JP2014138160A - Method for manufacturing wiring board - Google Patents

Abstract

The present invention provides a method for manufacturing a wiring board provided with a metal wiring that is excellent in conductive properties and high-definition of a pattern and also has excellent adhesion.
A method of manufacturing a wiring board including a base material and a metal wiring, the step (1) of making the surface of the base material water-repellent using a fluorine atom-containing gas, and a near-infrared laser Etching the water-repellent substrate surface 100a to form the groove 120 on the substrate surface (2), applying ink containing a metal element-containing material in the groove, and forming the metal wiring 140 in the groove And (3) forming a wiring board.
[Selection] Figure 2

Description

  The present invention relates to a method for manufacturing a wiring board.

  Conventionally, as a method of forming a wiring pattern on a wiring surface of a substrate, for example, a copper-clad laminate in which a copper foil is bonded to the surface of a glass epoxy substrate is used, and the copper foil of the copper-clad laminate is etched. Thus, a method for forming a desired wiring pattern is widely known.

  In recent years, a method has been devised in which a metal nano ink in which metal nanoparticles are dispersed in a solvent is drawn on a substrate by an ink jet apparatus to form a wiring pattern (Patent Document 1). The method disclosed in Patent Document 1 discloses a method of spraying PTFE (polytetrafluoroethylene) by spraying as a method of forming an ink-repellent film on the surface of a substrate.

JP 2009-64888 A

In recent years, miniaturization of metal wiring has progressed due to miniaturization of semiconductor integrated circuits and chip parts. Therefore, the improvement of the conductive property of the metal wiring in a wiring board and the improvement of adhesiveness are calculated | required. Moreover, the improvement of the pattern formation property (high definition) of a metal fine wire is also calculated | required.
However, the method of coating a fluororesin such as PTFE described in Patent Document 1 has a problem in that the adhesion of the metal wiring pattern to the base material is poor. This is considered to be due to the fact that the fluororesin has poor adhesion to metals and substrates. Further, in addition to adhesion, further improvements have been required with respect to the pattern formability of metal wiring and the conductive characteristics.

  An object of this invention is to provide the manufacturing method of a wiring board provided with the metal wiring which is excellent in electroconductivity and the high definition of a pattern, and also excellent in adhesiveness in view of the said situation.

  The present inventors have intensively studied the problems of the prior art, and found that the above problems can be solved by the following configuration.

(1) A method of manufacturing a wiring board comprising a base material and metal wiring, wherein the step (1) of making the surface of the base material water-repellent using a fluorine atom-containing gas, and using a near infrared laser, A step (2) of forming a groove on the substrate surface by etching the water-repellent substrate surface and a step of forming a metal wiring in the groove by applying an ink containing a metal element-containing material in the groove (3) The manufacturing method of a wiring board provided with.
(2) The fluorine atom-containing gas is at least one gas selected from the group consisting of CF ₄ , SF ₆ , CHF ₃ , CH ₂ F ₂ , CH ₃ F, C ₂ F ₆ , and C ₄ F _8. A method for manufacturing a wiring board according to (1).
(3) The manufacturing method of the wiring board according to either (1) or (2), wherein the depth of the groove is 0.1 to 50 μm.
(4) The method for manufacturing a wiring board according to any one of (1) to (3), wherein the method of applying ink is an inkjet method.
(5) The step (3) is a step in which an ink containing an electroless plating catalyst or a precursor thereof is applied in the groove, an electroless plating treatment is performed, and a metal wiring is formed in the groove. (1) The manufacturing method of the wiring board in any one of-(4).

  ADVANTAGE OF THE INVENTION According to this invention, while being excellent in the electrical conductivity and the high definition of a pattern, the manufacturing method of a wiring board provided with the metal wiring which is excellent also in adhesiveness can be provided.

It is a flowchart which shows the manufacturing process of the manufacturing method of the wiring board of this invention. It is typical sectional drawing which shows the manufacturing method of the wiring board of this invention in order of a process. It is a schematic block diagram (perspective view) which shows a 1st etching apparatus. It is a perspective view which shows the optical fiber array part and optical fiber of a laser recording apparatus. It is a schematic diagram which shows the light-projection part of an optical fiber array part. It is explanatory drawing for demonstrating the arrangement position and scanning line of an optical fiber edge part. It is the figure which looked at the 1st etching device by plane view. It is a block diagram which shows the structure of the control system of a 1st etching apparatus. It is a flowchart which shows the outline | summary of the process at the time of recording an image with a laser recording apparatus. It is explanatory drawing which illustrated typically the main part of the exposure head and the emitted laser beam. When the optical power control and the beam diameter D are set to 20 μm when the first etching apparatus is not applied, the right figure of (a) shows the spot diameter (spot shape) of the laser beam, and the left figure shows the optical power of the central section. (B) is a schematic diagram showing changes in optical power when a 21.2 μm convex thin line (remaining pixel region) is formed by scanning with a laser beam having the spot diameter (spot shape) shown in (a). (A) shows a pixel exposure amount signal of a laser beam, and (B) is a graph showing an integrated energy of optical power in a cross section along the line AA of (b) of the laser beam. FIG. 6C is a diagram schematically showing a cross-sectional shape along the line AA ′ of FIG. When the optical power control and the beam diameter D are set to 20 μm when the first etching apparatus is not applied, the right figure of (a) shows the spot diameter (spot shape) of the laser beam, and the left figure shows the optical power of the central section. (B) is a schematic diagram showing changes in optical power when a 21.2 μm convex thin line (remaining pixel region) is formed by scanning with a laser beam having the spot diameter (spot shape) shown in (a). (A) shows a pixel exposure amount signal of a laser beam, and (B) is a graph showing an integrated energy of optical power in a cross section along the line AA of (b) of the laser beam. FIG. 6C is a diagram schematically showing a cross-sectional shape along the line AA ′ of FIG. (A) shows the pixel exposure amount signal of the laser beam, and (B) shows the A− of the laser beam (b) when the optical power control to which the first etching apparatus is applied and the beam diameter D is 20 μm. It is a graph which shows the integrated energy of the optical power of the cross section along A line, (C) is a figure which shows typically the cross-sectional shape along AA 'of (b) of the convex thin line P. FIG. When the optical power control and the beam diameter D are not set to 40 μm when the first etching apparatus is applied, the right figure of (a) shows the spot diameter (spot shape) of the laser beam, and the left figure shows the optical power of the central section. It is a graph which shows distribution, (b) is a figure which shows typically the optical power change at the time of scanning with the laser beam of the spot diameter (spot shape) shown to (a) and forming a 21.2 micrometer convex fine line. (A) shows the pixel exposure amount signal of the laser beam, (B) is a graph showing the integrated energy of the optical power of the cross section along the line AA ′ of (b) of the laser beam, (C ) Is a diagram schematically showing a cross-sectional shape along the line AA ′ in FIG. When the optical power control and the beam diameter D are not set to 40 μm when the first etching apparatus is applied, the right figure of (a) shows the spot diameter (spot shape) of the laser beam, and the left figure shows the optical power of the central section. It is a graph which shows distribution, (b) is a figure which shows typically the optical power change at the time of scanning with the laser beam of the spot diameter (spot shape) shown to (a) and forming a 21.2 micrometer convex fine line. (A) shows the pixel exposure amount signal of the laser beam, (B) is a graph showing the integrated energy of the optical power of the cross section along the line AA ′ of (b) of the laser beam, (C ) Is a diagram schematically showing a cross-sectional shape along the line AA ′ in FIG. (A) shows the pixel exposure amount signal of the laser beam and (B) shows the integrated energy of the optical power of the laser beam when the optical power control and the beam diameter D are 40 μm to which the first etching apparatus is not applied. (C) is a figure which shows typically the cross-sectional shape of the convex thin wire | line P. FIG. (A) shows the pixel exposure amount signal of the laser beam, and (B) shows the integrated energy of the optical power of the laser beam when the optical power control and the beam diameter D are 40 μm to which the first etching apparatus is applied. (C) is a figure which shows typically the cross-sectional shape of the convex thin wire | line P. (C) is a figure which shows. (A) shows the pixel exposure amount signal of the laser beam and (B) shows the integrated energy of the optical power of the laser beam when the optical power control to which the first etching apparatus is applied and the beam diameter D is 20 μm. (C) is a figure which shows typically the cross-sectional shape of the convex fine wire P. FIG. (A) shows the pixel exposure amount signal of the laser beam and (B) shows the integrated energy of the optical power of the laser beam when the optical power control to which the first etching apparatus is applied and the beam diameter D is 20 μm. (C) is a figure which shows typically the cross-sectional shape of the convex fine wire P. FIG. (A) shows the pixel exposure amount signal of the laser beam and (B) shows the integrated energy of the optical power of the laser beam when the optical power control to which the first etching apparatus is applied and the beam diameter D is 20 μm. (C) is a figure which shows typically the cross-sectional shape of the convex thin wire | line P. (C) is a figure which shows. (A) shows the pixel exposure amount signal of the laser beam and (B) shows the integrated energy of the optical power of the laser beam when the optical power control and the beam diameter D are 40 μm to which the first etching apparatus is not applied. (C) is a figure which shows typically the cross-sectional shape of the convex thin wire | line P. FIG. It is explanatory drawing explaining optical power control in the case of forming a convex point of a planar view rectangle shape by applying a 1st etching apparatus. It is explanatory drawing explaining optical power control in the case of forming a convex point of a planar view rectangle shape by applying a 1st etching apparatus. It is a figure which shows the convex point part at the time of forming the convex point of planar view rectangular shape by the optical power control of FIG. It is a figure which shows the convex point part at the time of forming the convex point of planar view rectangular shape by the optical power control of FIG. It is explanatory drawing explaining optical power control in the case of forming a convex point of a planar view rectangle shape by applying a 1st etching apparatus. It is a block diagram of the 2nd etching apparatus to which a multi-beam exposure scanning apparatus is applied. It is a block diagram of the optical fiber array part arrange | positioned in an exposure head. It is an enlarged view of the light emission part of an optical fiber array part. It is a schematic diagram of the imaging optical system of an optical fiber array part. It is explanatory drawing which shows the example of arrangement | positioning of the optical fiber in an optical fiber array part, and the relationship of a scanning line. It is a top view which shows the outline | summary of the scanning exposure system in a 2nd etching apparatus. It is a block diagram which shows the structure of the control system in a 2nd etching apparatus. It is a figure shown about the etching of a base material. It is a figure which shows the upper surface and cross section of the base material after the etching by this embodiment. It is a graph which shows the power control example of the beam by a 2nd etching apparatus. It is a figure which shows the relationship between a non-exposure area | region and the convex small point actually formed. It is a graph which shows the example of power control in the case of interlace exposure. It is a schematic diagram which shows the modification of an optical fiber array light source. It is a figure shown about the etching of the base material by the optical fiber array light source of FIG. 40 is a graph showing an example of beam power control by the optical fiber array light source of FIG. It is explanatory drawing which shows the outline | summary of a groove | channel formation process.

Below, the suitable form of the manufacturing method of the wiring board of this invention is explained in full detail.
First, the feature of the present invention compared with the prior art is that the substrate surface is treated with water repellency using a fluorine atom-containing gas, then a groove is formed, and a wiring is formed in the groove. Can be mentioned. In the case of surface treatment of a base material using a fluorine-containing gas, compared to the case of surface treatment of a base material using a fluororesin such as PTFE, the conductive characteristics, adhesion, and pattern formability of the formed metal wiring Excellent. The reason is estimated as follows. When the fluorine-containing gas is used, either one or both of fluorine atoms and fluorocarbon groups can be introduced into the substrate surface while roughening the substrate surface at the nano level. Together, both can reduce the surface energy of the substrate and improve water repellency. As a result, even if the ink containing the metal element-containing material is applied to the substrate surface other than the groove, it is easily induced by the groove portion due to the water repellency and oil repellency of the substrate surface, resulting in the conductive characteristics of the metal wiring. , Adhesion and pattern formability are more excellent.

FIG. 1 is a flowchart showing a manufacturing process in an embodiment of a method for manufacturing a wiring board according to the present invention. As shown in FIG. 1, the method for manufacturing a wiring board includes a water repellent treatment step S12, a groove forming step S14, and a wiring forming step S16.
Moreover, FIG. 2 is typical sectional drawing which shows each manufacturing process in order in the manufacturing method of the wiring board of this invention.
Hereinafter, the materials used in each step and the procedure thereof will be described in detail with reference to FIG. First, the water repellent treatment step S12 will be described in detail.

<Water repellent treatment process>
The water repellent treatment step S12 is a step of making the surface of the substrate water repellent using a fluorine atom-containing gas. By this step S12, the base material 100 having the water repellent surface 100a is obtained (see FIG. 2A). By performing this step S12, the surface of the base material is water-repellent, and the ink is repelled from the surface of the base material and easily guided into the groove during the wiring formation step S16 described later.

The method for carrying out this step is not particularly limited, but it is preferable to impart water repellency to the surface of the substrate (perform water repellency treatment) by plasma treatment using a fluorine atom-containing gas. By carrying out this step, the surface of the substrate is roughened at the nano level, and either the fluorine atom or the fluorocarbon group is generated by the reaction between the fluorine radical or the fluorocarbon radical contained in the plasma and the substrate. One or both can be introduced to the substrate surface. Together, both can reduce the surface energy of the substrate and improve water repellency.
A known plasma processing apparatus can be used for the plasma processing. For example, a plasma processing apparatus that can be used for plasma surface processing or low-temperature ashing can be used. Specific examples of the form of the chamber include a flow tube type, a bell jar type, and the like, and as a form of the electrode for high frequency discharge, a parallel plate type, a coaxial cylindrical type, a curved counter plate type such as a cylinder, a sphere, etc. And an electrode such as a hyperboloid opposed flat plate type and a plurality of fine wire opposed flat plate types. The high frequency current can be applied by either a capacitive coupling method or an induction method using an external electrode. The output of the high-frequency power source is appropriately adjusted depending on the material and size of the base material, the type and volume fraction of the fluorine atom-containing gas used, the capacity and pressure of the chamber, and is, for example, 10 to 250 W.

The fluorine atom-containing gas is not particularly limited as long as it contains fluorine atoms, but CF ₄ , SF ₆ , CHF ₃ , CH ₂ F ₂ , CH ₃ F, C ₂ F ₆ , C ₄ F _{8 and the} like can be mentioned. It is done. Among these, CF ₄ is preferable. Note that an inert gas such as helium or nitrogen may be mixed with the fluorine atom-containing gas.

In the present invention, “water repellency” refers to the water of the substrate after the water repellent treatment with a fluorine atom-containing gas rather than the contact angle (θ) of the substrate before the water repellency treatment with water. It is defined that the contact angle (θ ₁ ) with respect to is larger by 5 ° or more, and the relationship between θ and θ ₁ can be expressed as Equation 1.
Formula 1: θ ₁ −θ ≧ 5

(Base material)
Below, the base material used by this process S12 is explained in full detail.
The kind in particular of base material used by this process S12 is not restrict | limited, What is necessary is just a base material in which a groove | channel can be formed with the near-infrared laser mentioned later. For example, a resin base material is mentioned. Further, the image recording layer described in paragraphs 0023 to 0143 of JP 2011-73370 A and the image recording layer described in paragraphs 0062 to 0169 of JP 4900913 A are used in this step S12. It can also be used as a substrate.
Especially, it is preferable that a base material contains the base material obtained by thermosetting the thermosetting layer containing (Component A) polymeric compound and (Component B) thermopolymerization initiator. Below, each component which comprises a thermosetting layer is explained in full detail.
In addition, the thermosetting composition containing (Component A) polymerizable compound and (Component B) thermal polymerization initiator used for forming the thermosetting layer is also referred to as “laser engraving composition”.

(Component A) Polymerizable compound The thermosetting layer contains (Component A) a polymerizable compound.
The polymerizable compound is preferably a compound having at least one ethylenically unsaturated bond. The polymerizable compound having at least one ethylenically unsaturated bond, which is a preferred polymerizable compound to be used, is selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers (ie, dimers, trimers), and oligomers, or mixtures thereof and copolymers thereof.
Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. Also, an addition reaction product of unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as hydroxyl group, amino group or mercapto group with monofunctional or polyfunctional isocyanates or epoxies, or the above unsaturated carboxylic acid. A dehydration condensation reaction product of an acid ester or amide with a monofunctional or polyfunctional carboxylic acid is also preferably used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanato group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or A substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group with a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, etc. .

  Methacrylic acid esters include diethylene glycol dimethacrylate, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butane. Diol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3 Methacryloxy-2-hydroxypropoxy) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane, tricyclodecane dimethanol dimethacrylate, and the like.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butaneol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate.

  Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.

  Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

  Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

Examples of other esters include aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, JP-A-59-5240, Those having an aromatic skeleton described in JP-A-59-5241 and JP-A-2-226149 and those containing an amino group described in JP-A-1-165613 are also preferably used.
The aforementioned ester monomers can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like.

  Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.

A urethane-based polymerizable compound produced using an addition reaction between an isocyanate and a hydroxyl group is also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following formula (I) to a polyisocyanate compound having two or more isocyanate groups Is mentioned.
_{CH 2 = C (R) COOCH} 2 CH (R ') OH (I)
(However, R and R ′ represent H or CH _3. )

  Further, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-322, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, and the like. Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable.

  Further, by using polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, JP-A-1-105238, etc. A composition for laser engraving having an excellent curing speed can be obtained.

  Other examples include reacting polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490. And polyfunctional acrylates and methacrylates such as epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and vinylphosphonic acid compounds described in JP-A-2-25493 are also included. be able to. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association Vol. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

From the viewpoint of curing speed, a structure having a high unsaturated group content per molecule is preferred, and in many cases, a bifunctional or higher functionality is preferred. Further, in order to increase the strength of the image area, that is, the cured film, those having three or more functionalities are preferable, and furthermore, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether type). A method of adjusting both curability and strength is also effective by using the compound) together.
The polymerizable compound is preferably 2% by weight to 90% by weight, more preferably 5% by weight to 85% by weight, and still more preferably 5% by weight to 30% by weight with respect to the total solid content of the laser engraving composition. Used in range. These may be used alone or in combination of two or more. The total solid content of the laser engraving composition means a component excluding the solvent.

(Component B) Thermal polymerization initiator The thermosetting layer contains (Component B) a thermal polymerization initiator.
As the thermal polymerization initiator, those known to those skilled in the art can be used without limitation. Hereinafter, although the radical polymerization initiator which is a preferable thermal polymerization initiator is explained in full detail, this invention is not restrict | limited by these description.

  In the present invention, preferred radical polymerization initiators include (a) aromatic ketones, (b) onium salt compounds, (c) organic peroxides, (d) thio compounds, (e) hexaarylbiimidazole compounds, (F) ketoxime ester compound, (g) borate compound, (h) azinium compound, (i) metallocene compound, (j) active ester compound, (k) compound having carbon halogen bond, (l) azo compound, etc. Is mentioned. Specific examples of the above (a) to (l) are given below, but the present invention is not limited to these.

  In the present invention, from the viewpoints of sensitivity and groove shape formability, (c) organic peroxides and (l) azo compounds are more preferred, and (c) organic peroxides are particularly preferred.

(A) aromatic ketones, (b) onium salt compounds, (d) thio compounds, (e) hexaarylbiimidazole compounds, (f) ketoxime ester compounds, (g) borate compounds, (h) azinium compounds, As (i) metallocene compounds, (j) active ester compounds, and (k) compounds having a carbon halogen bond, the compounds listed in paragraphs 0074 to 0118 of JP-A-2008-63554 can be preferably used. .
In addition, (c) the organic peroxide and (l) the azo compound are preferably the following compounds.

(C) Organic peroxide Preferred as a radical polymerization initiator that can be used in the present invention (c) As the organic peroxide, 3,3 ′, 4,4′-tetra (tertiarybutylperoxycarbonyl) benzophenone, 3 , 3 ′, 4,4′-tetra (tertiary amyl peroxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (tertiary hexylperoxycarbonyl) benzophenone, 3,3 ′, 4,4 ′ -Tetra (tertiary octylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (cumylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (p-isopropylcumylperoxycarbonyl) ) Benzophenone, ditertiary butyl diperoxyisophthalate, tertiary butyl peroxybenzoate Peroxide ester systems such as are preferred.

(L) Azo-based compound Preferred as a radical polymerization initiator usable in the present invention (l) As the azo-based compound, 2,2′-azobisisobutyronitrile, 2,2′-azobispropionitrile, 1 , 1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′- Azobis (4-methoxy-2,4-dimethylvaleronitrile), 4,4′-azobis (4-cyanovaleric acid), dimethyl 2,2′-azobisisobutyrate, 2,2′-azobis (2-methylpropionamide) Oxime), 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2- Hydro Ethyl] propionamide}, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2 '-Azobis (N-cyclohexyl-2-methylpropionamide), 2,2'-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2'-azobis (2,4,4- Trimethylpentane) and the like.

As the thermal polymerization initiator in the present invention, one kind may be used alone, or two or more kinds may be used in combination.
The content of the thermal polymerization initiator is preferably 0.001% by weight to 15% by weight and more preferably 0.002% by weight to 10% by weight with respect to the total weight of the laser engraving composition. By setting the content of the thermal polymerization initiator to 0.001% by weight or more, the effect of adding this is obtained, and the composition for laser engraving is rapidly crosslinked. Moreover, it is because the intensity | strength sufficient for using it as a base material is acquired, without other components being insufficient by content being 15 weight% or less.

(Component C) Photothermal Conversion Agent The thermosetting layer preferably further contains (Component C) a photothermal conversion agent.
The photothermal conversion agent preferably has a maximum absorption wavelength in the range of 700 nm to 1,300 nm. In the present invention, component C is preferably used as an infrared absorber. Component C is believed to absorb laser light and generate heat to promote thermal decomposition of the substrate and improve sensitivity.
The specific compound of component C preferably has an absorption maximum at a wavelength of 700 nm or more and 1,300 nm or less, and particularly preferably a dye or a pigment.

As the dye, commercially available dyes and known dyes described in documents such as “Dye Handbook” (edited by the Society for Synthetic Organic Chemistry, published in 1970) can be used.
Specifically, azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, diimmonium compounds, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes And the like.

  As preferable dyes, for example, cyanine dyes described in JP-A Nos. 58-125246, 59-84356, 59-202929, and 60-78787, Methine dyes described in JP-A-58-173696, JP-A-58-181690, JP-A-58-194595, JP-A-58-112793, JP-A-58-224793 Naphthoquinone dyes described in JP-A-59-48187, JP-A-59-73996, JP-A-60-52940, JP-A-60-63744, etc., JP-A-58-112792 And squarylium dyes described in Japanese Laid-Open Patent Publication No. Gazette and the like, and cyanine dyes described in British Patent 434,875. In addition, a near infrared absorption sensitizer described in US Pat. No. 5,156,938 is also preferably used, and a substituted arylbenzo (thio) described in US Pat. No. 3,881,924 is also suitable. ) Pyrylium salt, trimethine thiapyrylium salt described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A-58-181051, 58-220143, 59- No. 41363, No. 59-84248, No. 59-84249, No. 59-146063, No. 59-146061, and Pyrlium compounds described in JP-A-59-216146. In addition, the pentamethine thiopyrylium salt described in US Pat. No. 4,283,475, JP-B-5-13514, and JP-A-5-19702 Pyrylium compounds shown also preferably used. Moreover, as another example preferable as a dye, the near-infrared absorptive dye described as the formula (I) and (II) in US Patent 4,756,993 can be mentioned.

Other preferable examples of component C include specific indolenine cyanine dyes described in JP-A-2002-278057.
Among these dyes, cyanine dyes, squarylium dyes, pyrylium salts, nickel thiolate complexes, and indolenine cyanine dyes are preferable. Furthermore, cyanine dyes and indolenine cyanine dyes are preferred.

  Specific examples of cyanine dyes that can be suitably used include paragraphs 0017 to 0019 of JP-A-2001-133969, paragraphs 0012 to 0038 of JP-A-2002-40638, and paragraph 0012 of JP-A-2002-23360. To 0023 can be mentioned.

  The dye represented by the following formula (d) or formula (e) is preferred from the viewpoint of photothermal conversion.

In the formula (d), R ²⁹ to R ³² each independently represent a hydrogen atom, an alkyl group, or an aryl group. R ³³ and R ³⁴ each independently represents an alkyl group, a substituted oxy group, or a halogen atom. n and m each independently represents an integer of 0 to 4. R ²⁹ and R ³⁰ , or R ³¹ and R ³² may be combined to form a ring, and R ²⁹ and / or R ³⁰ is R ³³ and R ³¹ and / or R ³² is R ³⁴ taken together, may form a ring, further, when R ³³ or R ³⁴ there are a plurality, R ³³ or between R ³⁴ each other may be bonded to each other to form a ring. X ² and X ³ each independently represent a hydrogen atom, an alkyl group, or an aryl group, and at least one of X ² and X ³ represents a hydrogen atom or an alkyl group. Q is a trimethine group or a pentamethine group which may have a substituent, and may form a ring structure together with a divalent organic group. Z _c ⁻ represents a counter anion. However, when the dye represented by the formula (d) has an anionic substituent in the structure and charge neutralization is not necessary, Z _c ⁻ is not necessary. Preferred Z _c ⁻ is a halide ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion, particularly preferably perchloric acid, in view of the storage stability of the laser engraving composition. Ions, hexafluorophosphate ions, and aryl sulfonate ions.

  In the present invention, specific examples of the dye represented by the formula (d) that can be suitably used include those exemplified below.

In the formula (e), R ^{35 to} R ⁵⁰ are each independently a hydrogen atom, halogen atom, cyano group, alkyl group, aryl group, alkenyl group, alkynyl group, hydroxyl group, carbonyl group, thio group, sulfonyl group, sulfinyl group. , An oxy group, an amino group, and an onium salt structure, and when a substituent can be introduced into these groups, it may have a substituent. M represents two hydrogen atoms, a metal atom, a halometal group, or an oxymetal group, and examples of the metal atom contained therein include Group 1, Group 2, Group 13, Group 14 atom, First, Examples thereof include transition metals and lanthanoid elements in the second and third periods, and copper, magnesium, iron, zinc, cobalt, aluminum, titanium, or vanadium is particularly preferable.

  In the present invention, specific examples of the dye represented by the formula (e) that can be suitably used include those exemplified below.

  Examples of the pigment used in the present invention include commercially available pigments and color index (CI) manual, “Latest Pigment Handbook” (edited by Japan Pigment Technology Association, published in 1977), “Latest Pigment Application Technology” (CMC Publishing, 1986), “Printing Ink Technology”, CMC Publishing, 1984) can be used.

  Examples of the pigment include black pigment, yellow pigment, orange pigment, brown pigment, red pigment, purple pigment, blue pigment, green pigment, fluorescent pigment, and metal powder pigment. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments In addition, quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like can be used. Among these pigments, carbon black is particularly preferable.

  These pigments may be used without surface treatment, or may be used after surface treatment. The surface treatment method includes a method of surface coating with a resin or wax, a method of attaching a surfactant, a method of bonding a reactive substance (eg, silane coupling agent, epoxy compound, polyisocyanate, etc.) to the pigment surface, etc. Can be considered. The above-mentioned surface treatment methods are described in “Characteristics and Application of Metal Soap” (Shobobo), “Printing Ink Technology” (CMC Publishing, 1984) and “Latest Pigment Application Technology” (CMC Publishing, 1986). Yes.

  Furthermore, when the photothermal conversion agent is used in a combination (condition) in which the thermal decomposition temperature of the binder polymer is equal to or higher than the thermal decomposition temperature of the binder polymer, the etching sensitivity tends to further increase, which is preferable.

  Specific examples of the photothermal conversion agent include cyanine dyes such as heptamethine cyanine dyes, oxonol dyes such as pentamethine oxonol dyes, indolium dyes, benzindolinium dyes, benzothiazolium dyes, and quinolinium dyes. Examples thereof include phthalide compounds reacted with a dye and a developer. Not all cyanine dyes have the light absorption characteristics described above. The light absorption characteristics vary greatly depending on the type of substituent and position in the molecule, the number of conjugated bonds, the type of counterion, the surrounding environment in which the dye molecule is present, and the like.

  Further, commercially available laser dyes, supersaturated absorbing dyes, and near infrared absorbing dyes can also be used. For example, as a laser dye, trade names “ADS740PP”, “ADS745HT”, “ADS760MP”, “ADS740WS”, “ADS765WS”, “ADS745NH”, “ADS790NH”, “ADS800NH” of American Die Source (Canada), Trademarks “NK-3555”, “NK-3509”, and “NK-3519” manufactured by Hayashibara Biochemical Laboratories, Inc. can be mentioned. In addition, as the near-infrared absorbing dyes, trade names “ADS775MI”, “ADS775MP”, “ADS775HI”, “ADS775PI”, “ADS775PP”, “ADS780MT”, “ADS780BP”, “ADS793EI”, trade names “ADS775MI”, “ADS775MP”, “ADS775HI” , “ADS798MI”, “ADS798MP”, “ADS800AT”, “ADS805PI”, “ADS805PP”, “ADS805PA”, “ADS805PF”, “ADS812MI”, “ADS815EI”, “ADS818HI”, “ADS818HT”, “ADS8” ADS830AT, ADS838MT, ADS840MT, ADS845BI, ADS905AM, ADS956BI, ADS140T, DS140P, ADS145P, ADS1050P, ADS160A, ADS165A, ADS165P, ADS1100T, ADS1120F, ADS1120P, ADS780WS, ADS785WS, ADS790WS, SDS80WS , ADS820WS, ADS830WS, ADS850WS, ADS780HO, ADS810CO, ADS820HO, ADS821NH, ADS840NH, ADS880MC, ADS890MC, Yamamoto Corporation Trademarks “YKR-2200”, “YKR-2081”, “YKR-2900”, “YKR-2100”, “YKR-3071”, Arimoto Chemical Co., Ltd. , Trademark "SDO-1000B", (Ltd.) Hayashibara Biochemical Laboratories, Ltd., trademark "NK-3508", mention may be made of the "NKX-114". However, it is not limited only to these.

  Further, as the phthalide compound reacted with the developer, those described in Japanese Patent No. 3271226 can be used. Further, a phosphoric acid ester metal compound, for example, a complex of a phosphoric acid ester and a copper salt described in JP-A-6-345820 and WO99 / 10354 can be used. Furthermore, it is also possible to use fine particles having a volume average particle diameter having light absorption characteristics in the near infrared region, preferably 0.3 μm or less, more preferably 0.1 μm or less, and particularly preferably 0.08 μm or less. Examples thereof include metal oxides such as yttrium oxide, tin oxide and / or indium oxide, copper oxide, and iron oxide, or metals such as gold, silver, palladium, and platinum. Further, metal ions such as copper, tin, indium, yttrium, chromium, cobalt, titanium, nickel, vanadium, and rare earth elements are contained in particles such as glass having a volume average particle diameter of 5 μm or less, more preferably 1 μm or less. What was added can also be used. It can also be contained in microcapsules. In that case, the volume average particle diameter of the capsule is preferably 10 μm or less, more preferably 5 μm or less, and still more preferably 1 μm or less. What adsorb | sucked metal ions, such as copper, tin, indium, yttrium, and rare earth elements, can also be used for an ion exchanger particle. The ion exchanger particles may be resin particles or inorganic particles. Examples of the inorganic particles include amorphous zirconium phosphate, amorphous zirconium silicophosphate, amorphous zirconium hexametaphosphate, layered zirconium phosphate, reticulated zirconium phosphate, zirconium tungstate, zeolite, and the like. Examples of the resin particles include commonly used ion exchange resins and ion exchange cellulose.

As the photothermal conversion agent, carbon black can be particularly preferably mentioned from the viewpoint of stability and photothermal conversion efficiency. As long as there is no problem in dispersion stability in the composition for laser engraving, carbon black can be used for various purposes such as for color, rubber, dry battery, etc. Carbon black can also be preferably used.
The carbon black here includes, for example, furnace black, thermal black, channel black, lamp black, acetylene black, and the like. In addition, in order to facilitate dispersion, black colorants such as carbon black use a dispersant as necessary, and as a color chip or color paste previously dispersed in nitrocellulose or a binder, the laser engraving composition. Such chips and pastes can be easily obtained as commercial products.
In the present invention, it is also possible to use carbon black having a relatively low specific surface area and relatively low DBP absorption, and even fine carbon black having a large specific surface area.
Examples of suitable carbon black commercial products include Printex U (registered trademark), Printex A (registered trademark) or Specialzwarz 4 (registered trademark) (both manufactured by Degussa), Seast 600 ISAF-LS (Tokai Carbon Co., Ltd.) )), Asahi # 70 (N-300), Asahi # 80 (N-220) (manufactured by Asahi Carbon Co., Ltd.) and the like.

In the present invention, carbon black having an oil absorption of less than 150 ml / 100 g is preferred from the viewpoint of dispersibility in the laser engraving composition.
For such selection of carbon black, for example, “Carbon Black Handbook” edited by Carbon Black Association can be referred to.
Use of carbon black having an oil absorption of less than 150 ml / 100 g is preferable because good dispersibility can be obtained in the substrate. On the other hand, when carbon black having an oil absorption of 150 ml / 100 g or more is used, dispersibility in the composition for laser engraving tends to be poor, and carbon black tends to agglomerate. Uniformity occurs, which is not preferable. In order to prevent aggregation, it is necessary to enhance the dispersion of carbon black when preparing the coating solution.

  As a method for dispersing the component C, a known dispersion technique used in ink production, toner production, or the like can be used. Examples of the disperser include an ultrasonic disperser, a paint shaker, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a Dynatron, a three-roll mill, and a pressure kneader. Details are described in "Latest Pigment Applied Technology" (CMC Publishing, 1986).

  The content of component C varies depending on the molecular extinction coefficient inherent to the molecule, but is preferably in the range of 0.1 wt% to 15 wt% with respect to the total weight of the solid content of the laser engraving composition, Is in the range of 0.1 wt% to 10 wt%, particularly preferably 0.1 wt% to 5 wt%.

The volume average particle size of component C is preferably in the range of 0.001 μm to 10 μm, more preferably in the range of 0.05 μm to 10 μm, and particularly in the range of 0.1 μm to 7 μm. Is preferred.
The volume average particle size of Component C can be measured using a laser scattering type particle size distribution measuring device.

(Component D) A compound having a hydrolyzable silyl group and / or silanol group (Component D) A compound having a hydrolyzable silyl group and / or silanol group that is preferably used in the composition for laser engraving (hereinafter referred to as “component” as appropriate) The “hydrolyzable silyl group” in D) is a silyl group having a hydrolyzable group. Examples of the hydrolyzable group include an alkoxy group, a mercapto group, a halogen atom, an amide group, an acetoxy group. Group, amino group, isopropenoxy group and the like. The silyl group is hydrolyzed to become a silanol group, and the silanol group is dehydrated and condensed to form a siloxane bond. Such a hydrolyzable silyl group or silanol group is preferably represented by the following formula (1).

In the formula (1), at least one of R ^{1 to} R ³ is a hydrolysis selected from the group consisting of an alkoxy group, a mercapto group, a halogen atom, an amide group, an acetoxy group, an amino group, and an isopropenoxy group. Represents a sex group or a hydroxyl group. The remaining R ^{1 to} R ³ are each independently a hydrogen atom, a halogen atom, or a monovalent organic substituent (for example, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, and an aralkyl group can be exemplified). Represent.
In the formula (1), the hydrolyzable group bonded to the silicon atom is particularly preferably an alkoxy group or a halogen atom, and more preferably an alkoxy group.
As an alkoxy group, a C1-C30 alkoxy group is preferable. More preferably, it is a C1-C15 alkoxy group, More preferably, it is C1-C5, Most preferably, it is a C1-C3 alkoxy group, Most preferably, it is a methoxy group or an ethoxy group.
Examples of the halogen atom include F atom, Cl atom, Br atom, and I atom. From the viewpoint of ease of synthesis and stability, Cl atom and Br atom are preferable, and Cl atom is more preferable. is there.

Component D is preferably a compound having one or more groups represented by formula (1), and more preferably a compound having two or more groups. In particular, a compound having two or more hydrolyzable silyl groups is preferably used. That is, a compound having two or more silicon atoms having a hydrolyzable group bonded in the molecule is preferably used. The number of silicon atoms bonded to the hydrolyzable group contained in Component D is preferably 2 or more and 6 or less, and most preferably 2 or 3.
The hydrolyzable group can be bonded to one silicon atom in the range of 1 to 4, and the total number of hydrolyzable groups in the formula (1) is preferably in the range of 2 or 3. In particular, it is preferable that three hydrolyzable groups are bonded to a silicon atom. When two or more hydrolyzable groups are bonded to a silicon atom, they may be the same as or different from each other.

Specific examples of preferable alkoxy groups include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a tert-butoxy group, a phenoxy group, and a benzyloxy group. A plurality of these alkoxy groups may be used in combination, or a plurality of different alkoxy groups may be used in combination.
Examples of the alkoxysilyl group to which the alkoxy group is bonded include, for example, a trialkoxysilyl group such as a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a triphenoxysilyl group; a dimethoxymethylsilyl group, a diethoxymethylsilyl group And dialkoxymonoalkylsilyl groups such as methoxydimethylsilyl group and ethoxydimethylsilyl group.

Component D preferably has at least a sulfur atom, an ester bond, a urethane bond, an ether bond, a urea bond, or an imino group.
Among these, component D preferably contains a sulfur atom from the viewpoint of crosslinkability, and contains an ester bond, a urethane bond, or an ether bond (especially an ether bond contained in an oxyalkylene group) that is easily decomposed with alkaline water. It is preferable to do. The component D containing a sulfur atom functions as a vulcanizing agent or a vulcanization accelerator during the vulcanization treatment, and accelerates the reaction (crosslinking) of the polymer containing the conjugated diene monomer unit. As a result, the strength of the substrate is improved.
Component D is preferably a compound having no ethylenically unsaturated bond.

Component D includes a compound in which a plurality of groups represented by the above formula (1) are bonded via a divalent linking group. Such a divalent linking group includes sulfides from the viewpoint of effects. A linking group having a group (—S—), an imino group (—N (R) —), a urea group, or a urethane bond (—OCON (R) — or N (R) COO—) is preferable. R represents a hydrogen atom or a substituent. Examples of the substituent in R include an alkyl group, an aryl group, an alkenyl group, an alkynyl group, and an aralkyl group.
There is no restriction | limiting in particular as a synthesis method of the component D, It can synthesize | combine by a well-known method. As an example, a typical synthesis method of component D including a linking group having the above specific structure is shown below.

(Method for synthesizing a compound having a sulfide group as a linking group and a hydrolyzable silyl group and / or silanol group)
The synthesis method of component D having a sulfide group as a linking group is not particularly limited. Specifically, for example, reaction of component D having a halogenated hydrocarbon group and alkali sulfide, component D having a mercapto group and halogenation Reaction of hydrocarbon, reaction of component D having mercapto group and component D having halogenated hydrocarbon group, reaction of component D having halogenated hydrocarbon group and mercaptan, component D having ethylenically unsaturated double bond Reaction between the component D having an ethylenically unsaturated double bond and the component D having a mercapto group, the reaction between the compound having an ethylenically unsaturated double bond and the component D having a mercapto group, ketones, and Reaction of component D having mercapto group, reaction of component D having diazonium salt and mercapto group, component D having mercapto group and oxy Reaction of components D having a mercapto group and component D having an oxirane group, reaction of a component D having mercaptans and an oxirane group, reaction of component D having a mercapto group and aziridines, etc. A synthesis method can be exemplified.

(Method for synthesizing a compound having an imino group as a linking group and a hydrolyzable silyl group and / or silanol group)
The method for synthesizing component D having an imino group as a linking group is not particularly limited. Specifically, for example, reaction of component D having an amino group with a halogenated hydrocarbon, component D having an amino group and halogenated carbonization, for example. Reaction of component D having hydrogen group, reaction of component D having halogenated hydrocarbon group and amines, reaction of component D having amino group and oxirane, component D having amino group and component D having oxirane group Reaction of component D having amines and oxirane group, reaction of component D having amino group and aziridines, reaction of component D having ethylenically unsaturated double bond and amines, ethylenically unsaturated Reaction of component D having a heavy bond and component D having an amino group, reaction of a compound having an ethylenically unsaturated double bond and component D having an amino group, acetylenic unsaturated triple Reaction of a compound having an amino group with a component D having an amino group, reaction of a component D having an imine unsaturated double bond with an organic alkali metal compound, component D having an imine unsaturated double bond and an organic alkaline earth metal Synthetic methods such as the reaction of the compound and the reaction of the carbonyl compound and the component D having an amino group can be exemplified.

(Method for synthesizing a compound having a urea bond as a linking group and having a hydrolyzable silyl group and / or a silanol group)
The synthesis method of component D having a urea group as a linking group is not particularly limited. Specifically, for example, reaction of component D having amino group and isocyanate esters, component D having amino group and isocyanate ester, and the like. Examples thereof include synthesis methods such as the reaction of component D having an amine and the reaction of component D having an amine and an isocyanate.

  Component D is preferably a compound represented by the following formula (A-1) or formula (A-2).

(In Formula (A-1) and Formula (A-2), R ^B represents an ester bond, an amide bond, a urethane bond, a urea bond, or an imino group, L ¹ represents an n-valent linking group, and L ² represents a divalent linking group, L ^s1 represents an m-valent linking group, L ³ represents a divalent linking group, n and m each independently represents an integer of 1 or more, and R ^{1 to} R ³ each independently represents a hydrogen atom, a halogen atom, or a monovalent organic substituent, provided that at least one of R ^{1 to} R ³ is an alkoxy group, a mercapto group, a halogen atom, an amide group, an acetoxy group Represents a hydrolyzable group selected from the group consisting of a group, an amino group, and an isopropenoxy group, or a hydroxyl group.)

R < ¹ > -R < ³ > in Formula (A-1) and Formula (A-2) is synonymous with R < ¹ > -R < ³ > in the said Formula (1), and its preferable range is also the same.
R ^B is, in view of film strength, it is preferably an ester bond or a urethane bond, and more preferably an ester bond.
The divalent or n-valent linking group in L ^{1 to} L ³ is a group composed of at least one atom selected from the group consisting of a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom and a sulfur atom. Are preferable, and a group composed of at least one atom selected from the group consisting of a carbon atom, a hydrogen atom, an oxygen atom and a sulfur atom is more preferable. The number of carbon atoms of L ^{1 to} L ³ is preferably 2 to 60, and more preferably 2 to 30.
The m-valent linking group in L ^s1 is a group composed of a sulfur atom and at least one atom selected from the group consisting of a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom and a sulfur atom. An alkylene group or a group obtained by combining two or more alkylene groups, sulfide groups, and imino groups is more preferable. The number of carbon atoms of L ^s1 is preferably 2 to 60, and more preferably 6 to 30.
n and m are each independently preferably an integer of 1 to 10, more preferably an integer of 2 to 10, still more preferably an integer of 2 to 6, and particularly preferably 2. .
The n-valent linking group of L ¹ and / or the divalent linking group of L ² or the divalent linking group of L ³ must have an ether bond from the viewpoint of the removal property (rinsing property) of etching residue. It is more preferable to have an ether bond contained in the oxyalkylene group.
Among the compounds represented by formula (A-1) or formula (A-2), from the viewpoint of crosslinkability and the like, in formula (A-1), an n-valent linking group of L ¹ and / or L ² The divalent linking group is preferably a group having a sulfur atom.

  Specific examples of component D are shown below. For example, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxy Silane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, p-styryltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacrylic Roxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxy Silane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercapto Propyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, dimethoxy-3-mercaptopropylmethylsilane, 2- (2-aminoethylthioethyl) diethoxymethylsilane, 3- (2-acetoxyethyl) Thiopropyl) dimethoxymethylsilane, 2- (2-aminoethylthioethyl) triethoxysilane, dimethoxymethyl-3- (3-phenoxypropylthiopropyl) silane, bis (triethoxysilylpropyl) disulfide, bis (tri Toxisilylpropyl) tetrasulfide, 1,4-bis (triethoxysilyl) benzene, bis (triethoxysilyl) ethane, 1,6-bis (trimethoxysilyl) hexane, 1,8-bis (triethoxysilyl) octane 1,2-bis (trimethoxysilyl) decane, bis (triethoxysilylpropyl) amine, bis (trimethoxysilylpropyl) urea, γ-chloropropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, trimethylsilanol, Examples thereof include diphenylsilanediol and triphenylsilanol. In addition, the compounds shown below are preferred, but the present invention is not limited to these compounds.

In each formula, R represents a partial structure selected from the following structures. When a plurality of R and R ¹ are present in the molecule, these may be the same or different from each other, and are preferably the same in terms of synthesis suitability.

In each formula, R represents the partial structure shown below. R ¹ has the same meaning as described above. When a plurality of R and R ¹ are present in the molecule, these may be the same or different from each other, and are preferably the same in terms of synthesis suitability.

  Component D can be obtained by appropriately synthesizing, but it is preferable from the viewpoint of cost to use a commercially available product. Examples of component D include commercially available silane products and silane coupling agents commercially available from Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Co., Ltd., Momentive Performance Materials Co., Ltd., Chisso Co., Ltd., etc. Since the product corresponds to this, these commercially available products may be appropriately selected and used for the laser engraving composition according to the purpose.

As component D, a partially hydrolyzed condensate obtained by using one compound having a hydrolyzable silyl group and / or silanol group or a partially cohydrolyzed condensate obtained by using two or more compounds is used. Can do. Hereinafter, these compounds may be referred to as “partial (co) hydrolysis condensates”.
Among silane compounds as partial (co) hydrolysis condensate precursors, from the viewpoint of versatility, cost, and film compatibility, it has a substituent selected from a methyl group and a phenyl group as a substituent on silicon. It is preferably a silane compound. Specifically, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane Is exemplified as a preferred precursor.
In this case, as a partial (co) hydrolysis condensate, dimers of the silane compound as described above (1 mol of water was allowed to act on 2 mol of the silane compound to remove 2 mol of alcohol to form disiloxane units. To 100-mer, preferably 2 to 50-mer, more preferably 2 to 30-mer, and a partial cohydrolysis condensate using two or more silane compounds as raw materials. It is also possible to use it.

  In addition, as such a partial (co) hydrolysis condensate, you may use what is marketed as a silicone alkoxy oligomer (for example, it is marketed from Shin-Etsu Chemical Co., Ltd.), etc. You may use what was manufactured by removing by-products, such as alcohol and hydrochloric acid, after making the hydrolysis water of less than an equivalent react with a hydrolysable silane compound based on a conventional method. In production, for example, when using alkoxysilanes or acyloxysilanes as described above as the precursor hydrolyzable silane compound, acids such as hydrochloric acid and sulfuric acid, sodium hydroxide, hydroxide Alkaline metal such as potassium or hydroxide of alkaline earth metal, alkaline organic substance such as triethylamine may be used as a reaction catalyst, and it may be partially hydrolyzed and condensed. And water and alcohol may be reacted.

Component D in the composition for laser engraving may be used alone or in combination of two or more.
The content of component D contained in the composition for laser engraving is preferably in the range of 0.1 to 80% by weight, more preferably in the range of 1 to 40% by weight in terms of solid content, and most preferably Preferably it is the range of 5-30 weight%.

(Component E) Binder polymer The composition for laser engraving preferably contains (Component E) a binder polymer.
The binder polymer is preferably a binder resin having a weight average molecular weight of 500 to 1,000,000, and is not particularly limited, but a general polymer compound is appropriately selected, and one kind is used alone, or Two or more types can be used in combination, and it is preferable to select in consideration of various performances such as etching property, ink acceptability, and etching residue dispersibility.
As binder polymer, polystyrene resin, polyester resin, polyamide resin, polysulfone resin, polyethersulfone resin, polyimide resin, hydrophilic polymer containing hydroxyethylene unit, acrylic resin, acetal resin, epoxy resin, polycarbonate resin, rubber, thermoplastic It can be used by selecting from an elastomer or the like.
For example, from the viewpoint of etching sensitivity, a polymer including a partial structure that is thermally decomposed by exposure or heating is preferable. Preferred examples of such a polymer include those described in paragraph 0038 of JP2008-163081A. For example, when the purpose is to form a soft and flexible film, a soft resin or a thermoplastic elastomer is selected. This is described in detail in paragraphs 0039 to 0040 of JP 2008-163081 A. Further, from the viewpoint of easy preparation of the laser engraving composition, it is preferable to use a hydrophilic or alcoholic polymer. As the hydrophilic polymer, those described in detail in paragraph 0041 of JP-A-2008-163081 can be used.

  The binder polymer is more preferably a non-elastomeric binder than an elastomer binder as a binder polymer in terms of etching shape and rinsing properties. Here, the non-elastomeric binder means a binder polymer having a glass transition temperature (Tg) of 20 ° C. or higher. In addition, when it has several glass transition temperature, all the glass transition temperatures are 20 degreeC or more. That is, an elastomer is generally defined scientifically as a polymer having a glass transition temperature of room temperature or lower (see Science Dictionaries 2nd Edition, Editor International Science Promotion Foundation, published by Maruzen Co., Ltd., P154). ). Therefore, a non-elastomer refers to a polymer having a glass transition temperature exceeding normal temperature. Although there is no restriction | limiting in the upper limit of the glass transition temperature of a binder polymer, it is preferable from a viewpoint of handleability that it is 200 degrees C or less, and it is more preferable that it is 25 degreeC or more and 120 degrees C or less.

  In addition, when used for the purpose of curing by heating or exposure to improve strength, polymers having hydroxyl groups, alkoxy groups, hydrolyzable silyl groups and silanol groups, ethylenically unsaturated bonds, etc. in the molecule Is preferably used.

  The reactive functional group may be present anywhere in the polymer molecule, but is preferably present in the side chain of the chain polymer. Examples of such polymers include vinyl copolymers (copolymers of vinyl monomers such as polyvinyl alcohol and polyvinyl acetal and derivatives thereof), acrylic resins (copolymers of acrylic monomers such as hydroxyethyl (meth) acrylate), and the like. Derivatives) can be preferably exemplified.

The method for introducing the reactive functional group into the binder polymer is not particularly limited, and is a method of addition (co) polymerization or polycondensation of a monomer having a reactive functional group, a polymer having a group derivable to the reactive functional group. And a method of deriving the polymer into a reactive functional group by a polymer reaction.
As the binder polymer, a binder polymer (E-1) having a hydroxyl group is preferably used. E-1 will be described below.

(E-1) Binder polymer having a hydroxyl group As the vaninder polymer in the composition for laser engraving, (E-1) a binder polymer having a hydroxyl group (hereinafter also referred to as “specific polymer”) is preferable. This specific polymer is preferably insoluble in water and soluble in an alcohol having 1 to 4 carbon atoms.
Preferred examples of E-1 include polyvinyl acetal and derivatives thereof, an acrylic resin having a hydroxyl group in the side chain, and an epoxy resin having a hydroxyl group in the side chain.

  E-1 preferably has a glass transition temperature (Tg) of 20 ° C. or higher. When combined with Component C, that is, a photothermal conversion agent, the etching sensitivity is improved by setting the glass transition temperature (Tg) of the binder polymer to 20 ° C. or higher. Hereinafter, the binder polymer having such a glass transition temperature is also referred to as “non-elastomer”. Although there is no restriction | limiting in the upper limit of the glass transition temperature of a binder polymer, it is preferable from a viewpoint of handleability that it is 200 degrees C or less, and it is more preferable that it is 25 degreeC or more and 120 degrees C or less.

When a polymer having a glass transition temperature of room temperature (20 ° C.) or higher is used, the specific polymer takes a glass state at room temperature. Therefore, compared to a rubber state, the thermal molecular motion is considerably suppressed. It is in. In addition to the heat imparted by the laser during laser irradiation, the heat generated by the function of the (component C) photothermal conversion agent is transferred to the specific polymer present in the surroundings, which is thermally decomposed and dissipated, resulting in etching. It is estimated that a recess is formed.
When a specific polymer is used, if a photothermal conversion agent is present in a state where thermal molecular motion of the specific polymer is suppressed, heat transfer to the specific polymer and thermal decomposition are considered to occur effectively. It is presumed that the etching sensitivity is further increased by such effects.

Specific examples of the non-elastomer polymer preferably used in the present invention are listed below.

(1) Polyvinyl acetal and derivatives thereof Polyvinyl acetal is a compound obtained by cyclic acetalization of polyvinyl alcohol (obtained by saponifying polyvinyl acetate). Further, the polyvinyl acetal derivative is obtained by modifying polyvinyl acetal or adding other copolymerization components.
The acetal content in the polyvinyl acetal derivative is preferably 30 to 90%, more preferably 50 to 85%, assuming that the total number of moles of the raw vinyl acetate monomer is 100%, and the mole percentage of vinyl alcohol units to be acetalized. 55 to 78% is particularly preferable.
The vinyl alcohol unit in the polyvinyl acetal derivative is preferably 10 to 70 mol%, more preferably 15 to 50 mol%, particularly preferably 22 to 45 mol%, based on the total number of moles of the starting vinyl acetate monomer.
Moreover, the polyvinyl acetal may have a vinyl acetate unit as another component, and as its content, 0.01-20 mol% is preferable and 0.1-10 mol% is more preferable. The polyvinyl acetal derivative may further have other copolymer units.
Examples of the polyvinyl acetal include polyvinyl butyral, polyvinyl propylal, polyvinyl ethylal, and polyvinyl methylal. Among these, polyvinyl butyral derivative (PVB) is preferable.
Polyvinyl butyral is usually a polymer obtained by converting polyvinyl alcohol into butyral. A polyvinyl butyral derivative may also be used.
Examples of polyvinyl butyral derivatives include acid-modified PVB in which at least part of the hydroxyl group is modified to an acid group such as a carboxyl group, modified PVB in which part of the hydroxyl group is modified to a (meth) acryloyl group, and at least part of the hydroxyl group is an amino group. Modified PVB, modified PVB in which ethylene glycol, propylene glycol, or a multimer thereof is introduced into at least a part of the hydroxyl group.
The molecular weight of the polyvinyl acetal is preferably 5,000 to 800,000, more preferably 8,000 to 500,000 as a weight average molecular weight from the viewpoint of maintaining a balance between etching sensitivity and film property. Further, from the viewpoint of improving the rinse property of etching residue, it is particularly preferably 50,000 to 300,000.

Hereinafter, although polyvinyl butyral (PVB) and its derivative (s) are mentioned and demonstrated as a particularly preferable example of polyvinyl acetal, it is not limited to this.
The structure of polyvinyl butyral is as shown below, and includes these structural units.

  In the above formula, l, m and n represent the content (mol%) of each repeating unit in the above formula in polyvinyl butyral, and satisfy the relationship of l + m + n = 100. The butyral content (value of l in the above formula) in polyvinyl butyral and its derivatives is preferably 30 to 90 mol%, more preferably 40 to 85 mol%, particularly preferably 45 to 78 mol%. From the viewpoint of the balance between etching sensitivity and film property, the weight average molecular weight of polyvinyl butyral and its derivatives is preferably 5,000 to 800,000, more preferably 8,000 to 500,000, and improved rinse property of etching residue. From this viewpoint, 50,000 to 300,000 are particularly preferable.

Derivatives of PVB are also available as commercial products, and preferred specific examples thereof include “ESREC B” series and “ESREC K” manufactured by Sekisui Chemical Co., Ltd. from the viewpoint of alcohol solubility (particularly ethanol). (KS) "series," Denkabutyral "manufactured by Denki Kagaku Kogyo Co., Ltd. are preferred. More preferably, from the viewpoint of alcohol solubility (especially ethanol), “S Lec B” series manufactured by Sekisui Chemical Co., Ltd. and “Denka Butyral” manufactured by Denki Kagaku Kogyo Co., Ltd. are preferred. Among these, particularly preferred commercial products are shown below together with the values of l, m, and n and the molecular weight in the above formula. In the “S Lec B” series manufactured by Sekisui Chemical Co., Ltd., “BL-1” (l = 61, m = 3, n = 36 weight average molecular weight 19000), “BL-1H” (l = 67 , M = 3, n = 30 weight average molecular weight 2 million), “BL-2” (l = 61, m = 3, n = 36 weight average molecular weight about 27,000), “BL-5” ( l = 75, m = 4, n = 21 weight average molecular weight 32,000), “BL-S” (l = 74, m = 4, n = 22 weight average molecular weight 23,000), “BM-S (L = 73, m = 5, n = 22 weight average molecular weight 53,000), “BH-S” (l = 73, m = 5, n = 22 weight average molecular weight 66,000), In the “Denkabutyral” series manufactured by Denki Kagaku Kogyo Co., Ltd., “# 3000-1” (l = 71, m = 1, n = 28 weight average molecular weight 74,000), “# 3000-2 "(l = 71, m = 1, n = 28 weight average molecular weight 90000),"# 3000-4 "(l = 71, m = 1, n = 28 weight average molecular weight 17,000 ), “# 4000-2” (l = 71, m = 1, n = 28 weight average molecular weight 152,000), “# 6000-C” (l = 64, m = 1, n = 35 weight average molecular weight) 308,000), “# 6000-EP” (l = 56, m = 15, n = 29 weight average molecular weight 381,000), “# 6000-CS” (l = 74, m = 1, n = 25 weight average molecular weight 322,000) and “# 6000-AS” (l = 73, m = 1, n = 26 weight average molecular weight 242,000).
When forming a thermosetting layer using a PVB derivative as a specific polymer, a method of casting and drying a solution dissolved in a solvent is preferable from the viewpoint of the smoothness of the film surface.

(2) Acrylic resin The acrylic resin that can be used as the specific polymer may be an acrylic resin obtained by using a known acrylic monomer and has a hydroxyl group in the molecule.
As the acrylic monomer used for the synthesis of the acrylic resin having a hydroxyl group, for example, (meth) acrylic acid esters and crotonic acid esters (meth) acrylamides having a hydroxyl group in the molecule are preferable. Specific examples of such a monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.
In the present invention, “(meth) acryl” is a term including one or both of “acryl” and “methacryl”, and “(meth) acrylate” is “acryl”. And “methacrylic”, or both.

Moreover, as an acrylic resin, acrylic monomers other than the acrylic monomer which has the said hydroxyl group can also be included as a copolymerization component. Examples of the acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (Meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, di Tylene glycol monoethyl ether (meth) acrylate, diethylene glycol monophenyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, Polyethylene glycol monomethyl ether (meth) acrylate, polypropylene glycol monomethyl ether (meth) acrylate, monomethyl ether (meth) acrylate of a copolymer of ethylene glycol and propylene glycol, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) a Relate and the like.
Furthermore, a modified acrylic resin comprising an acrylic monomer having a urethane group or a urea group can also be preferably used.
Among these, alkyl (meth) acrylates such as lauryl (meth) acrylate and (meth) acrylates having an aliphatic cyclic structure such as t-butylcyclohexyl methacrylate are particularly preferable from the viewpoint of water-based ink resistance.

(3) Novolak resin Moreover, the novolak resin which is resin which condensed phenols and aldehydes on acidic conditions can be used as a specific polymer.
Preferred novolak resins include, for example, novolak resins obtained from phenol and formaldehyde, novolak resins obtained from m-cresol and formaldehyde, novolak resins obtained from p-cresol and formaldehyde, novolak resins obtained from o-cresol and formaldehyde, Novolak resin obtained from octylphenol and formaldehyde, novolak resin obtained from m- / p-mixed cresol and formaldehyde, phenol / cresol (m-, p-, o- or m- / p-, m- / o-, o Any of-/ p-mixing may be used) and a novolak resin obtained from formaldehyde.
These novolak resins preferably have a weight average molecular weight of 800 to 200,000 and a number average molecular weight of 400 to 60,000.

It is also possible to use an epoxy resin having a hydroxyl group in the side chain as the specific polymer. As a preferred specific example, an epoxy resin obtained by polymerizing an adduct of bisphenol A and epichlorohydrin as a raw material monomer is preferable.
These epoxy resins preferably have a weight average molecular weight of 800 to 200,000 and a number average molecular weight of 400 to 60,000.

Among the specific polymers, polyvinyl butyral derivatives are particularly preferable.
The content of the hydroxyl group contained in the specific polymer is preferably 0.1 to 15 mmol / g, more preferably 0.5 to 7 mmol / g, in any aspect of the polymer.

In the thermosetting layer, in addition to the specific polymer, a known polymer that is not included in the specific polymer, such as a polymer having no hydroxyl group, can be used alone or in combination with the specific polymer. Hereinafter, such a polymer is also referred to as a general polymer.
The general polymer constitutes the main component contained in the thermosetting layer together with the specific polymer. A general polymer compound not included in the specific polymer is appropriately selected, and one or more are used. be able to. In particular, it is necessary to select a binder polymer in consideration of various performances such as etching property, ink acceptability, and etching residue dispersibility.

  General polymers include polystyrene resin, polyester resin, polyamide resin, polyurea polyamideimide resin, polyurethane resin, polysulfone resin, polyethersulfone resin, polyimide resin, polycarbonate resin, hydrophilic polymer containing hydroxyethylene units, acrylic resin, acetal resin , Polycarbonate resin, rubber, thermoplastic elastomer and the like.

  For example, from the viewpoint of etching sensitivity, a polymer including a partial structure that is thermally decomposed by exposure or heating is preferable. Preferred examples of such a polymer include those described in paragraph 0038 of JP2008-163081A. For example, when the purpose is to form a soft and flexible film, a soft resin or a thermoplastic elastomer is selected. This is described in detail in paragraphs 0039 to 0040 of JP 2008-163081 A. Furthermore, it is preferable to use a hydrophilic or alcoholic polymer from the viewpoint of easy preparation of the composition for laser engraving and improvement of resistance to oil-based ink in the obtained flexographic printing plate. As the hydrophilic polymer, those described in detail in paragraph 0041 of JP-A-2008-163081 can be used.

In the composition for laser engraving, only one type of component E may be used, or two or more types may be used in combination.
The content of component E in the composition for laser engraving is 2 to 95% by weight with respect to the total weight of the composition for laser engraving, from the viewpoint of satisfying a good balance of form retention, water resistance and etching sensitivity of the coating film. Preferably, it is 5 to 80% by weight, more preferably 10 to 60% by weight.

(Component F) Alcohol exchange reaction catalyst When the composition for laser engraving contains Component D, it is preferable to contain (Component F) an alcohol exchange reaction catalyst in order to promote the reaction between Component D and the specific binder polymer.
The alcohol exchange reaction catalyst can be applied without limitation as long as it is a commonly used reaction catalyst.
Hereinafter, an acid or basic catalyst, which is a typical alcohol exchange reaction catalyst, and a metal complex catalyst will be sequentially described.

-Acid or basic catalyst-
As the catalyst, an acid or a basic compound is used as it is, or a catalyst dissolved in water or a solvent such as an organic solvent (hereinafter referred to as an acidic catalyst and a basic catalyst, respectively). The concentration at the time of dissolving in the solvent is not particularly limited, and may be appropriately selected according to the characteristics of the acid or basic compound used, the desired content of the catalyst, and the like.
The type of acidic catalyst or basic catalyst is not particularly limited. Specifically, examples of the acidic catalyst include hydrogen halides such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, Examples of the basic catalyst include carboxylic acids such as formic acid and acetic acid, substituted carboxylic acids obtained by substituting R in the structural formula represented by RCOOH with other elements or substituents, sulfonic acids such as benzenesulfonic acid, and phosphoric acid. Include ammoniacal bases such as aqueous ammonia and amines such as ethylamine and aniline. From the viewpoint of promptly promoting the alcohol exchange reaction in the layer, methanesulfonic acid, p-toluenesulfonic acid, pyridinium p-toluenesulfonate, phosphoric acid, phosphonic acid, acetic acid, 1,8-diazabicyclo [5.4.0] ] Undec-7-ene and hexamethylenetetramine are preferable, and methanesulfonic acid, p-toluenesulfonic acid, phosphoric acid, 1,8-diazabicyclo [5.4.0] undec-7-ene and hexamethylenetetramine are particularly preferable. .

-Metal complex catalyst-
The metal complex catalyst used as the alcohol exchange reaction catalyst is preferably a metal element selected from the group consisting of groups 2, 4, 5 and 13 of the periodic table and a β-diketone (preferably acetylacetone), ketoester, hydroxy It is composed of an oxo or hydroxy oxygen compound selected from the group consisting of carboxylic acids or esters thereof, amino alcohols, and enolic active hydrogen compounds.
Further, among the constituent metal elements, group 2 elements such as Mg, Ca, St, and Ba, group 4 elements such as Ti and Zr, group 5 elements such as V, Nb, and Ta, and 13 such as Al and Ga. Group elements are preferred and each form a complex with excellent catalytic effect. Among them, complexes obtained from Zr, Al or Ti are excellent, and ethyl orthotitanate is particularly preferable.
These are excellent in stability in aqueous coating solutions and in gelation promotion effect in sol-gel reaction during heat drying. Among them, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), di ( Particularly preferred are acetylacetonato) titanium complex and zirconium tris (ethylacetoacetate).

  In the composition for laser engraving, only one alcohol exchange reaction catalyst may be used, or two or more kinds may be used in combination. The content of the alcohol exchange reaction catalyst in the composition for laser engraving is preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight, based on the specific binder polymer having a hydroxyl group. preferable.

(Other ingredients)
To the composition for laser engraving, other components suitable for its use, production method and the like can be added as appropriate. Hereinafter, preferred additives will be exemplified.
(Polymerization inhibitor)
In the present invention, in addition to the above basic components, a small amount of thermal polymerization is carried out to prevent unnecessary thermal polymerization of a compound having a polymerizable ethylenically unsaturated bond during the production or storage of a laser engraving composition. An inhibitor may be added. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t- Butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.
The addition amount of the thermal polymerization inhibitor is preferably 0.01% by weight or more and 10% by weight or less based on the total weight of the laser engraving composition.
If necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide may be added to prevent polymerization inhibition by oxygen. The addition amount of the higher fatty acid derivative is preferably 0.5% by weight to 15% by weight with respect to the total weight of the laser engraving composition.

(filler)
The filler may be an organic compound, an inorganic compound, or a mixture thereof. For example, examples of the organic compound include carbon black, carbon nanotube, fullerene, and graphite. Examples of the inorganic compound include silica, alumina, aluminum, and calcium carbonate.

(Plasticizer)
The plasticizer has a function of softening the composition for laser engraving and needs to have good compatibility with the binder polymer. Examples of plasticizers include diethylene glycol, dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. The amount added is preferably 60% by weight or less, more preferably 50% by weight or less, based on the total weight of the solid content.

(Coloring agent)
Furthermore, for the purpose of coloring the laser engraving composition, a colorant such as a dye or a pigment may be added. As the colorant, it is particularly preferable to use a pigment. Specific examples include phthalocyanine pigments, azo pigments, pigments such as titanium oxide, and dyes such as ethyl violet, crystal violet, azo dyes, anthraquinone dyes, and cyanine dyes. The addition amount of the colorant is preferably 0.5% by weight to 10% by weight with respect to the total weight of the laser engraving composition.

(Co-sensitizer)
By using a certain kind of additive (hereinafter referred to as a co-sensitizer), the sensitivity at the time of photocuring the composition for laser engraving can be further improved. These mechanisms of action are not clear, but many are thought to be based on the following chemical processes. That is, a co-sensitizer reacts with various intermediate active species (radicals, cations) generated in the course of a photoreaction initiated by a photopolymerization initiator and a subsequent polymerization reaction, thereby generating a new active radical. Presumed. These can be broadly divided into (i) those that can be reduced to produce active radicals, (ii) those that can be oxidized to produce active radicals, and (iii) radicals that are more active by reacting with less active radicals. Can be categorized into those that act as chain transfer agents, but often there is no generality as to which of these individual compounds belong. Examples of co-sensitizers include trihalomethyl-s-triazines, trihalomethyloxadiazoles and diaryliodonium salts, triarylsulfonium salts, N-alkoxypyridinium (azinium) salts, alkylate complexes, alkylamine compounds, α- Examples thereof include substituted methylcarbonyl compounds, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, and 2-mercaptobenzimidazoles. More specific examples of these co-sensitizers are described, for example, in JP-A-9-236913 as additives for the purpose of improving sensitivity, and these are also applied in the present invention. be able to.

  A co-sensitizer can be used individually or in combination of 2 or more types. The amount used is preferably 0.05 parts by weight or more and 100 parts by weight or less, more preferably 1 part by weight or more and 80 parts by weight or less, still more preferably 3 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the polymerizable compound. Is appropriate.

(solvent)
In the present invention, it is preferable to mainly use an aprotic organic solvent as the solvent used in preparing the laser engraving composition. More specifically, it is preferable to use aprotic organic solvent / protic organic solvent = 100/0 to 50/50 (weight ratio). More preferably, it is 100 / 0-70 / 30, Most preferably, it is 100 / 0-90 / 10.
Preferred specific examples of the aprotic organic solvent include acetonitrile, tetrahydrofuran, dioxane, toluene, propylene glycol monomethyl ether acetate, methyl ethyl ketone, acetone, methyl isobutyl ketone, ethyl acetate, butyl acetate, ethyl lactate, N, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide.
Preferred specific examples of the protic organic solvent are methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-methoxy-2-propanol, ethylene glycol, diethylene glycol, and 1,3-propanediol.
Further, the amount of the solvent to be used is not particularly limited, but it is preferably used so that the solid content in the laser engraving composition is 30 to 95% by weight, more preferably 45 to 90% by weight, and 60 to 88% by weight. % Is more preferable.

The manufacturing method of the base material mentioned above has the thermosetting layer formation process which forms the thermosetting layer containing the component A and the component B, and the thermosetting process which thermosets this thermosetting layer in this order. It is preferable. Moreover, it is preferable to have the lamination process which laminates | stacks an oxygen interruption | blocking film on this thermosetting layer between the said thermosetting layer formation process and a thermosetting process. Moreover, it is preferable to further have the process (henceforth a support body provision process) which provides an adhesive agent on the surface opposite to the surface which contact | connects the oxygen interruption | blocking film of a thermosetting layer, and bonds a support body.
Hereinafter, each process is explained in full detail.

(Thermosetting layer forming process)
The formation of the thermosetting layer is not particularly limited. For example, after preparing a composition for laser engraving and, if necessary, removing the solvent from the composition for laser engraving, an endless belt or a metal is formed. Examples thereof include a method of melt extrusion onto a substrate such as a drum or a support. Alternatively, the laser engraving composition may be cast on a substrate or a support and dried in an oven to remove the solvent from the laser engraving composition.

In the present invention, an existing resin molding method can be used as a method of molding the thermosetting layer into a sheet or cylinder. For example, a casting method, a method of extruding a resin from a nozzle or a die with a machine such as a pump or an extruder, adjusting the thickness with a blade, or adjusting the thickness by calendering with a roll can be exemplified. In that case, it is also possible to perform molding while heating within a range that does not deteriorate the performance of the resin. Moreover, you may perform a rolling process, a grinding process, etc. as needed. In many cases, it is formed on a support underlay called a back film made of a material such as PET or nickel, but it may be formed directly on a cylinder of a printing machine. A cylindrical substrate made of fiber reinforced plastic (FRP), plastic, or metal can also be used. The cylindrical substrate can be hollow with a constant thickness for weight reduction. The role of the back film or cylindrical substrate is to ensure dimensional stability. Therefore, it is necessary to select one having high dimensional stability.
Specific examples of materials include polyester resin, polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin, polybismaleimide resin, polysulfone resin, polycarbonate resin, polyphenylene ether resin, polyphenylene thioether resin, polyethersulfone resin, all Examples thereof include liquid crystal resins composed of aromatic polyester resins, wholly aromatic polyamide resins, and epoxy resins.
Further, these resins can be laminated and used. For example, a sheet or the like in which layers of polyethylene terephthalate having a thickness of 50 μm are laminated on both surfaces of a 4.5 μm thick wholly aromatic polyamide film may be used. In addition, a porous sheet, for example, a cloth formed by knitting fibers, a nonwoven fabric, a film in which pores are formed, or the like can be used as a back film. When a porous sheet is used as the back film, the substrate and the back film are integrated by curing after impregnating the composition for laser engraving into the holes, so that high adhesion can be obtained.
The fibers forming the cloth or nonwoven fabric include glass fibers, alumina fibers, carbon fibers, alumina / silica fibers, boron fibers, high silicon fibers, potassium titanate fibers, inorganic fibers such as sapphire fibers, and natural fibers such as cotton and linen. Examples thereof include semi-synthetic fibers such as fibers, rayon and acetate, and synthetic fibers such as nylon, polyester, acrylic, vinylon, polyvinyl chloride, polyolefin, polyurethane, polyimide, and aramid. Further, cellulose produced by bacteria is a highly crystalline nanofiber, and is a material capable of producing a thin nonwoven fabric with high dimensional stability.

  The thickness of the thermosetting layer may be arbitrarily set according to the purpose of use, but is preferably in the range of 0.05 mm or more and 10 mm or less. More preferably, it is in the range of 0.1 mm or more and 7 mm or less in view of easy etching. In some cases, a plurality of materials having different compositions may be stacked. The thickness of the thermosetting layer is preferably 0.0005 mm or more and 10 mm or less, more preferably 0.005 mm or more and 7 mm or less.

(Thermosetting process)
The above-described thermosetting layer can be crosslinked by heat to obtain a substrate. Crosslinking is not particularly limited as long as the composition for laser engraving is cured, and polymerization reaction by component A (polymerizable compound) or component D (compound having hydrolyzable silyl group and / or silanol group) and Examples thereof include a crosslinked structure by reaction with Component E (binder polymer).
Examples of the heating means for curing by heat include a method of heating for a predetermined time in a hot air oven or a far infrared oven, and a method of contacting a heated roll for a predetermined time.
In addition, when implementing the lamination process mentioned later, a thermosetting process is performed in the state by which the thermosetting layer and the oxygen interruption | blocking film were laminated | stacked.

(Lamination process)
The method for laminating the oxygen barrier film on the thermosetting layer is not particularly limited, but it is preferable to laminate the oxygen barrier film in close contact so that no gas enters between the thermosetting layer and the oxygen barrier film.
After casting or coating the laser engraving composition on the support surface or plate cylinder, an oxygen barrier film may be laminated and dried in an oven, a thermosetting layer is laminated on the oxygen barrier film, and then A method of laminating the support may be used and is not particularly limited.

(Support application process)
In this invention, it is preferable to have the process (supporting body provision process) which provides an adhesive agent to the surface opposite to the surface which contact | connects the oxygen interruption | blocking film of a thermosetting layer, and bonds a support body.
Although a support body provision process can also be performed before a thermosetting process and can also be performed after a thermosetting process, it is preferable to carry out after a thermosetting process. When a thermosetting layer is formed on a substrate such as an endless belt, it is preferable to have a support applying step.

It does not specifically limit as an adhesive agent to be used, A photocurable adhesive agent, a thermosetting adhesive agent, an anaerobic adhesive agent etc. are illustrated. Among these, a photocurable adhesive is preferable because of easy control of the curing reaction.
The photocurable adhesive may be liquid or solid at room temperature (20 ° C.). When it is liquid at room temperature, the viscosity is preferably 100 Pa · s to 10 kPa · s, more preferably 500 Pa · s to 5 kPa · s, and further preferably 1 kPa · s to 5 kPa · s. The above viscosity range is preferable because dripping is suppressed when an adhesive is applied.
Moreover, when it is a solid form about room temperature, it is preferable to heat to the temperature which a photocurable adhesive agent softens. In addition, it is preferable to dissolve and dissolve the solvent in a solvent, and then remove the solvent by drying. However, a solventless hot-melt photocurable adhesive may be applied in a heated state.

  When using a photocurable adhesive as an adhesive, it is preferable to use a transparent support. Since the transparent support has a high light transmittance, it can be irradiated with light from the support side in order to cure the photocurable adhesive, and a curing reaction can be carried out with a small dose.

  Below, the member used at the said process is explained in full detail.

(Oxygen barrier film)
Hereinafter, the oxygen barrier film used in the present invention will be described.
In the present invention, the oxygen barrier film preferably has an oxygen permeability of 30 ml / m ² · day · atm or less at 25 ° C. and 1 atm, more preferably 10 ml / m ² · day · atm or less. It is particularly preferably 5 ml / m ² · day · atm or less.
Oxygen permeability was measured in accordance with the gas permeability test method described in JIS-K7126B and ASTM-D3985, using OX-TRAN 2/21 manufactured by Mocon Co., Ltd. under an environment of 25 ° C. and 60% RH (ml / m ² · day · atm).

  The material of the oxygen barrier film is not particularly limited as long as it is a resin that satisfies the above-described preferred aspect of oxygen permeability. Polyvinyl chloride film, polyvinyl fluoride film, polyvinyl alcohol film, polystyrene film, polycarbonate A resin such as a film, a polyvinyl acetate film, a polyester film, a nylon film, a polyvinylidene chloride film, and a polyacrylonitrile film can be preferably mentioned, and more preferably, a polyester film, a nylon film, a polyvinylidene chloride film, a polyacrylonitrile film. Particularly preferred is a polyvinylidene chloride film.

  The thickness of the oxygen barrier film depends on the material of the oxygen barrier film, but if it is too thin, wrinkles will occur when laminating, causing etching surface defects, and if it is too thick, handling will be inconvenient and costly. Therefore, it is preferably 10 μm or more and 300 μm or less, and more preferably 50 μm or more and 200 μm or less.

(Support)
For the support, a material having flexibility and excellent dimensional stability is preferably used. For example, a polyethylene terephthalate film (PET), a polyethylene naphthalate film (PEN), a polybutylene terephthalate film, or polycarbonate is used. Preferable examples can be given. The thickness of the support is preferably from 50 μm to 350 μm, more preferably from 100 μm to 250 μm. Further, if necessary, it is preferable to provide a known adhesive conventionally used for this kind of purpose on the surface in order to improve the adhesion between the support and the thermosetting layer.
Moreover, adhesiveness with a thermosetting layer or an adhesive bond layer can be improved by performing a physical and chemical treatment on the surface of the support. Examples of the physical treatment method include a sand blast method, a wet blast method in which a liquid containing particles is jetted, a corona discharge treatment method, a plasma treatment method, an ultraviolet ray or vacuum ultraviolet ray irradiation method, and the like. The chemical treatment method includes a strong acid / strong alkali treatment method, an oxidant treatment method, a coupling agent treatment method, and the like.

(Adhesive layer)
When forming a thermosetting layer on a support body, you may provide an adhesive layer between both in order to strengthen the adhesive force between layers.
As a material (adhesive) that can be used for the adhesive layer, for example, I.I. Those described in the edition of Skeist, “Handbook of Adhesives”, the second edition (1977) can be used.

(Protective film, slip coat layer)
For the purpose of preventing scratches and dents on the substrate surface, a protective film may be provided on the substrate surface. The thickness of the protective film is preferably 25 to 500 μm, more preferably 50 to 200 μm. As the protective film, for example, a polyester film such as PET, or a polyolefin film such as PE (polyethylene) or PP (polypropylene) can be used. The surface of the film may be matted. The protective film is preferably peelable.

When the protective film or the oxygen barrier film cannot be peeled off, a slip coat layer may be provided between both layers.
The material used for the slip coat layer is a resin that is soluble or dispersible in water, such as polyvinyl alcohol, polyvinyl acetate, partially saponified polyvinyl alcohol, hydroxyalkyl cellulose, alkyl cellulose, polyamide resin, etc. It is preferable that Among these, partially saponified polyvinyl alcohol having a saponification degree of 60 to 99 mol%, hydroxyalkyl cellulose having 1 to 5 carbon atoms in the alkyl group, and alkyl cellulose are particularly preferably used from the viewpoint of tackiness.

(Other layers)
In the present invention, a cushion layer made of a resin or rubber having cushioning properties can be formed between the support and other layers.

<Groove formation process>
The groove forming step S14 is a step of etching the surface of the water-repellent substrate 100 using a near infrared laser to form the groove 120 on the surface of the substrate (see FIG. 2B). By this step S14, a groove in which a metal wiring described later is installed is formed.
Hereinafter, the procedure of this process S14 is explained in full detail.

The near-infrared laser to be used usually has a wavelength of about 770 to 1500 nm, preferably about 800 to 900 nm, and particularly preferably about 830 to 850 nm in consideration of the sensitivity of the image sensor. .
The output of the near infrared laser is not particularly limited, but is preferably 100 mW or more, and more preferably 1000 mW or more. The upper limit is not particularly limited, but is usually 20000 mW or less from the viewpoint of heat resistance of the substrate.
Further, the amount of irradiation energy is not particularly limited but is preferably ^{0.1~100J / cm 2, 0.5~20J / cm} 2 is more preferable.

The groove pattern is provided corresponding to the pattern of the metal wiring formed on the substrate.
The length, depth, and width of the groove are not particularly limited and can be adjusted as appropriate.
Among these, the depth of the groove is preferably 0.1 to 50 μm, and more preferably 0.2 to 10 μm, from the viewpoint that a thick metal wiring excellent in conductive characteristics can be formed.
Moreover, 0.1-500 micrometers is preferable and the width | variety of a groove | channel is preferable at the point which can form the metal wiring excellent in the electroconductive characteristic, and 1-100 micrometers is more preferable.

  In this step, the near-infrared laser beam and the substrate that is the object to be irradiated need only be scanned relatively. For example, by placing a substrate, which is an object to be irradiated, on an XY axis stage that can move in the horizontal direction with respect to the scanning surface, and moving the stage with the laser light fixed, the laser light can be moved. A method of scanning the surface of the base material is mentioned. Of course, the method may be a method in which the base material is fixed and the laser light is scanned, or a method in which the laser light and the base material that is the object to be irradiated move together.

  In addition, although the apparatus used at this process can use a well-known apparatus, Two etching apparatuses mentioned later are mentioned preferably especially. Below, the structure of each etching apparatus is explained in full detail.

[First etching apparatus]
The first etching apparatus is an apparatus that etches the surface of a base material (hereinafter also referred to as engraving (recording) or engraving) by scanning the recording medium with a light beam at a predetermined pixel pitch. The optical power of the light beam that engraves a partial area or the entire area in the adjacent area adjacent to the convex part leaving the convex shape is set so that the upper surface of the convex part is equal to or lower than the engraving threshold energy. The optical power of the light beam in the adjacent area close to the outside of the area is higher than that in the adjacent area.
Hereinafter, the first etching apparatus will be described in detail with reference to the drawings.
FIG. 3 shows the configuration of the first etching apparatus 11. The first etching apparatus 11 rotates the drum 50 having the base material mounted on the outer peripheral surface in the main scanning direction, and emits a plurality of laser beams according to the image data of the image to be engraved (recorded) on the base material. While simultaneously ejecting, the exposure head 30 is scanned at a predetermined pitch in the sub-scanning direction orthogonal to the main scanning direction, thereby etching the two-dimensional image on the substrate at a high speed.

  FIG. 3 is a schematic configuration diagram (perspective view) showing the first etching apparatus 11. As shown in FIG. 3, the first etching apparatus 11 is rotationally driven in the direction of arrow R in FIG. 3 so that a base material on which an image is recorded by being engraved with a laser beam is mounted and the base material moves in the main scanning direction. The drum 50 and the laser recording apparatus 10 are configured. The laser recording apparatus 10 includes a light source unit 20 as a fiber array light source that generates a plurality of laser beams, an exposure head 30 that exposes a plurality of laser beams generated by the light source unit 20 onto a base material, and a sub-head of the exposure head 30. And an exposure head moving unit 40 that moves along the scanning direction. The rotation direction R of the drum 50 is the main scanning direction, and the direction (details will be described later) in which the exposure head 30 moves along the axial direction (longitudinal direction) of the drum 50 indicated by the arrow S is the sub-scanning direction. The

  The light source unit 20 includes 32 semiconductor lasers 21A and 21B (64 in total) each composed of a broad area semiconductor laser in which one end portions of the optical fibers 22A and 22B are individually coupled, and the semiconductor lasers 21A and 21A, Light source boards 24A and 24B having 21B disposed on the surface, and a plurality of adapters for SC type optical connectors 25A and 25B (the same number as semiconductor lasers 21A and 21B) are provided at one end of the light source boards 24A and 24B. The LD driver circuit 26 that drives the semiconductor lasers 21A and 21B according to the image data of the image that is horizontally attached to the other end portions of the adapter boards 23A and 23B and the light source boards 24A and 24B and engraved (recorded) on the base material. LD driver boards 27A and 27B provided with (see FIG. 8). That.

  SC optical connectors 25A and 25B are provided at the other ends of the optical fibers 22A and 22B, respectively, and the SC optical connectors 25A and 25B are connected to adapter boards 23A and 23B. Therefore, the laser beams emitted from the respective semiconductor lasers 21A and 21B are transmitted to the SC type optical connectors 25A and 25B connected to the adapter boards 23A and 23B through the optical fibers 22A and 22B, respectively.

  In addition, output terminals for driving signals of the semiconductor lasers 21A and 21B in the LD driver circuit 26 provided on the LD driver substrates 27A and 27B are individually connected to the semiconductor lasers 21A and 21B. The driving of 21B is individually controlled by the LD driver circuit 26 (see FIG. 8).

  On the other hand, the exposure head 30 includes an optical fiber array unit 300 (see FIG. 4) that collectively emits the laser beams emitted from the plurality of semiconductor lasers 21A and 21B. The optical fiber array unit 300 includes laser beams emitted from the semiconductor lasers 21A and 21B by a plurality of optical fibers 70A and 70B connected to SC type optical connectors 25A and 25B connected to adapter boards 23A and 23B, respectively. Is transmitted.

  FIG. 5 shows a view of the light emitting section 280 (see FIG. 4) of the optical fiber array section 300 viewed in the direction of arrow A shown in FIG. As shown in FIG. 5, the light emitting section 280 of the optical fiber array section 300 has two bases 302A and 302B. The bases 302A and 302B are formed on one side so that the same number as the semiconductor lasers 21A and 21B, that is, 32 V-shaped grooves 282A and 282B are adjacent to each other at a predetermined interval. The bases 302A and 302B are arranged so that the V-shaped grooves 282A and 282B face each other.

  One optical fiber end 71A at the other end of the optical fiber 70A is fitted into each V-shaped groove 282A of the base 302A. Similarly, one optical fiber end 71B at the other end of each optical fiber 70B is fitted into each V-shaped groove 282B of the base 302B. Therefore, a plurality of laser beams emitted from the respective semiconductor lasers 21A and 21B, in this embodiment, 64 (32 × 2) laser beams are emitted simultaneously from the light emitting unit 280 of the optical fiber array unit 300.

  In other words, the optical fiber array unit 300 of the present embodiment is configured by arranging a plurality of optical fiber end portions 71A and 72B (in the present embodiment, 32 × 2 = 64 in total) linearly along a predetermined direction. The optical fiber end groups 301A and 301B are configured to be provided in two rows in parallel to a direction orthogonal to the predetermined direction.

  As shown in FIGS. 3 and 5, in the laser recording apparatus 10 according to the present embodiment, the optical fiber array unit 300 (exposure head 30) configured as described above has the predetermined direction with respect to the sub-scanning direction. And inclined. Further, as shown in FIGS. 5 and 6, the optical fiber array unit 300 is viewed in the main scanning direction so that the optical fiber end group 301A and the optical fiber end group 301B are arranged in the sub scanning direction without overlapping. It is arranged.

  As shown in FIG. 3, in the exposure head 30, a collimator lens 32, an opening member 33, and an imaging lens 34 are arranged in order from the optical fiber array unit 300 side. The opening member 33 is arranged so that the opening is positioned at the far field when viewed from the optical fiber array unit 300 side. As a result, the same light quantity limiting effect can be given to all the laser beams emitted from the optical fiber end portions 71A and 71B of the plurality of optical fibers 70A and 70B in the optical fiber array unit 300.

  In the present embodiment, a multimode optical fiber having a relatively large core diameter is applied to the optical fibers 22A and 22B in order to increase the output of the laser beam. Specifically, in this embodiment, the core diameter is 105 μm. The semiconductor lasers 21A and 21B use 8.5w (6397-L3) as the maximum output. The core diameters of the optical fibers 70A and 70B are set to 105 μm.

  As shown in FIG. 10, the laser beam is imaged in the vicinity of the exposure surface (surface) FA of the base material F by the imaging means constituted by the collimator lens 32 and the imaging lens 34 (the opening member 33 is shown in FIG. 10). 10 is not shown). In the present embodiment, it is desirable from the viewpoint of fine line reproducibility and the like that the imaging position (imaging position) X is set on the exposure surface FA. The laser beam emitted from the optical fiber end 71A (optical fiber end group 301A) is used as a laser beam LA, and the laser beam emitted from the optical fiber end 71B (optical fiber end group 301B) is used as a laser beam. LB. In addition, when it is not necessary to distinguish both, it is simply described as “laser beam”.

  Then, an optical fiber end 71B at the end of the optical fiber end group 301B is arranged next to the optical fiber end 71A at the end of the optical fiber end group 301A (see also FIG. 5). In FIG. 6, for the sake of clarity, the number of optical fiber end portions 71A and 71B is smaller than the actual number.

  As shown in FIG. 7, the base material F on which an image is recorded by engraving with a laser beam is mounted on the outer peripheral surface of a drum 50 that is driven to rotate in the direction of arrow R. The base material F is mounted on the outer peripheral surface of the drum 50 by a belt-shaped chuck member 98 whose longitudinal direction is the rotation axis direction of the drum 50. More specifically, the base member F is mounted on the outer peripheral surface of the drum 50 by attaching the chuck member 98 to the drum 50 so as to press the upper part of the end portion FT of the base member F. The chuck member 98 is a non-recording area.

  As shown in FIGS. 3 and 7, the exposure head moving unit 40 is provided with a ball screw 41 and two rails 42 (see FIG. 3) arranged so that the longitudinal direction is along the sub-scanning direction. By operating the sub-scanning motor 43 that rotationally drives the ball screw 41, the pedestal portion 310 provided with the exposure head 30 can be moved in the sub-scanning direction while being guided by the rails 42. The drum 50 can be rotated in the direction of arrow R in FIG. 3 by operating a main scanning motor 51 (see FIG. 8), whereby main scanning is performed. The exposure head 30 is provided on the pedestal portion 310.

  In the present embodiment, as described above, exposure and scanning are performed with 64 laser beams LA and LB at a time.

  Next, the configuration of the control system of the first etching apparatus 11 (see FIG. 3) according to the present embodiment will be described.

  As shown in FIG. 8, the control system of the first etching apparatus 11 includes an LD driver circuit 26 that drives the semiconductor lasers 21A and 21B according to image data, and a main scanning motor drive circuit 81 that drives the main scanning motor 51. A sub-scanning motor driving circuit 82 for driving the sub-scanning motor 43, an actuator driving circuit 299 for driving the actuator 304, a control circuit for controlling the main scanning motor driving circuit 81, the sub-scanning motor driving circuit 82, and the actuator driving circuit. 80. Image data indicating an image to be engraved (recorded) on the substrate F is supplied to the control circuit 80.

  Next, an outline of a process of engraving (recording) the base material F by the first etching apparatus 11 (see FIG. 3) configured as described above will be described. FIG. 9 is a flowchart showing a process flow when image recording is performed by the first etching apparatus 11.

  As shown in FIG. 9, first, image data of an image to be engraved (recorded) on the substrate F is transferred from an image memory (not shown) temporarily stored to the control circuit 80 (step 100). The control circuit 80 sends the adjusted signal to the LD driver circuit 26, main data based on the transferred image data, resolution data indicating a predetermined resolution of the recorded image, data indicating shallow engraving, deep engraving, and the like. This is supplied to the scanning motor drive circuit 81, the sub-scan motor drive circuit 82, and the actuator drive circuit 299.

  Next, the main scanning motor drive circuit 81 controls the main scanning motor 51 so as to rotate the drum 50 in the direction of arrow R in FIG. 3 based on the signal supplied from the control circuit 80 (step 102).

  The sub-scanning motor drive circuit 82 sets a feed interval in the sub-scanning direction of the exposure head 30 by the sub-scanning motor 43 (step 104).

  Next, the LD driver circuit 26 controls driving of the semiconductor lasers 21A and 21B according to the image data (step 106).

  The laser beams LA and LB emitted from the respective semiconductor lasers 21A and 21B are optical fiber end portions 71A of the optical fiber array section 300 through the optical fibers 22A and 22B, the SC type optical connectors 25A and 25B, and the optical fibers 70A and 70B. 71B and the collimator lens 32, as shown in FIGS. 3 and 10, the light beam is limited by the aperture member 33 and the recording plate on the drum 50 through the imaging lens 34. An image is formed (condensed) in the vicinity of the F exposure surface FA (the imaging surface X and FA may coincide).

  In this case, beam spots are formed on the base material F according to the laser beams LA and LB emitted from the respective semiconductor lasers 21. With these beam spots, the exposure head 30 is fed in the sub-scanning direction at the pitch of the feed interval set in step 104 described above, and the resolution is determined by the resolution data by the rotation of the drum 50 started in step 102 described above. A two-dimensional image having the resolution shown is engraved (formed) on the substrate F (step 108).

  When the engraving (recording) of the two-dimensional image on the substrate F is completed, the main scanning motor drive circuit 81 stops the rotation drive of the main scanning motor 51 (step 110), and then ends the present process.

  Next, the optical power control of the laser beams LA and LB in step 108 will be described, and the operation and effect of this embodiment will be described.

  As shown in FIG. 6, when the optical fiber end group 301A and the optical fiber end group 301B are viewed in the main scanning direction, the interval between the optical fiber end portions 71A and 71B, that is, the interval between the scanning lines K (pixel pitch). ) Is 10.58 μm (resolution: 2400 dpi). In other words, one pixel is 10.58 μm.

  In addition, a description will be given of a case where the convex fine line P is formed in which the surface FA of the base material F is left convex. The convex thin line P has a longitudinal direction in the sub-scanning direction and a desired width (width in the main scanning direction) of 21.2 μm.

  First, the case where the spot diameter D of the laser beam is set to φ20 μm will be described with reference to FIGS.

  In each figure, the right figure in (a) shows the spot diameter (spot shape) of the laser beam, and the left figure is a graph showing the optical power distribution in the central section. (B) is a figure which shows typically the optical power change at the time of scanning with the laser beam of the spot diameter (spot shape) shown to (a) and forming the 21.2 micrometer convex fine line P. FIG. The darker the color, the stronger the optical power, and the thinner the color, the weaker the optical power. (A) shows a pixel exposure amount signal of the laser beam. (B) is a graph which shows the integrated energy of the optical power of the cross section along the AA line of (b) of a laser beam. (C) is a figure which shows typically the cross-sectional shape (vertical cross-sectional shape when a convex direction is made into an upper direction) along AA of (b) of the convex fine wire P. FIG. Further, G in the drawing indicates one pixel width (10.58 μm). In FIG. 13, the figures corresponding to (a) and (b) are omitted, and only the figures corresponding to (A) to (C) are shown. Furthermore, the arrow R direction in the figure is the laser beam scanning direction (in this embodiment, the main scanning direction).

  The engraving threshold energy (see (B)) is the energy of the laser beam necessary for engraving the surface of the base material F, and engraving the base material F if the energy is not larger than the engraving threshold energy. I can't. In other words, if the energy is below the engraving threshold energy, the surface of the substrate F is not engraved even if the laser beam is irradiated. This engraving threshold energy varies depending on the type (material, etc.) of the base material F.

  FIG. 11 shows a case where optical power control is performed with the pixel exposure amount signal of the laser beam turned off only in the portion corresponding to the 21.2 μm wide convex fine line P (light to which the first etching apparatus 11 is not applied). Power control). In this case, even if the pixel exposure amount signal of the laser beam is turned off, the region of the convex fine line P is exposed. For this reason, as shown in FIG. 11C, since the width of the upper surface P5 of the convex fine line P becomes a portion that is equal to or smaller than the engraving threshold energy, the cross-sectional shape of the convex fine line P is substantially trapezoidal. Therefore, the width of the upper surface P5 of the convex fine line P is less than the desired 21.2 μm.

  FIG. 12 shows the case where optical power control is performed by turning off the pixel exposure amount signal of the laser beam for one pixel (both for two pixels) on the upstream and downstream sides in the scanning direction of the 21.2 μm wide convex thin line P. Is shown. In this case, since the convex fine line P portion is not completely exposed, the width of the upper surface P5 of the convex fine line P can be brought close to the desired 21.2 μm (21.2 μm width is ensured or substantially ensured). In addition, since the width of the upper surface P5 of the convex thin line P is a portion that is equal to or less than the engraving threshold energy, the width is exactly the α1 portion in the drawing. Further, as shown in FIG. 12C, the base of the trapezoid is about 20 μm.

  In the case of FIG. 12, the width of the upper surface P5 of the convex fine line P can be brought close to the desired value of about 20 μm, but as shown in FIG. The inclination angle of P2 is gentle. That is, the angle of the edge portion E formed by the upper surface P5 and the side wall surfaces P1 and P2 is lying (the angle is larger than 90 °). However, in order to print the fine line after printing with high definition, it is necessary to raise this edge portion E (need to be close to 90 °). That is, it is necessary to make the inclination angles of the side wall surfaces P1 and P2 close to vertical.

  Therefore, in the first etching apparatus 11 of the present embodiment, as shown in FIG. 13, the inclination angle of the wall surfaces P1 and P2 is made close to vertical by increasing the optical power for one pixel outside the laser beam turned off. Yes. That is, the edge portion E is more erected (closer to 90 °). As a result, the cross-sectional shape of the convex fine line P (vertical cross section when the convex direction is the upward direction as shown in the figure) can be made closer to a rectangular shape.

  In addition, since the width of the upper surface P5 of the convex thin line P is a portion that is equal to or less than the engraving threshold energy, the width of the α2 portion in the figure is wide, but the inclination angles of the wall surfaces P1 and P2 are close to vertical. , Very little and no problem. Further, the width for raising the optical power of the laser beam is increased or the width for turning off the pixel exposure amount signal is slightly narrowed so that the width is narrowed by α2 (to bring the width closer to the desired 21.2 μm). Etc., and may be adjusted.

  As described above, in the first etching apparatus 11 of the present embodiment, the optical power is turned off by one pixel on the upstream side and the downstream side in the scanning direction in the adjacent region adjacent to the convex fine line P, and the laser beam is turned off outside. By increasing the optical power of one adjacent pixel (proximity region), the inclination angles of the wall surfaces P1 and P2 are made closer to the vertical (the edge portion E is more upright (closer to 90 °)).

  As described above, even if the beam diameter D is as large as 20 μm (even if the beam diameter D is larger than one pixel), the optical power control of the first etching apparatus 11 is applied, so that the width of the upper surface P5 of the convex thin line P is increased. Can be made closer to the desired width (21.2 μm in the present embodiment), and the cross-sectional shape of the convex thin wire P can be made closer to a rectangular shape. That is, the convex fine line P can be engraved with high precision.

  As shown in FIG. 20, the upstream side and the downstream side in the scanning direction of the convex fine line P having a width of about 20 μm are each for one pixel (both for two pixels), and the pixel exposure amount signal of the laser beam is turned off (the optical power is turned off). Instead of setting to 0 (zero)), the optical power control may be performed so that the exposure is performed with the engraving threshold energy or less.

  Next, the case where the spot diameter D of the laser beam is set to φ40 μm will be described with reference to FIGS.

  In each figure, as in the case where the spot diameter D is φ20 μm, the right figure in (a) shows the spot diameter (spot shape) of the laser beam, and the left figure is a graph showing the optical power distribution in the central section. (B) is a figure which shows typically the optical power change at the time of scanning with the laser beam of the spot diameter (spot shape) shown to (a), and forming the 20 micrometer convex fine wire P. FIG. The darker the color, the stronger the amount of light, and the thinner the color, the weaker the optical power. (A) shows a pixel exposure amount signal of the laser beam. (B) is a graph which shows the integrated energy of the optical power of the cross section along the AA line of (b) of a laser beam. (C) is a figure which shows typically the cross-sectional shape (vertical cross section when a convex direction is made into an upper direction) along AA of (b) of the convex fine wire P. FIG. Further, G in the drawing indicates one pixel width (10.58 μm). In FIGS. 16 and 17, the figures corresponding to (a) and (b) are omitted, and only the figures corresponding to (A) to (C) are shown. Furthermore, the arrow R direction in the figure is the laser beam scanning direction (in this embodiment, the main scanning direction).

  FIG. 14 shows a case where optical power control is performed in which the exposure signal of the laser beam is turned off only in a portion corresponding to the 21.2 μm wide convex fine line P (optical power control to which the first etching apparatus 11 is not applied). ). In this case, even if the pixel exposure amount signal of the laser beam is turned off, even the convex fine line P is exposed. Further, since the spot diameter D is as large as φ40 μm, as shown in FIG. 14B, the laser beam overlaps on the convex fine line P, and the accumulated energy becomes large. Therefore, as shown in FIG. P is not formed.

  FIG. 15 shows the case where optical power control is performed by turning off the pixel exposure signal of the laser beam for one pixel (both for two pixels) on the upstream and downstream sides of the 21.2 μm wide convex thin line P in the scanning direction. (Optical power control to which the first etching apparatus 11 is not applied). Even in this case, since the spot diameter D is as large as φ40 μm, even the convex fine line P is exposed. For this reason, as shown in FIG. 15C, the width of the upper surface P5 of the convex thin line P becomes a portion that is equal to or smaller than the engraving threshold energy, so that the cross-sectional shape is substantially trapezoidal. Therefore, the width of the upper surface P5 of the convex fine line P is less than the desired 20 μm.

  FIG. 16 further shows optical power control in which the pixel exposure amount signal of the laser beam is turned off for two pixels (both for four pixels) on the upstream and downstream sides in the scanning direction of the 21.2 μm wide convex thin line P. (Optical power control to which the first etching apparatus 11 is not applied). In this case, since the convex thin line P portion is not almost completely exposed, the width of the upper surface P5 of the convex fine line P can be made close to the desired 21.2 μm.

  However, in the case of FIG. 16, the width of the upper surface P5 of the convex fine line P can be brought close to the desired 21.2 μm, but as shown in FIG. 16C, the upstream side and the downstream side of the convex fine line P in the scanning direction. The inclination angles of the wall surfaces P1 and P2 are gentle. That is, the angle of the edge portion E formed by the upper surface P5 and the side wall surfaces P1 and P2 is lying (the angle is larger than 90 °). In order to make fine lines after printing have higher definition, it is necessary to raise this edge portion E (need to be close to 90 °). That is, it is necessary to make the inclination angles of the side wall surfaces P1 and P2 close to vertical.

  Therefore, as in the case where the beam diameter D is 20 μm, the first etching apparatus 11 is applied to increase the optical power for one pixel outside the laser beam as shown in FIG. , P2 is made closer to vertical (by raising the edge portion E (by making it closer to 90 °)), the cross-sectional shape of the convex thin line P can be made closer to a rectangular shape.

  As described above, even if the beam diameter D is as large as 40 μm (even if the beam diameter D is larger than one pixel and larger than the width of the convex thin line P), the first etching apparatus 11 can be used to apply the convexity. The width of the upper surface P5 of the fine line P can be made close to the desired 20 μm, and the cross-sectional shape of the convex fine line P can be made close to a rectangular shape. That is, even if the beam diameter D is as large as 40 μm, the convex fine line P can be engraved with high precision.

  In addition, as shown in FIG. 21, instead of turning off the pixel exposure amount signal of the laser beam in the scanning direction upstream and downstream of the convex thin line P having a width of about 20 μm for two pixels (both for four pixels), You may perform optical power control which exposes with below engraving threshold energy. In this case as well, by increasing the amount of power for one outer pixel with the laser beam equal to or lower than the engraving threshold energy and making the slopes of the wall surfaces P1 and P2 close to vertical (by making the edge E more upright (closer to 90 °). )), The cross-sectional shape of the convex fine wire P is made close to a rectangular shape.

  The laser beam diameter D may be the same for the laser beam LA and the laser beam LB (see FIG. 10) or may be different. For example, the beam diameter D of the laser beam LA may be 20 μm for shallow carving, and the laser beam LB may be 40 μm for deep carving.

  Next, when increasing the amount of power for one pixel outside the laser beam turned off (or less than the engraving threshold energy), pulse exposure is performed so that the slopes of the wall surfaces P1 and P2 are made closer to the vertical (edge). The optical power control will be described by raising the portion E more (by approaching 90 °). In other words, the optical power control that brings the cross-sectional shape of the convex thin line P closer to a rectangular shape will be described.

  Here, an example in which the beam diameter D is about 20 μm will be described, but the same applies even when the beam diameter D is 40 μm.

  FIG. 18 shows a case where pulse exposure is performed with a pulse width of 0.5 pixels. As can be seen from FIG. 18, it is understood that the inclination of the wall surfaces P1 and P2 can be made more vertical by performing pulse exposure. At this time, it is desirable to increase the maximum value of the optical power so that the integrated energy is substantially the same as in FIG.

  Further, FIG. 19 shows a case where pulse exposure is performed with a pulse width of 0.25 pixel. As can be seen from FIG. 19, it can be seen that the inclination of the wall surfaces P1 and P2 can be made more vertical by further narrowing the pulse width. At this time, it is desirable to further increase the maximum value of the optical power so that the integrated energy is substantially the same as in the case of FIG. 13 (FIG. 18).

  In the above embodiment, the region for controlling the optical power is performed on the upstream side and the downstream side in the main scanning direction, respectively, but may be applied only to either the upstream side or the downstream side.

  Further, the optical power control according to the present invention may be applied to at least one of the upstream side and the downstream side in the sub-scanning direction instead of the upstream side and the downstream side in the scanning direction (main scanning direction). In other words. The width of the upper surface P5 in the cross section along the line B-B 'shown in FIG. 11 may be close to the desired 21.2 μm, and the cross sectional shape may be close to a rectangular shape (side wall surfaces P3 and P4 are also close to vertical).

  Up to now, the convex thin line P has been described. Next, optical power control in the case of forming a convex point Q having a rectangular shape in plan view (leaving the convex point Q) will be described. Here, the size of the desired convex point Q is 21.2 μm × 21.2 μm. Further, the control of the beam diameter D, the pulse width, and the like are the same as those of the convex thin line P described so far, and the description thereof is omitted.

  FIG. 22 shows that one pixel (pixel A, pixel B, pixel C, pixel D) adjacent to the corners QA, QB, QC, QD of the convex point Q does not turn off the laser beam (below the threshold energy). It is explanatory drawing explaining the case where it sets to the proximity | contact area | region R which raised power. FIG. 24 is a diagram schematically showing the shape of the convex point Q in plan view when the optical power is controlled as shown in FIG. In FIG. 23, the laser beam is turned off for one pixel (including pixel A, pixel B, pixel C, and pixel D) over the entire circumference of the convex point Q, and the optical power is increased over the entire outer circumference. It is explanatory drawing explaining the case where it sets to the proximity | contact area | region R. FIG. FIG. 25 is a diagram schematically showing the shape of the convex portion Q when the optical power is controlled as shown in FIG. In FIG. 26, one pixel adjacent to some corners of the convex point Q (in this case, corners QA, QB, QC, QD) is set in the proximity region R where the optical power is increased without turning off the laser beam. It is explanatory drawing explaining the case where it did.

  As shown in FIG. 22, when exposure is performed without turning off the laser beam for one pixel (pixel A, pixel B, pixel C, pixel D) adjacent to the corners QA, QB, QC, QD of the convex point Q, As shown in FIG. 24, the shape of the convex point Q does not sufficiently approach the rectangular shape in plan view. Note that FIG. 24 is shown deformed (distorted) for easy understanding.

  On the other hand, as shown in FIG. 23, the laser beam is turned off for one pixel (including pixel A, pixel B, pixel C, and pixel D) over the entire circumference of the convex point Q, and the entire outer circumference thereof. When the optical power is increased over the range, the shape of the convex point Q approaches a rectangular shape in plan view as shown in FIG.

  As shown in FIGS. 22 and 24, the laser beam is not turned off for one pixel (pixel A, pixel B, pixel C, pixel D) adjacent to the corners QA, QB, QC, QD of the convex point Q. When the optical power is increased, the first etching apparatus 11 is also included.

  In addition, as shown in FIG. 26, even when the optical power is increased without turning off the laser beam for one pixel adjacent to some corners QA, QB, QD of the convex point Q, the first etching apparatus 11 is used. included. Also in this case, as shown in FIG. 26, it is preferable to increase the optical power of the laser beam over the entire circumference (as shown in FIG. 23).

  However, as described above, as shown in FIG. 23 and FIG. 25, adjacent to one corner (pixel A, pixel B, pixel C, pixel D) adjacent to the corners QA, QB, QC, QD of the convex point Q. By not exposing the region to be exposed (set so that the upper surface of the convex portion Q is equal to or lower than the threshold energy), the convex point portion Q having a desired rectangular shape in plan view can be obtained more effectively.

  Even in the case where the shape in plan view is a convex point portion other than a rectangular shape in plan view (for example, a circular shape or a triangular shape), the surface of the recording medium is partially or entirely in the adjacent region adjacent to the convex point portion ( By setting the optical power of the light beam engraving over the entire circumference of the convex point portion so that the exposure of the light beam applied to the upper surface of the convex point portion is equal to or lower than the engraving threshold energy, the first etching apparatus 11 Compared with the case where no is applied, it can be made closer to the convex portion of the desired size and shape.

  In addition, in the case where the shape in plan view is a polygonal point other than the plan view rectangular shape (for example, a triangular shape or a pentagonal shape), the region set below the engraving threshold energy in the adjacent region By including the area adjacent to the corner of the convex part of the projection, the corner of the convex part is formed more clearly than when exposing all the areas adjacent to the corner of the convex part of the polygonal shape in plan view. (The corners are not chamfered).

[Second etching equipment]
FIG. 27 is a configuration diagram of a second etching apparatus to which the multi-beam exposure scanning apparatus is applied. The illustrated second etching apparatus 110 fixes a sheet-like base material F (corresponding to a “recording medium”) to the outer peripheral surface of a drum 50 having a cylindrical shape, and the drum 50 is fixed in the direction indicated by the arrow R in FIG. A plurality of laser beams corresponding to image data of an image to be engraved (recorded) on the base material F from the exposure head 30 of the laser recording apparatus 10 toward the base material F, The exposure head 30 is scanned at a predetermined pitch in the sub-scanning direction (arrow S direction in FIG. 27) orthogonal to the main scanning direction, thereby engraving (recording) a two-dimensional image on the surface of the substrate F at high speed.

  The laser recording apparatus 10 used in the second etching apparatus 110 includes a light source unit 20 that generates a plurality of laser beams, an exposure head 30 that irradiates the substrate F with the plurality of laser beams generated by the light source unit 20, and exposure. And an exposure head moving unit 40 that moves the head 30 along the sub-scanning direction.

  The light source unit 20 includes a plurality of semiconductor lasers 21 (a total of 32 in this case), and the light of each semiconductor laser 21 is individually supplied to the optical fiber array unit 300 of the exposure head 30 via the optical fibers 22 and 70. Is transmitted.

  In this example, a broad area semiconductor laser (wavelength: 915 nm) is used as the semiconductor laser 21, and these semiconductor lasers 21 are arranged side by side on the light source substrate 24. Each semiconductor laser 21 is individually coupled to one end of an optical fiber 22, and the other end of the optical fiber 22 is connected to an adapter of an FC type optical connector 25.

  The adapter substrate 23 that supports the FC optical connector 25 is vertically attached to one end of the light source substrate 24. Further, an LD driver substrate 27 mounted with an LD driver circuit (not shown in FIG. 27, reference numeral 26 in FIG. 33) for driving the semiconductor laser 21 is attached to the other end portion of the light source substrate 24. Each semiconductor laser 21 is connected to a corresponding LD driver circuit via an individual wiring member 29, and each semiconductor laser 21 is individually driven and controlled.

  In the present embodiment, a multimode optical fiber having a relatively large core diameter is applied to the optical fiber 70 in order to increase the output of the laser beam. Specifically, in this embodiment, an optical fiber having a core diameter of 105 μm is used. Further, a semiconductor laser 21 having a maximum output of about 10 W is used. Specifically, for example, a core having a core diameter of 105 μm and an output of 10 W (6398-L4) sold by JDS Uniphase can be used.

  On the other hand, the exposure head 30 is provided with an optical fiber array unit 300 that collectively emits the laser beams emitted from the plurality of semiconductor lasers 21. The light emitting section (not shown in FIG. 27, reference numeral 280 in FIG. 28) of the optical fiber array section 300 has a structure in which the emitting ends of 32 optical fibers 70 guided from each semiconductor laser 21 are arranged in a line. (See FIG. 29).

  Further, in the exposure head 30, a collimator lens 32, an opening member 33, and an imaging lens 34 are arranged in order from the light emitting unit side of the optical fiber array unit 300. An imaging optical system is configured by the combination of the collimator lens 32 and the imaging lens 34. The opening member 33 is disposed so that the opening is positioned at the far field when viewed from the optical fiber array unit 300 side. As a result, an equivalent light amount limiting effect can be given to all laser beams emitted from the optical fiber array unit 300.

  The exposure head moving unit 40 includes a ball screw 41 and two rails 42 arranged so that the longitudinal direction thereof is along the sub-scanning direction, and a sub-scanning motor (not shown in FIG. 27) that rotationally drives the ball screw 41. , The exposure head 30 arranged on the ball screw 41 can be moved in the sub-scanning direction while being guided by the rail 42. In addition, the drum 50 can be driven to rotate in the direction of arrow R in FIG. 27 by operating a main scanning motor (not shown in FIG. 27, reference numeral 51 in FIG. 33), thereby performing main scanning.

  FIG. 28 is a configuration diagram of the optical fiber array section 300, and FIG. 29 is an enlarged view of the light emitting section 280 (viewed in the direction of arrow A in FIG. 28). As shown in FIG. 29, in the light emitting section 280 of the optical fiber array section 300, optical fibers 70 having a core diameter of 105 μm that emit 32 lights at equal intervals are arranged in a straight line.

  The optical fiber array unit 300 includes a base (V-groove substrate) 302, and the base 302 is formed so that the same number of semiconductor lasers 21, that is, 32 V-shaped grooves 282 are adjacent to each other at a predetermined interval. Has been. One optical fiber end 71 of the other end of the optical fiber 70 is fitted into each V-shaped groove 282 of the base 302. Thereby, the optical fiber end group 301 arranged in a straight line is configured. Accordingly, a plurality (32) of these laser beams are simultaneously emitted from the light emitting part 280 of the optical fiber array part 300.

  FIG. 30 is a schematic diagram of an imaging system of the optical fiber array unit 300. As shown in FIG. 30, the light emitting section 280 of the optical fiber array section 300 is exposed to the exposure surface (surface) FA of the base material F at a predetermined imaging magnification by the imaging means composed of the collimator lens 32 and the imaging lens 34. The image is formed in the vicinity of. In the present embodiment, the imaging magnification is set to 1/3, and the spot diameter of the laser beam LA emitted from the optical fiber end portion 71 having a core diameter of 105 μm is thus 35 μm.

  In the exposure head 30 having such an imaging system, the adjacent fiber interval (L1 in FIG. 29) of the optical fiber array unit 300 described in FIG. 29 and the optical fiber end group 301 when the optical fiber array unit 300 is fixed. By appropriately designing the inclination angle (angle θ in 31) in the arrangement direction (array direction), as shown in FIG. 31, a scanning line that is exposed by a laser beam emitted from an optical fiber arranged at an adjacent position The interval P1 of (main scanning line) K can be set to 10.58 μm (equivalent to a resolution of 2400 dpi in the sub-scanning direction).

  By using the exposure head 30 configured as described above, it is possible to simultaneously scan and expose a range of 32 lines (one swath).

  FIG. 32 is a plan view showing an outline of a scanning exposure system in the second etching apparatus 110 shown in FIG. The exposure head 30 includes a focus position changing mechanism 60 and an intermittent feed mechanism 90 in the sub-scanning direction.

  The focus position changing mechanism 60 has a motor 61 and a ball screw 41 that move the exposure head 30 back and forth relative to the surface of the drum 50, and can move the focus position by about 339 μm in about 0.1 seconds under the control of the motor 61. it can. The intermittent feed mechanism 90 constitutes the exposure head moving unit 40 described with reference to FIG. 27, and includes a ball screw 41 and a sub-scanning motor 43 that rotates the ball screw 41, as shown in FIG. The exposure head 30 is fixed to the stage 44 on the ball screw 41. Under the control of the sub-scanning motor 43, the exposure head 30 is moved in the direction of the axis 52 of the drum 50 for one swath (in the case of 2400 dpi) in about 0.1 second. (10.58 μm × 64 ch = 677.3 μm) can be intermittently fed.

  In FIG. 32, reference numerals 46 and 47 denote bearings that rotatably support the ball screw 41. Reference numeral 55 denotes a chuck member that chucks the substrate F on the drum 50. The position of the chuck member 55 is a non-recording area where exposure (recording) by the exposure head 30 is not performed. While rotating the drum 50, the substrate F on the rotating drum 50 is irradiated with a laser beam of 32 channels from the exposure head 30 so that the exposure range 92 for 32 channels (one swath) can be formed without a gap. Exposure is performed, and engraving (image recording) of 1 swath width is performed on the surface of the substrate F. Then, when the chuck member 55 passes in front of the exposure head 30 by the rotation of the drum 50 (at the non-recording area of the base material F), intermittent feeding is performed in the sub-scanning direction to expose the next one swath. To do. A desired image is formed on the entire surface of the substrate F by repeating exposure scanning by intermittent feeding in the sub-scanning direction.

  In this example, the sheet-like base material F is used, but a cylindrical recording medium (sleeve type) can also be used.

(Control system configuration)
FIG. 33 is a block diagram showing the configuration of the control system of the second etching apparatus 110. As shown in FIG. 33, the second etching apparatus 110 includes an LD driver circuit 26 that drives each semiconductor laser 21 in accordance with two-dimensional image data to be engraved, a main scanning motor 51 that rotates the drum 50, A main scanning motor driving circuit 81 for driving the scanning motor 51, a sub scanning motor driving circuit 82 for driving the sub scanning motor 43, and a control circuit 80 are provided. The control circuit 80 controls the LD driver circuit 26 and each motor drive circuit (81, 82).

  Image data indicating an image to be engraved (recorded) on the substrate F is supplied to the control circuit 80. The control circuit 80 controls the driving of the main scanning motor 51 and the sub-scanning motor 43 based on the image data, and outputs the outputs (on / off control and laser beam power control) of each semiconductor laser 21 individually. Control.

  In the second etching apparatus 110 configured as described above, the base material F (recording medium) can be engraved. As shown in FIG. 34, engraving is performed by exposing the exposed area 202 of the substrate F, and the non-exposed area 201 is not exposed. For the exposure region, the leftmost channel ch1 (first beam) first emits and engraves, then the right adjacent channel ch2 (second beam) emits and engraves, and then sequentially adjacent channels. The ch3 to ch32 beams are emitted to engrave the swath width. When engraving of one swath width is completed, the same engraving is sequentially performed by moving the swath width in the sub-scanning direction.

(Method for forming convex small dots)
Next, an exposure scanning process for forming a small convex point having a steep shape in the second etching apparatus 110 configured as described above will be described. In the present embodiment, three main scans (exposure scans) are performed at the same sub-scanning position.

  FIG. 35 is a diagram showing a cross section of the upper surface and the main scanning direction and the sub-scanning direction of the non-exposure region 211 in the region to be formed as the convex small points of the substrate F and the exposure region 212 other than the non-exposure region 211 It is.

  First, the first exposure scan is performed on the exposure region 212. As a result, as shown in FIG. 35A, the exposure region 212 is engraved, and the non-exposure region 211 is formed as a small convex point.

  Next, a second exposure scan is performed on the exposure region 212. Here, in the exposure region 212, the first exposure region 212a located at one dot (one pixel at a resolution of 2400 dpi) or two dots around the non-exposure region 211 and the other second exposure region 212b are optical lasers. The optical power (the amount of light reached) of the beam is varied.

  For example, assuming that the light power applied to the exposure region 212 during the first exposure scan is 1, the light power applied to the first exposure region 212a is 0.9 and the second power during the second exposure scan. The optical power to the exposure area 212b is assumed to be 1.2.

  As the exposure area 212 is engraved in the first exposure scan, a step is formed between the surface of the non-exposure area 211 and the surface of the exposure area 212 as shown in FIG. Therefore, the heat of the surface of the exposure region 212 generated by performing the exposure scan on the exposure region 212 is less in the non-exposure region than in the first exposure scan performed in the state where there is no step during the second exposure scan. It is difficult to reach 211. As a result, the optical power to the exposure region 212 can be made stronger than in the first exposure scan, and the engraving can be deeper.

  However, in the first exposure scan, the shape of the small protrusions to be formed to some extent is formed in the non-exposure area 211, so that the optical power to the first exposure area 212a is the same during the first exposure scan. There is no need to be stronger.

  Therefore, in order to reduce the influence of the heat accumulation in the non-exposure region 211 while making the optical power to the second exposure region 212b stronger than that in the first exposure scan, The optical power is set lower than that in the first exposure scanning. As a result, as shown in FIG. 35B, the exposure region 212 is deeply engraved, and the non-exposure region 211 is formed as a steep convex small point.

  Note that the size of the first exposure region 212a may be determined according to the shape of the convex small point to be formed. For example, a region of 1 dot or 2 dots around the convex small point (1 adjacent to the convex small point). A pixel or a region of two pixels).

  Further, in the third exposure scanning, the exposure scanning is performed on the first exposure region 212a and the second exposure region 212b.

  Also in the third exposure scanning, the optical power of the optical laser beam is made different between the first exposure region 212a and the second exposure region 212b. For example, assuming that the light power applied to the exposure region 212 during the first exposure scan is 1, the light power applied to the first exposure region 212a is 0.9 and the second power during the third exposure scan. The light power to the exposure area 212b is set to 1.5.

  Due to the second exposure scan, the level difference formed between the surface of the exposure region 212 and the surface of the non-exposure region 211 is further increased, so that the heat of the surface of the exposure region 212 is not easily transmitted to the non-exposure region 211. ing. Therefore, the optical power to the exposure area 212 can be made stronger than that in the second exposure scan.

  Similarly to the second exposure scanning, in order to reduce the influence of heat accumulation on the non-exposure region 211, the optical power to the first exposure region 212a is made lower than that during the first exposure scanning. .

  Therefore, at the time of the third exposure scan, the optical power to the second exposure region 212b is made stronger than that at the time of the second exposure scan, while the light power to the first exposure region 212a is the same at the time of the first exposure scan. Lower than. As a result, as shown in FIG. 35C, the exposure region 212 is further engraved, and the non-exposure region 211 is formed as a steeper convex small point.

  As described above, by performing exposure scanning three times at the same sub-scanning position and controlling the optical power of the laser beam as described above, a convex shape having a steep shape as shown in FIG. A point can be formed.

  In the present embodiment, the second and subsequent exposures lower the optical power to the first exposure region 212a and increase the optical power to the second exposure region 212b as compared to the first exposure. Any one of them may be equal to the optical power of the first exposure. Further, exposure scanning may be performed four or more times at the same sub-scanning position. In this case, it is preferable to gradually increase the optical power to the second exposure region 212b in the fourth and subsequent exposures.

  Further, in the present embodiment, the exposure areas 212 shown in FIG. 35A, the first exposure areas 212a shown in FIGS. 35B and 35C, and the second exposure areas 212b, respectively. On the other hand, the exposure is performed with a uniform light power in each exposure area, but the light power is distributed in each area such that the light power is reduced as it is closer to the non-exposure area 211 in each area. Also good.

(Power control between each channel of the beam)
In FIG. 34, if exposure scanning is performed with the optical powers of the channels ch1 to ch32 set equal, the exposure region 202 is first engraved with the first beam (ch1), and the base material F is warmed by the residual heat. It is done. Since the second beam (ch2) for engraving the next adjacent line is irradiated there and engraved, the energy of ch2 is applied in a state where the temperature of the substrate F is high due to the influence of residual heat due to the engraving of ch1. It will be. In this way, a phenomenon occurs in which engraving by the subsequent beam proceeds excessively due to the influence of heat by engraving of the preceding adjacent beam.

  Although the phenomenon that the engraving proceeds excessively always occurs in the exposure area 202, it becomes a problem particularly at the boundary between the non-exposure area 201 and the exposure area 202.

  For example, the outer periphery of the left side of the non-exposure area 201 in FIG. 34B is engraved with ch4, but if the engraving with ch4 proceeds excessively under the influence of heat from the engraving of ch1 to ch3, the non-exposure area 201 May not be engraved into the desired shape.

  Note that such a problem does not occur on the outer periphery of the left side of the non-exposure area 201 in FIG. In the case of FIG. 34A, the outer periphery of the left side of the non-exposure area 201 is engraved with ch1, but since there is no scanning beam preceding ch1 in one swath, there is no influence of residual heat. As described above, the influence of heat differs depending on the positional relationship between the small convex point to be formed and the channel of each beam.

  In order to avoid this phenomenon, the second etching apparatus 110 controls the optical power between the channels of each beam based on the information on which channel is used for which position. An example is shown in FIG. In FIG. 36, the horizontal axis represents the channel number (ch), and the vertical axis represents the optical power of the beam as a relative value (the power of ch1 is normalized to 1). As shown in FIG. 36, the optical powers of the channels ch1, ch2, and ch3 corresponding to the start portion for starting engraving are set as ch1> ch2> ch3, and the optical powers after ch3 (intermediate portion) are made substantially constant. Then, the optical power of the last (end of writing) channel (ch32) in the swath is increased (for example, ch32 = ch2).

  As described with reference to FIG. 34, when convex small dots are formed by the beam arrangement of the channel groups arranged obliquely, a time difference occurs in the light emission timing (timing for pixel exposure) of each channel. First, the ch1 beam is emitted, and the next ch2 beam is emitted when exposure scanning is performed. At this time, since the surface temperature of the base material F corresponding to the beam position of ch2 is increased due to the influence of the heat of the preceding ch1 beam, the optical power of ch2 is changed to ch1 in consideration of the influence of the heat of the adjacent beam. Lower than.

  In FIG. 36, the optical power of ch2 is set to 0.7 with respect to the optical power of ch1 (standardized to 1), but the light quantity ratio of adjacent beams to the beam scanned first is , 0.4 to 0.9.

  Similarly for ch3, considering the heat accumulation by the beams of the preceding ch2 and ch1, the optical power of ch3 is further lowered than that of ch2 (in FIG. 36, it is set to 0.5).

  However, after ch3, the heat condition is saturated and becomes almost the same condition, so that the optical power is substantially constant in the middle part of the line. By controlling in this way, it becomes possible to engrave appropriately regardless of the positional relationship between the convex small point and the channel of each beam.

  Note that FIG. 36 is merely an example of a beam spot diameter of 35 μm and a resolution of 2400 dpi (scanning line interval = 10.6 μm), and the optical power between channels is optimized according to conditions such as spot diameter, spot arrangement, and scanning speed. There is a need to. For example, depending on conditions, the optical power relationship between the beams may be ch1 ≧ ch2≈ch3≈ch4... Or ch1> ch2> ch3> ch4 (≈ch5≈ch6...). Good.

  It is effective to control such optical power in the range of several pixels (about 2 to 4 pixels) for writing, and to perform optical power control between beams for at least two adjacent pixels (ch1 and ch2). Is effective.

  The last channel (here, ch32) differs from the other intermediate channels (ch4 to ch31) in that there is no heat contribution from the next adjacent beam, so the optical power may be increased, Depending on the conditions, it may be the same as the previous channel (ch31).

  As illustrated above, when a desired shape is formed by engraving the vicinity of the surface of the substrate F with a laser by a multi-beam exposure system, the light emission amount based on the light emission state of the beam around the laser emitting pixel Shall be controlled. The amount of light is controlled by a few pixels in the sub-scanning direction centering on the emitted beam, and when the other beams are not emitted first, the amount of light is a, and the pixel A is exposed by a beam (first beam) with this amount of light a. After that, when a certain amount of light is used when the adjacent beam (second beam) exposes the pixel B adjacent to the pixel A, the light amount b is set.

(Relationship between non-exposure area and actual small convex point)
In order to form a convex small point, in consideration of the fact that the peripheral area of the non-exposed area is engraved by the residual heat when the boundary of the non-exposed area is engraved, it is actually more than the convex small point. There are cases where exposure is not performed in a large range. For example, as shown in FIG. 37, in the case where 2 × 2 dot small dots are formed under the conditions of a spot diameter of 35 μm and a scanning line interval = 10.6 μm, the non-exposed region 211 is set to 1 dot around the small dots. By setting this range, the final convex small dot 214 of 2 × 2 dots may be formed.

  Therefore, when this embodiment is applied under such conditions, it is necessary to engrave the 4 × 4 dot range as the non-exposed region 211 in FIG. 35 and the region outside that one dot as the exposed region 212. is there.

  As described above, the relationship between the non-exposure area and the actually formed convex small points varies depending on various conditions of the beam and the substrate, but this embodiment can be applied to the non-exposure area as the non-exposure area. That's fine.

(In the case of interlaced exposure)
FIG. 36 illustrates an example in which non-interlaced exposure is performed in which all pixels in one swath are exposed at a time without spacing the pixels during exposure scanning. However, in the case of interlaced exposure in which one pixel is spaced in the sub-scanning direction. Can be applied similarly.

  FIG. 38 shows an example of optical power control between channels in the case of performing interlaced exposure with a gap of 1 ch under conditions of a spot diameter of 35 μm and a resolution of 2400 dpi (scanning line interval = 10.6 μm).

  Since the interlace exposure is also affected by the heat of the adjacent beam, the optical power after ch2 is lowered with respect to the optical power of ch1 (1 by standardization). In the figure, the optical power of ch2 is set to “0.7”, but the present invention is not limited to this, and the light quantity ratio of the adjacent beam to the beam scanned first is in the range of 0.5 to 0.9. Is set as appropriate.

  In the case of interlaced exposure, since the density of the beam in the sub-scanning direction is lower (sparse) than in non-interlaced exposure, the influence of heat between adjacent beams is smaller than in the case of non-interlaced exposure. For this reason, compared with the case of non-interlaced exposure (FIG. 36), the reduction amount of the optical power after ch2 in interlaced exposure (FIG. 38) is small.

(When using other beam arrangements)
In the above embodiment, the beam arrangement in which 32 lines (one swath) are arranged in one row in an oblique direction by the exposure head 30 having the one-row optical fiber array arrangement described in FIG. 29 is illustrated. The arrangement is not limited to such a single row.

  FIG. 39 shows another example of the optical fiber array unit light source. The illustrated optical fiber array unit light source 500 includes optical fiber array units 501, 502, 503, and 504 combined in four stages. In each stage array, 16 optical fibers 70 each having a core diameter of 105 μm are arranged in a line in a straight line, and a total of 64 optical fibers 70 are arranged in an oblique matrix form in four stages. It has become.

  As shown in FIG. 39, the channel numbers belonging to the optical fiber array unit 501 at the uppermost stage (first stage) are 4M + 1 (M = 0, 1, 2,...) From the right end and the channels belonging to the second stage (reference numeral 502). The number of channels is 4M + 2 from the right end, the number of channels belonging to the third stage (reference 503) is 4M + 3 from the right end, and the number of channels belonging to the fourth lowest stage (reference 503) is 4M + 4 from the right end. The block is composed of 16 rows of 4 channels that share a common channel.

  The adjacent fiber spacing (L1 in FIG. 39) and the spacing of each stage (L2) in the row of the optical fiber array units 501, 502, 503, and 504 of each stage, and the relative position in the row direction (L3 in FIG. 39), Further, by appropriately designing the inclination angle of the array unit, as shown in FIG. 40, the interval P1 between the scanning lines (main scanning lines) K exposed by the optical fiber of the adjacent channel and the right end of the block consisting of 4 channels. The spacing P2 between the scanning lines exposed in the channel (channel belonging to the upper stage of the array) and the leftmost channel (channel belonging to the lower stage of the array) adjacent to the channel is equal to 10.58 μm (corresponding to a resolution of 2400 dpi in the sub-scanning direction). Can be set to

  When engraving fine lines along the sub-scanning direction with such a beam arrangement, the optical power between channels of each beam is controlled as shown in FIG. 41, for example.

  In FIG. 41, the horizontal axis indicates the channel number, and the vertical axis indicates the optical power (ch1 normalized to 1). As shown in the figure, in correspondence with repetition of swath blocks in units of 4 lines, the optical power between the channels within this repetition unit is expressed as ch (4M + 1)> ch (4M + 2)> ch (4M + 3)> ch (4M + 4). Set as follows.

  Using the above configuration, the base material F can be engraved as shown in FIG. At this time, by performing exposure scanning three times at the same sub-scanning position and controlling the optical power of the laser beam, a small convex point having a steep shape is formed as shown in FIG. be able to.

  Note that the form of the optical fiber array unit light source is not limited to the example described with reference to FIG. 39, and an arbitrary array stage number and swath block repetition number can be realized by a method similar to FIG. 39, and an appropriate two-dimensional array can be realized.

(Spiral exposure method)
32 is not limited to the scanning exposure method by intermittent feeding in the sub-scanning direction described above, and the surface of the substrate F is scanned in a spiral shape by moving the exposure head 30 at a constant speed in the sub-scanning direction while the drum is rotating. A spiral exposure method may be employed.

  For example, if one swath of the exposure head 30 is 32 channels and four scans are required for one main scanning line, exposure is performed for 32 ÷ 4 = 8 channels while the drum 50 rotates once. Control may be made so that the head 30 moves in the sub-scanning direction. By performing sub-scanning in this way, each main scanning line can be exposed and scanned a desired number of times (in this case, four times), and the entire surface of the substrate F can be exposed and scanned.

  The intermittent feed method is effective when the rotational speed of the drum is relatively slow. On the other hand, the spiral exposure method is effective when the rotational speed of the drum is relatively high.

Next, the groove forming process using the second etching apparatus will be described.
FIG. 42 shows an outline of the process. The base material 700 to be etched (engraved) has an engraving layer 704 (rubber layer or resin layer) on a substrate 702, and a protective cover film 706 is stuck on the engraving layer 704. Yes. At the time of processing, as shown in FIG. 42 (a), the cover film 706 is peeled to expose the engraving layer 704, and the engraving layer 704 is irradiated with laser light to remove a part of the engraving layer 704. A desired three-dimensional shape is formed (see FIG. 42B). A specific laser etching method is as described with reference to FIGS. Note that dust generated during laser etching is sucked and collected by a suction device (not shown).

  After the groove forming step is completed, as shown in FIG. 42C, water cleaning is performed by the cleaning device 710 (cleaning step), and then a drying step (not shown) is performed.

<Wiring formation process>
The wiring formation step S16 is a step of applying the ink containing the metal element-containing material in the groove formed in the groove formation step S14 to form the metal wiring 140 in the groove 120 (FIG. 2C). By implementing this process S16, the metal wiring 140 is formed on the base material 100, and the wiring board 160 is obtained.
First, the ink containing the metal element-containing material used in this step S16 will be described in detail, and then the procedure of this step S16 will be described in detail.

(Ink containing metal element-containing compound)
The metal element-containing compound is a compound containing a metal element (metal atom) and is a material for forming a metal wiring.
The type of metal element (metal atom) contained in the metal element-containing compound is not particularly limited, but Pd, Ag, Cu, Ni, Al, Fe, Co, Mo, It is preferably an alloy composed of at least one selected from the group consisting of Au, or a metal element selected from the above group.
Examples of the metal element-containing compound include so-called metal salts, metal oxides, metal hydroxides, and the like.

As the metal element-containing compound, metal particles may be used. The types of metal atoms contained in the metal particles are as described above.
The average diameter of the metal particles is not particularly limited, but is preferably 1 to 500 nm, more preferably 5 to 100 nm, from the viewpoint of easy ejection by an ink jet method described later.

The ink contains a solvent as necessary.
The type of solvent that can be used is not particularly limited, and examples thereof include alcohol solvents such as water, methanol, ethanol, propanol, isopropanol, ethylene glycol, glycerin, and propylene glycol monomethyl ether, acids such as acetic acid, acetone, methyl ethyl ketone, and cyclohexanone. Ketone solvents, amide solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, nitrile solvents such as acetonitrile and propionitrile, ester solvents such as methyl acetate and ethyl acetate, carbonates such as dimethyl carbonate and diethyl carbonate In addition to these, ether solvents, glycol solvents, amine solvents, thiol solvents, halogen solvents and the like can be mentioned.

(Procedure of step S16)
The method for applying the ink described above into the groove is not particularly limited, and a known method (immersion method, coating method, etc.) can be adopted. In particular, it is preferable to apply ink into the groove by an ink jet method.
After applying the ink into the groove, heat treatment may be performed as necessary. By performing the heat treatment, the solvent and organic substances are decomposed and removed, and a metal wiring having excellent conductive characteristics can be formed. The conditions for the heat treatment are selected according to the materials used, but usually heat treatment at 70 to 500 ° C. (preferably 100 to 300 ° C.) for 1 minute to 2 hours (preferably 5 minutes to 1 hour). It is preferable to implement.

(Preferred embodiment of step S16)
As a suitable aspect of process S16, the process of providing the ink containing an electroless-plating catalyst or its precursor in a groove | channel, performing an electroless-plating process, and forming a metal wiring in a groove | channel is mentioned. By performing this treatment, a metal wiring having excellent adhesion to the substrate can be formed.

As will be described later, when the plating treatment is performed in this step S16, an electroless plating catalyst or a precursor thereof is used as the metal element-containing compound.
Below, an electroless-plating catalyst or its precursor is explained in full detail, and the procedure of electroless-plating is explained in full detail after that.

Any electroless plating catalyst can be used as long as it becomes an active nucleus at the time of electroless plating. Specifically, a metal having a catalytic ability for autocatalytic reduction reaction (lower ionization tendency than Ni). And those known as metals that can be electrolessly plated). Specific examples include Pd, Ag, Cu, Ni, Al, Fe, and Co. Among these, Ag, Pd, and Cu are particularly preferable because of their high catalytic ability.
The electroless plating catalyst may be used as a metal colloid. In general, a metal colloid can be prepared by reducing metal ions in a solution containing a charged surfactant or a charged protective agent. The charge of the metal colloid can be controlled by the surfactant or protective agent used here.

  The electroless plating catalyst precursor can be used without particular limitation as long as it can become an electroless plating catalyst by a chemical reaction. The metal ions of the metals mentioned as the electroless plating catalyst are mainly used. The metal ion that is an electroless plating catalyst precursor becomes a zero-valent metal that is an electroless plating catalyst by a reduction reaction. The metal ion, which is an electroless plating catalyst precursor, may be used as an electroless plating catalyst after being applied to the layer to be plated and before being immersed in the electroless plating bath, by separately changing to a zero-valent metal by a reduction reaction. The electroless plating catalyst precursor may be immersed in an electroless plating bath and changed to a metal (electroless plating catalyst) by a reducing agent in the electroless plating bath.

The metal ion that is the electroless plating catalyst precursor is preferably applied to the layer to be plated using a metal salt. The metal salt used is not particularly limited as long as it is dissolved in a suitable solvent and dissociated into a metal ion and a base (anion), and M (NO ₃ ) _n , MCl _n , M _{2 / n} (SO ₄ ), M _{3 / n} (PO ₄ ) (M represents an n-valent metal atom), and the like. As a metal ion, the thing which said metal salt dissociated can be used suitably. Specific examples include, for example, Ag ions, Cu ions, Al ions, Ni ions, Co ions, Fe ions, and Pd ions. Among them, those capable of multidentate coordination are preferable, and in particular, functionalities capable of coordination. In view of the number of types of groups and catalytic ability, Ag ions and Pd ions are preferred.

The electroless plating performed in this step refers to an operation of depositing a metal by a chemical reaction using a solution in which metal ions to be deposited as a plating are dissolved.
The electroless plating is performed, for example, by immersing the base material provided with the electroless plating catalyst in water and removing the excess electroless plating catalyst (metal) and then immersing it in an electroless plating bath. As the electroless plating bath used, a known electroless plating bath can be used. In addition, as an electroless-plating bath, the case where an alkaline electroless-plating bath (pH is preferable about 9-14) is preferable from the point of availability.
In addition, when the substrate to which the electroless plating catalyst precursor has been applied is immersed in the electroless plating bath, the substrate is washed with water to remove excess precursors (such as metal salts), and then in the electroless plating bath Soak in. In this case, reduction of the plating catalyst precursor and subsequent electroless plating are performed in the electroless plating bath. As the electroless plating bath used here, a known electroless plating bath can be used as described above.
In addition, the reduction of the electroless plating catalyst precursor may be performed as a separate step before electroless plating by preparing a catalyst activation liquid (reducing liquid) separately from the embodiment using the electroless plating liquid as described above. Is possible. The catalyst activation liquid is a liquid in which a reducing agent capable of reducing an electroless plating catalyst precursor (mainly metal ions) to zero-valent metal is dissolved, and the concentration of the reducing agent with respect to the whole liquid is 0.1 to 50% by mass. Preferably, 1-30 mass% is more preferable. As the reducing agent, it is possible to use a boron-based reducing agent such as sodium borohydride or dimethylamine borane, or a reducing agent such as formaldehyde or hypophosphorous acid.

  As a composition of a general electroless plating bath, for example, in addition to a solvent (for example, water), 1. metal ions for plating; 2. reducing agent; Additives (stabilizers) that improve the stability of metal ions are mainly included. In addition to these, the plating bath may contain known additives such as a plating bath stabilizer.

  The organic solvent used in the plating bath needs to be a solvent that can be used in water, and in this respect, ketones such as acetone and alcohols such as methanol, ethanol, and isopropanol are preferably used.

  As the types of metals used in the electroless plating bath, for example, copper, tin, lead, nickel, gold, silver, palladium, and rhodium are known. Among them, copper and gold are particularly preferable from the viewpoint of conductivity. preferable. Moreover, the optimal reducing agent and additive are selected according to the said metal.

<Wiring board>
The wiring board obtained through the above steps includes a base material and metal wiring.
The obtained wiring board can be used for various applications. For example, a printed wiring board, a frame wiring for a touch panel, a bus line, and the like can be given.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these Examples.

<Example 1>
(Method for producing composition for laser etching)
40 parts by weight of Denkabutyral (manufactured by Denki Kagaku Kogyo Co., Ltd., Tg: 68 ° C. (component E)) in a three-necked flask equipped with a stirring spatula and a cooling tube, 20 parts by weight of diethylene glycol as a plasticizer, and tetrahydrofuran as a solvent 150 parts by weight were added and heated at 70 ° C. for 120 minutes with stirring to dissolve the binder. In this binder dispersion, 0.005 part by weight of perbutyl Z (t-butylperoxybenzoate) (manufactured by NOF Corporation (component B)) as a polymerization initiator and KBM802 (Shin-Etsu Chemical Co., Ltd.) as a chain transfer agent 3 parts by weight, (C-1) carbon black Asahi # 80 N-220 (manufactured by Asahi Carbon Co., Ltd.), 5 parts by weight, 1,8-diazabicyclo [5.4.0] undec-7-ene (sum) 0.5 parts by weight of Kojun Pharmaceutical Co., Ltd.), the following (Component A) polymerizable compound, (Component D) silane coupling agent (compound having hydrolyzable silyl group and / or silanol group) A laser etching composition was obtained by adding 15 parts by weight and 6 parts by weight, respectively, and stirring.
Here, the compounds of Component A and Component D used in this example are shown below.
(Component A: polymerizable compound)
Tricyclodecane dimethanol dimethacrylate (DCP) (manufactured by Shin-Nakamura Chemical Co., Ltd.)
(Component D)
Tris (3-trimethoxysilylpropyl) isocyanurate (X-12-965, manufactured by Shin-Etsu Chemical Co., Ltd.)

The following film was used as the oxygen barrier film.
Polyvinylidene chloride film: Saran Wrap (registered trademark) (manufactured by Asahi Kasei Corporation)

(Water repellent treatment process)
Gently cast the laser etching composition to the extent that it does not flow onto the PET substrate (support), and apply the oxygen barrier film to prevent air from entering between the laser etching composition and the oxygen barrier film, Heating was performed in an oven at 100 ° C. for 5 hours to remove the solvent and perform thermal crosslinking, thereby forming a laser etching material (base material). Thereafter, the oxygen barrier film was peeled off, and the atmospheric pressure plasma treatment of the substrate surface was performed using CF ₄ gas.

(Groove formation process)
Using HELIOS 6010 (Stork Prints), the substrate surface obtained in the above water-repellent treatment step was irradiated with a near infrared laser to etch the substrate surface, and a lattice of line / space = 20 μm / 200 μm. Grooves were formed so as to form a shape. The depth of the groove was 3 μm.

(Wiring formation process (1))
An electroless plating catalyst-containing ink was applied into the groove on the substrate surface formed in the groove forming step using a DMP printer manufactured by Dimatix. As the electroless plating catalyst-containing ink, Flow Metal SW1020 manufactured by Bando Co., Ltd. was used.
Next, the following electroless plating solution was prepared, the base material provided with the electroless plating catalyst obtained above was immersed in the electroless plating solution, and electroless copper plating was performed at 45 ° C.
[Electroless copper plating solution]
Copper sulfate 0.03 mol / L
Formalin 0.1 mol / L
Triethanolamine 0.1 mol / L
2,2'-bipyridyl 0.01 g / L
Adjust pH to 12.5 with aqueous sodium hydroxide solution

(Pattern formability evaluation)
The metal wiring pattern of the formed wiring board was observed with an optical microscope, the metal wiring width was measured, and evaluated according to the following criteria.
“A”: wiring width is 18 μm or more and less than 22 μm “B”: wiring width is 22 μm or more and less than 25 μm “C”: wiring width is 25 μm or more

(Resistance evaluation)
The volume resistivity of the metal wiring in the obtained wiring board was calculated using a surface resistance measuring device (Loresta GP) manufactured by Mitsubishi Chemical Analytic, and evaluated according to the following criteria.
“A”: Less than 1Ω / □ “B”: 1Ω / □ or more and less than 100Ω / □ “C”: 100Ω / □ or more

(Adhesion evaluation)
The adhesion of the metal wiring of the obtained wiring board was evaluated according to the following procedure.
A cellophane tape manufactured by Nichiban Co., Ltd. was bonded onto the obtained conductive pattern, and after peeling in the direction of 180 degrees, that is, in the direction in which the wiring was extended, the resistance was measured. When the conductive pattern is peeled off, the resistance value increases (conductivity deteriorates). Resistance before tape bonding / resistance after peeling (conductivity deterioration degree) was determined by measurement and evaluated as follows.
“A”: Degree of conductivity is less than 1.2 “B”: Degree of conductivity is 1.2 or more and less than 3.0 “C”: Degree of conductivity is 3.0 or more and / or laser etching Adhesion of the material to the tape is observed (visual observation).

<Example 2>
A wiring board was manufactured according to the same procedure as in Example 1 except that the following (Wiring forming process (Part 2)) was performed instead of (Wiring forming process (Part 1)) performed in Example 1. Various evaluations were conducted.
In the wiring formation process (part 2), the electroless plating process is not performed.

(Wiring formation process (2))
A metal-containing ink (Flow Metal SW1020 manufactured by Bando Co., Ltd.) was printed in the groove on the substrate surface formed in the groove forming step using a DMP printer manufactured by Dimatix.

<Comparative Example 1>
A wiring board was manufactured according to the same procedure as in Example 1 except that the (groove forming step) performed in Example 1 was not performed, and various evaluations were performed.

<Comparative example 2>
A wiring board was manufactured and evaluated in accordance with the same procedure as in Example 2 except that PTFE was applied and dried instead of the plasma treatment using CF ₄ gas performed in Example 2.
PTFE was dissolved in 2-methylpyrrolidone and applied such that the PTFE thickness after drying was 0.5 μm.
This method corresponds to the method of Patent Document 1.

As shown in Table 1, in the embodiments of Examples 1 and 2, it was confirmed that a wiring excellent in pattern forming property, conductive property, and adhesion was obtained.
On the other hand, in the comparative example 1 which did not implement a groove | channel formation process, all of pattern formation property, electroconductivity, and adhesiveness were inferior.
In Comparative Example 2 using PTFE instead of fluorine-containing gas, the adhesion of the wiring was inferior.

DESCRIPTION OF SYMBOLS 10 Laser recording apparatus 11 1st etching apparatus 20 Light source unit (fiber light source)
21, 21A, 21B Semiconductor laser 22, 22A, 22B, 70, 70A, 70B Optical fiber 23, 23A, 23B Adapter substrate 24, 24A, 24B Light source substrate 25 FC type optical connector 25A, 25B SC type optical connector 26 LD driver circuit 27, 27A, 27B LD driver board 29 Wiring member 30 Exposure head 32 Collimator lens 33 Aperture member 34 Imaging lens 40 Exposure head moving part 41 Ball screw 42 Rail 43 Sub-scanning motor 44 Stage 50 Drum 51 Main scanning motor 52 Axis 55, 98 Chuck member 60 Focus position changing mechanism 61 Motor 71A, 71B Optical fiber end portion 80 Control circuit 81 Main scanning motor driving circuit 82 Sub scanning motor driving circuit 90 Intermittent feeding mechanism 92 Exposure range 100, 700 Base material 11 Second etching apparatus 120 Groove 140 Metal wiring 160 Wiring substrate 201, 211 Non-exposed area 202, 212 Exposed area 280 Light emitting part 282, 282A, 282B V-shaped groove 299 Actuator drive circuit 300 Optical fiber array part 301, 301A, 301B Optical fiber End group 302, 302A, 302B Base 304 Actuator 310 Base 500 Optical fiber array unit light source 501, 502, 503, 504 Optical fiber array unit 702 Substrate 704 Engraving layer 706 Cover film 710 Cleaning device

Claims (5)

A method of manufacturing a wiring board comprising a base material and metal wiring,
A step (1) of making the surface of the substrate water repellent using a fluorine atom-containing gas;
Etching the water-repellent substrate surface using a near-infrared laser to form a groove in the substrate surface (2);
And a step (3) of forming a metal wiring in the groove by applying an ink containing a metal element-containing material in the groove. The fluorine atom-containing gas is at least one gas selected from the group consisting of CF ₄ , SF ₆ , CHF ₃ , CH ₂ F ₂ , CH ₃ F, C ₂ F ₆ , and C ₄ F ₈ ; The manufacturing method of the wiring board of Claim 1.   The method for manufacturing a wiring board according to claim 1, wherein the groove has a depth of 0.1 to 50 μm.   The manufacturing method of the wiring board in any one of Claims 1-3 whose method of providing the said ink is an inkjet method.   The step (3) is a step of applying an electroless plating catalyst or an ink containing a precursor thereof in the groove, performing an electroless plating process, and forming a metal wiring in the groove. 5. A method for manufacturing a wiring board according to any one of 4 above.