polarizing layer of a predetermined pattern by printing, and using the gravure plate 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 gravure plate 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 gravure plate of the present invention.

  According to the present invention, the printing plate can have cushioning properties, and direct gravure printing can be performed on a hard substrate without using a blanket roll, and a color filter is formed on the glass for a liquid crystal panel. Therefore, it is suitable for color printing a matrix image or color printing an image on a compact disk or the like, and printing on a rough surface such as corrugated cardboard printing can be performed well.

  In particular, the negative photosensitive composition used in the present invention does not require burning and overcoating before exposure, and has excellent sensitivity, adhesion and storage stability, and this negative photosensitive composition is used. Thus, the gravure cell of the present invention formed by photolithography has a remarkable effect of having a sharp gravure cell shape that is practical and compatible with gravure printing. Furthermore, by using the gravure plate 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 transition of ink materials and coating materials can be achieved. It becomes easy and it becomes possible to obtain a final product with excellent performance.

  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.

  The gravure plate having cushioning properties of the present invention is a plate base material provided with a cushion layer made of rubber or a resin having cushioning properties on the surface, a negative photosensitive composition layer formed on the surface of the cushion layer, A gravure cell formed on the surface of the negative photosensitive composition layer, the negative photosensitive composition layer comprising a negative photosensitive composition, and the negative photosensitive composition will be described later. It is formed with the negative photosensitive composition of the 1st and 2nd aspect. The negative photosensitive compositions of the first and second aspects used in the present invention are described below.

  The first aspect of the negative photosensitive composition used in the present invention includes (A) a polymer having a carboxyl group and an ethylenically unsaturated bond, (B) a near-infrared absorbing dye, and (C) at least A monomer having one 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; F) A sulfonyl compound represented by the following formula (1) is contained.

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.

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

  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 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 the process of the manufacturing method of the gravure plate of this invention by using the above-mentioned negative photosensitive composition as a photosensitive solution is demonstrated with reference to FIGS.
FIG. 1 is an explanatory view schematically showing an example of a process for producing a gravure plate having cushioning properties according to the present invention. (A) is a hollow roll having a cushion layer made of a rubber or a resin having cushioning properties formed on the surface. (Plate base material) whole sectional view, (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 the surface of the negative photosensitive composition layer The partial expanded sectional view which shows the state which provided the mask in (d) is the partial expanded sectional view which shows the state which formed the gravure cell in the surface of a negative photosensitive composition layer, (e) is a negative photosensitive composition It is a partial expanded sectional view which shows the state which formed the reinforcement coating layer on the surface of the layer. FIG. 2 is a flowchart showing the steps of the manufacturing method shown in FIG. FIG. 3 is a flowchart showing the order of steps of the gravure cell forming process according to 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 (step 100 in FIG. 2). In FIG. 1, the code | symbol 10 is a plate base material and what provided the cushion layer 11b on the surface of the hollow roll 11a is used. 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, the negative photosensitive composition layer 12 is formed on the surface of the cushion layer 11b (FIG. 1 (b), step 102 in FIG. 2). The film thickness of the negative photosensitive composition layer 12 is not particularly limited, and is determined according to the cell depth 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 negative photosensitive composition layer 12 is formed by coating to have a thickness of 5 to 6 μm, and the cell is 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 negative 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 formation of the negative photosensitive composition layer 12, cost, and development.

  The negative photosensitive composition layer 12 is formed using the negative photosensitive composition of the first and second aspects described above. The negative photosensitive composition is usually used as a solution (photosensitive solution) in which the above components are dissolved in a solvent such as a cellosolve solvent or a propylene glycol solvent. An example of a method for forming the negative photosensitive composition layer 12 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 (step 200 in FIG. 3).
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 this photosensitive solution may be appropriately set according to the desired film thickness of the negative photosensitive composition layer 12, but is preferably in the range of 1 to 10 μm in terms of dry film thickness. More preferably, it is set to ˜7 μm. 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 negative photosensitive composition layer 12 composed of a negative photosensitive film (step 202 in FIG. 3). 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 used in the present invention has an effect of exhibiting sufficient adhesion without performing a burning process (heating process) before exposure.

  Subsequently, the gravure cell 14 is formed on the surface of the negative photosensitive composition layer 12 by photolithography (step 104 in FIG. 2). The photolithography procedure is as follows.

As shown in FIG.1 (c), the mask 13 which has a mask image which is a gravure image is laminated | stacked on the surface of the negative photosensitive composition layer 12, or it closely_contact | adheres.
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. And can save energy.

  Subsequently, light (ultraviolet rays or the like) 20 is irradiated for a necessary time, and the negative photosensitive composition layer 12 is exposed through the mask 13 (FIG. 1C and step 204 in FIG. 3). By this exposure treatment, a necessary part of the negative photosensitive composition layer 12 is caused to undergo a photoreaction, and the exposed part is insolubilized in the developer.

The light source for image exposure of the negative photosensitive composition layer is preferably a semiconductor laser or YAG laser that generates an infrared laser beam having a wavelength of 700 to 1,100 nm. For example, the semiconductor laser 20 having a wavelength of 830 nm and an intensity of 220 mJ / cm ^2. Is preferably used. 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, the mask 13 on the exposed negative photosensitive composition layer 12 is removed, and development is performed (step 206 in FIG. 3). This development process dissolves and removes the unexposed portions, leaving only the insolubilized exposed portions 12a that have undergone photoreaction. As shown in FIG. 1D, it is preferable to form the gravure cell 14 by dissolving the unexposed portion in a developer so that the cushion layer 11b is exposed.

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 the unexposed portion (step 208 in FIG. 3). 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.
In this embodiment, the gravure cell 14 is formed on the negative photosensitive composition layer 12 so that the cushion layer 11b is exposed. However, as shown in FIG. 4 to be described later, the gravure cell 11b is not exposed. The cell 14 can also be formed.

  Next, as shown in FIG. 1E, a reinforcing coating layer 18 is formed on the surface of the negative photosensitive composition layer 12 on which the cells 14 are formed (step 106 in FIG. 2). As a result, a gravure printing roll (gravure version) 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. 4 is a drawing similar to FIG. 1 showing another example of the process of the method for producing a gravure plate having cushioning properties of the present invention. In the process of the method of the present invention shown in FIG. 1, an example is shown in which the gravure cell 14 is formed so that the cushion layer 11b is exposed on the photosensitive composition layer 12, but as shown in FIG. The gravure cell 14 can also be formed so that the layer 11b is not exposed. In FIG. 4, the configuration and operation of the other steps are the same as those in FIG. In this case, since the unexposed portion is dissolved in the developer so as not to expose the gravure plate 1b having cushioning properties, the gravure cell 14 is formed. Thus, the part of the photosensitive composition layer 12 that has not undergone photoreaction needs to be photoreacted to be stabilized.

  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 to 6 and Comparative Production Example 1)
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.

Example 1
The following experiment was conducted using the test photosensitive solution obtained in Production Example 1.
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 tungsten layer was formed by sputtering on the upper surface of the cushion layer of the plate-making roll on which this gravure cell was formed. The sputtering conditions are as follows.
Tungsten sample: solid tungsten target, atmosphere: argon gas atmosphere, film formation temperature: 200 to 300 ° C., film formation time: 60 minutes, film formation thickness: 0.1 μm.

Next, a tungsten carbide layer was formed on the top surface of the tungsten layer. The sputtering conditions are as follows.
Tungsten sample: solid tungsten target, atmosphere: hydrocarbon gas gradually increased in an argon gas atmosphere, film formation temperature: 200 to 300 ° C., film formation time: 60 minutes, film formation thickness: 0.1 μm.

Further, a diamond-like carbon (DLC) film was formed on the upper surface of the tungsten carbide layer by sputtering. The sputtering conditions are as follows.
DLC sample: solid carbon target, atmosphere: argon gas atmosphere, deposition temperature: 200 to 300 ° C., deposition time: 150 minutes, deposition thickness: 1 μm.
In this way, a gravure printing roll (gravure cylinder) was completed.

  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.

(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.

(Experimental example 1)
An experiment was conducted to form a gravure cell in the same procedure as in Example 1 except that the test photosensitive solution obtained in Comparative Production Example 1 was used as the test photosensitive solution. It was found that the stability of the liquid film was poor and it was impossible to form a stable recess, and this test photosensitive solution was not practical as a photosensitive solution for gravure cell formation.

(Example 10)
A gravure cell was formed on the surface of the cushion layer of the plate making roll in the same procedure as in Example 1. Next, a silicon dioxide film was formed on the surface of the cushion layer on which the 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 11)
A gravure cylinder 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 (including a tungsten layer and a tungsten carbide layer) by sputtering. It was confirmed that the same results as in Example 1 were obtained.

Example 12
A gravure cylinder was manufactured in the same procedure as in Example 1 except that a chromium plating layer was formed by a conventional method instead of a DLC layer (including a tungsten layer and a tungsten carbide layer) as a reinforcing coating layer. When a printing test was performed using this gravure cylinder, good printing performance was shown as in Example 1.

BRIEF DESCRIPTION OF THE DRAWINGS It is explanatory drawing which shows typically the manufacturing process of the gravure plate which has the cushioning property of this invention, (a) is the whole of the hollow roll (plate base material) which formed the cushion layer which consists of resin which has rubber | gum or cushioning properties Sectional drawing, (b) is a partially enlarged sectional view showing a state in which a photosensitive composition layer is formed on the surface of the cushion layer, and (c) is a partially enlarged sectional view showing a state in which a mask is provided on the surface of the photosensitive composition layer. FIG. 4D is a partially enlarged sectional view showing a state in which a gravure cell is formed on the surface of the photosensitive composition layer, and FIG. 5E is a partially enlarged sectional view showing a state in which a reinforcing coating layer is formed. It is a flowchart which shows the manufacturing method of the gravure plate which has cushioning properties of this invention. It is a flowchart which shows the process order of the formation process of the gravure cell in this invention. It is drawing similar to FIG. 1 which shows the other example of the process of the manufacturing method of the gravure plate which has cushioning properties of this invention.

Explanation of symbols

10: Plate base material, 10a: Gravure plate (gravure plate making roll), 11a: Hollow roll, 11b: Cushion layer, 12: Photosensitive composition layer, 12a: Insolubilized exposed part (wall of gravure cell), 13: Mask , 14: gravure cell, 18: reinforced coating layer, 20: light.

Claims (25)

A plate base material provided with a cushion layer made of rubber or a resin having cushioning properties on the surface;
A negative photosensitive composition layer formed on the surface of the cushion layer;
A gravure cell formed on the surface of the negative photosensitive composition layer;
The negative photosensitive composition layer comprises 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);
A gravure version having a cushioning characteristic, comprising

Wherein (1), Q represents an aryl group or a heterocyclic group, a halogen atom X ¹ to X ³ are each independently]   2. The gravure plate according to claim 1, wherein the amino alcohol derivative is a (meth) acrylic acid ester of amino alcohol.   The gravure plate according to claim 1, wherein the cyclic amine is a morpholino group-containing compound or a piperazine compound.   The compound (F) represented by the formula (1) is tribromomethylphenyl sulfone or 2-[(tribromomethyl) sulfonyl] pyridine. Gravure version. A plate base material provided with a cushion layer made of rubber or a resin having cushioning properties on the surface;
A negative photosensitive composition layer formed on the surface of the cushion layer;
A gravure cell formed on the surface of the negative photosensitive composition layer;
The negative photosensitive composition layer comprises 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);
A gravure version having a cushioning characteristic, comprising

The gravure plate according to claim 5, wherein 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]   7. The (I) triazine compound is 2,4-diamino-6-vinyl-s-triazine and / or 2,4-diamino-6-methacryloyloxyethyl-s-triazine. A gravure version.   The gravure plate according to any one of claims 1 to 7, wherein the negative photosensitive composition further contains (J) a silane coupling agent.   The gravure plate according to any one of claims 1 to 8, wherein the negative photosensitive composition further contains (K) a polymerization inhibitor.   The gravure cell is formed on the surface of the photosensitive composition layer such that the cushion layer is exposed or the cushion layer is not exposed. 10. Gravure version.   The gravure plate according to any one of claims 1 to 10, further comprising a reinforcing coating layer formed on a surface of the negative photosensitive composition layer on which the gravure cell is formed.   The gravure plate according to claim 11, wherein the reinforcing coating layer is a DLC layer, a silicon dioxide coating, or a chromium plating layer.   The gravure plate according to claim 12, wherein the silicon dioxide film is formed using a perhydropolysilazane solution. A method for producing a gravure plate having cushioning properties according to any one of claims 1 to 4,
Forming a negative photosensitive composition layer on the surface of a cushion layer made of rubber or a resin having cushioning properties;
Forming a gravure cell on the surface of the negative photosensitive composition layer;
Including
The negative photosensitive composition layer comprises 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);
A method for producing a gravure plate having cushioning properties, comprising:

Wherein (1), Q represents an aryl group or a heterocyclic group, a halogen atom X ¹ to X ³ are each independently] A method for producing a gravure plate having cushioning properties according to any one of claims 5 to 7,
Forming a negative photosensitive composition layer on the surface of a cushion layer made of rubber or a resin having cushioning properties;
Forming a gravure cell on the surface of the negative photosensitive composition layer;
Including
The negative photosensitive composition layer comprises 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);
A method for producing a gravure plate having cushioning properties, comprising:

  16. The method for producing a gravure plate having cushioning properties according to claim 14, further comprising a step of forming a reinforcing coating layer that covers a surface of the negative photosensitive composition layer on which the gravure cell is formed. .   A printed matter produced using the gravure plate according to any one of claims 1 to 13.   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 gravure plate according to claim 1.   A gravure according to any one of claims 1 to 13, wherein the microlens is produced by disposing a microlens forming ink on a surface of a sheet-like substrate in a protruding shape at a predetermined interval by printing. A microlens characterized in that the microlens forming ink is printed using a plate.   It is a 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: The said gravure plate in any one of Claims 1-13 Wallpaper characterized by printing wallpaper ink.   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 on the surface of an electromagnetic wave shielding base material, Comprising: The electromagnetic wave shielding sheet of any one of Claims 1-13 An electromagnetic wave shielding sheet, wherein the conductive paste is printed using a gravure plate.   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: The gravure of any one of Claims 1-13 A color filter, wherein the color filter ink is printed using a plate.   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 gravure plate of any one of Claims 1-13 A polarizing plate, wherein the polarizing ink is used for printing.   It is a ceramic capacitor manufactured by arrange | positioning so that an internal electrode may be formed by printing a conductive paste on a ceramic base material, Comprising: The said electroconductivity using the gravure plate of any one of Claims 1-13 Ceramic capacitor, characterized in that a functional paste is printed.   14. An electronic paper produced 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, characterized in that the microencapsulated cell is applied using the gravure plate according to any one of the above.

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