JP2004247759A - Manufacturing method of composite member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a minute wiring pattern and conductive pattern at a low cost. <P>SOLUTION: In this method for manufacturing a composite member in which a conductive part is selectively formed on a specified section of an insulating porous material, formation for the conductive part is performed through a step for installing an electrode, a step for modifying a surface part, a step for infiltrating with electroplating liquid, and a step for electrolytic plating. The step for installing an electrode is a step for installing an electrode in the porous material. The step for modifying a surface part is a step for modifying a part of the porous material and changing its surface energy to form a pattern in which affinity for a water of a modified part is made different from that of a unmodified part. The step for infiltrating with electroplating liquid is a step for selectively infiltrating an insulating region of the modified part or the unmodified part in the selected porous material with the electroplating liquid while contacting with a surface of the electrode. The step for electrolytic plating is a step for depositing electrolytic plating in the region by electrifying the electrode to form the conductive part. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention forms a fine conductive pattern on or in a substrate, such as a wiring substrate such as a flexible substrate, a multilayer wiring substrate, an interposer, and a three-dimensional wiring, or an antenna, a coil, a sensor, an electrochemical cell, or a micromachine. The present invention relates to a method of manufacturing a composite member for manufacturing a composite member.

  In order to reduce the size of electronic devices such as mobile phones and wearable computers, a method capable of producing fine wiring patterns at low cost is essential.

  Furthermore, such a low-cost method for manufacturing a wiring pattern is indispensable for manufacturing a DNA chip, various sensors, and the like.

  Further, in the manufacture of various antennas and coils, it is necessary to three-dimensionally form wiring on a three-dimensional member. Such a three-dimensional wiring fabrication technique is also important for wiring on a housing of an electronic device and for wiring of a micromachine or an optoelectronic device.

  Generally, to form a wiring pattern, a Cu layer is first formed on a base material, and then a resist pattern is masked, and then the Cu layer is etched. However, such a method is complicated and difficult to miniaturize and three-dimensionally interconnect.

  Therefore, as a method of manufacturing a wiring pattern that is low-cost and capable of three-dimensional wiring, there is a method of selectively electroless plating only an exposed portion or an unexposed portion. For example, the present inventors have already proposed in Japanese Patent Application No. 2001-96683 a method using a photosensitive substance that generates or eliminates an ion-exchange group.

  To describe the proposed method in more detail, the photosensitive layer formed on the substrate is exposed to form a pattern of cation exchange groups, and metal ions and metal colloids are adsorbed to the cation exchange groups. Then, the metal pattern or the metal colloid thus adsorbed is used as a catalyst nucleus for plating to form a wiring pattern by electroless plating.

  Such a method does not require the formation or etching of a resist pattern, and the process is very simple. Therefore, the cost can be reduced, and the wiring pattern can be easily made finer and three-dimensional.

  However, there is a major problem in such a method.

  For example, an electroless plating solution of copper, which is important as a wiring material, generally shows very strong alkalinity. On the other hand, since the cation exchange group is an acidic group or a salt thereof, it becomes a hydrophilic salt in a strongly alkaline plating solution.

  Therefore, the photosensitive layer after the generation of the cation exchange group has poor resistance to the plating solution which is an aqueous solution, and may be dissolved in the plating solution during plating or peeled off from the substrate. These problems become more serious when the amount of cation exchange groups present in the photosensitive layer is increased in order to increase the adsorption amount of plating nuclei. For this reason, there is a demand for a method that can be applied well to a strongly alkaline plating solution.

  Another problem is that when a porous body is used as the base material, the conductivity of a conductive pattern such as a wiring pattern is not sufficient.

  For example, as a method of forming a conductive pattern in a porous body by electroless plating, various methods are known as disclosed in Patent Document 1, Patent Document 2, and Patent Document 3.

However, in the conductive pattern formed by such a method, the filling rate of the plating metal into the porous body is not sufficient, and it is often difficult to increase the conductivity of the conductive pattern. This is because in the electroless plating, the plating metal is simultaneously deposited from the inner surface of the hole in the region to be the conductive pattern. For this reason, when the deposition proceeds and the filling rate of the plating metal into the pores increases, the pores are narrowed and the plating solution cannot be sufficiently supplied from outside the porous body. Therefore, precipitation stops halfway, and it is difficult to obtain a sufficient filling rate. In particular, the periphery of the region to be the conductive pattern is first filled with plating to form a film, and the central portion of the region is likely to remain without being plated.
JP-A-55-161306, JP-A-7-207450 U.S. Pat. No. 5,498,467 etc.

  As described above, selective electroless plating is inexpensive and can produce a three-dimensional wiring pattern. However, if ion-exchange groups are increased in order to increase the amount of catalyst nuclei adsorbed, photosensitivity increases. There was a problem that the layer was dissolved in the plating solution or peeled off.

  Further, when a wiring pattern or the like is formed by electroless plating in a porous body, the filling rate of plating metal or the like into the pores cannot be increased, and it has been difficult to obtain a sufficient conductivity.

  Therefore, the present invention is a method for producing a composite member in which a conductive portion (conductive pattern) such as a wiring pattern is formed on a base material, and it is possible to introduce a sufficient ion-exchange group in producing the conductive portion. In addition, it is possible to provide a method in which the photosensitive layer is not dissolved in the plating solution and does not peel off, or by filling a plating metal or the like at a high filling rate to form a conductive portion such as a wiring pattern having a sufficient conductivity. It is an object of the present invention to provide a method for forming a porous body.

A method of manufacturing a composite member according to a first aspect is a method of manufacturing a composite member in which a conductive portion is selectively formed at a predetermined portion of a base material, wherein the formation of the conductive portion includes the following pattern forming step, suction step, And a plating step.
Photosensitive layer forming step: a step of forming or swelling a photosensitive layer by irradiating the surface of the base material with energy rays to generate or lose an anion exchangeable group,
Energy beam irradiation step: a step of irradiating the photosensitive layer with energy rays to form a pattern of an anion exchange group in which an anion exchange group is disposed in an irradiated portion or a non-irradiated portion;
Adsorbing step: adsorbing a metal-containing ion or a metal-containing compound or a metal colloid on the pattern of the anion-exchangeable group;
Plating step: a step of forming a conductive pattern by applying electroless plating to the pattern of the anion-exchange group adsorbing the metal-containing ions, metal-containing compounds, or metal colloids.

A method for manufacturing a composite member according to a second aspect is a method for manufacturing a composite member in which a conductive portion is selectively formed on a predetermined portion of a base material, wherein the conductive portion is formed by the following photosensitive layer forming step, It is characterized in that it is performed through a line irradiation step, an adsorption step, and a plating step.
Photosensitive layer forming step: forming a photosensitive layer having at least an acyl oxime derivative group-containing compound or an azide derivative group-containing compound in which an anion exchange group is generated by irradiating the substrate surface with energy rays;
Energy beam irradiation step: irradiating the photosensitive layer with energy rays to form a pattern of an anion exchange group in which an anion exchange group is disposed in an irradiated portion or an unirradiated portion;
Adsorbing step: adsorbing a metal-containing ion or a metal-containing compound or a metal colloid on the pattern of the anion-exchangeable group;
Plating step: a step of forming a conductive pattern by applying electroless plating to the pattern of the anion-exchange group adsorbing the metal-containing ions, metal-containing compounds, or metal colloids.

Further, the method for manufacturing a composite member according to the third aspect of the present invention is a method for manufacturing a composite member in which a conductive portion is selectively formed on a predetermined portion of an insulating porous body. , A surface modification step, a plating solution infiltration step, and an electrolytic plating step.
Electrode setting step: a step of setting an electrode on the porous body;
Surface Partial Reforming Step: A part of the porous body is modified to change its surface energy, and a pattern is obtained in which the affinity of the modified part for water is different from the affinity of the non-reformed part for water. Forming,
Plating solution infiltration step: a step of selectively infiltrating a plating solution into an insulated region of the modified or non-modified portion in the porous body selected in contact with the electrode surface;
Electroplating step: a step of energizing the electrodes to deposit electroplating in the region to form a conductive portion.

  In the third aspect of the present invention, it is preferable that the photosensitive layer is a photosensitive layer in which an ion-exchange group is generated or eliminated by irradiation with energy rays. Further, the ion exchange group is preferably an anion exchange group.

  In the first, second, and third aspects of the present invention, the anion exchange group is preferably an amino group.

  Further, the porous member for forming a composite member according to the fourth aspect has a porous body having pores and an anion exchange group formed by irradiation of energy rays formed on the surface of the pores. Alternatively, it is characterized by comprising a photosensitive layer to be lost.

  In the fourth aspect, it is preferable that at least one surface of the porous body is covered with a protective film. Further, it is preferable that an electrode is provided in close contact with the porous body.

  Further, the photosensitive compound for forming a composite member according to the fifth aspect is characterized in that it has a photosensitive group that generates or disappears an anion-exchangeable group upon irradiation with light, and a crosslinkable group. is there.

  Further, the composition for forming a composite member according to the sixth aspect has a compound having a photosensitive group which generates or disappears an anion exchange group upon irradiation with light, and a compound having a crosslinkable group. It is a feature.

  To produce a composite member using the photosensitive compound for forming a composite member of the fifth embodiment or the composition for forming a composite member of the sixth embodiment, an anion exchange group is generated by irradiating light. Alternatively, a composition of a compound having a disappearing photosensitive group and a crosslinkable group at the same time, or a compound having a photosensitive group that generates or disappears an anion exchange group upon irradiation with light, and a compound having a crosslinkable group If necessary, at least one of additives selected from the group consisting of a solvent, a photobase generator, a photoacid generator, an acid multiplying agent, a catalyst, a crosslinking aid, a radical generator, and a sensitizer. It is preferable to mix seeds and use them as a photosensitive material for forming a composite member.

  According to the first or second aspect of the method of manufacturing a composite member, a fine process which can be used as a multilayer wiring board or the like can be performed by a simple process of exposing and plating a substrate on which a photosensitive layer is formed. It is possible to manufacture conductive patterns such as simple wiring. At this time, the photosensitive layer does not dissolve in the plating solution and does not peel off, and a sufficient amount of plating catalyst can be adsorbed. For this reason, the conductivity of the conductive portion formed by plating can be improved. Further, abnormal deposition of plating and corrosion of the conductive portion can be prevented. For this reason, a highly reliable wiring board or the like having good conductivity can be provided.

  Further, according to the third aspect of the method of manufacturing a composite member of the present invention, the conductivity can be improved by sufficiently increasing the metal filling rate of the conductive portion.

  The porous member for forming a composite member, the photosensitive compound for forming a composite member, and the photosensitive composition for forming a composite member of the present invention can be used in the method for producing a composite member.

  Furthermore, since the method for manufacturing a composite member of the present invention can perform each process continuously on a “reel-to-reel” basis, there is an advantage that the throughput at the time of manufacturing can be increased. Is very large.

[I] Method of manufacturing composite member (first embodiment)
First, each manufacturing process in the first embodiment of the method for manufacturing a composite member will be described.

  In the following description, each step will be described in order to facilitate understanding of the method of manufacturing a composite member according to the first aspect.

(1) Manufacturing Process The manufacturing method of a composite member according to the first aspect basically includes a photosensitive layer forming process, an energy beam irradiating process, an adsorption process, and a plating process.

(A) Photosensitive Layer Forming Step First, a swellable photosensitive layer is formed on the surface of a base material by the generation or disappearance of an anion exchange group by irradiation with energy rays. When a wiring board or the like is manufactured, an insulating base material is used.

  The shape of the base material is not particularly limited, and the present invention can be applied to base materials having various shapes such as a plate, a line, a tube, and a sphere. In particular, if a porous substrate is used, it is possible to form a conductive pattern inside the porous material.

  The method for forming the photosensitive layer on the substrate is not particularly limited, but is generally formed by applying a solution of a photosensitizer to the substrate. The layer thickness of the photosensitive layer to be applied is not particularly limited, but is generally set to about 0.5 to 1000 nm, preferably 1 to 100 nm, more preferably 20 to 50 nm. good.

(B) Energy Beam Irradiation Step The substrate on which the photosensitive layer is formed is irradiated with energy rays to form a pattern of an anion exchangeable group. For example, when using a photosensitive layer that generates an anion exchange group by irradiation with energy rays, the photosensitive layer formed on the base material is irradiated with a pattern, and the irradiated portion of the photosensitive layer is irradiated with the anion exchange group. Generate. For pattern irradiation, an exposure mask may be used, a laser beam may be scanned, or the like, or light from a light source may be modulated by a micromirror array in which a large number of minute mirrors are arranged in a matrix. good.

  When a porous base material is used, a conductive pattern can be formed inside the porous material by exposing it to light through the porous material.

The conditions for the above-mentioned energy beam irradiation are generally carried out by, for example, using a high-pressure mercury lamp or the like as a light source and exposing through a mask according to a pattern with an exposure amount of about 0.1 to 10000 mJ / cm ² . For the exposure, a mask may be used, scanning with a laser beam may be performed, or light from a light source may be modulated by a micromirror array in which a large number of minute mirrors are arranged in a matrix.

(C) Adsorption Step Next, a plating catalyst (plating nucleus) or a precursor thereof, a metal-containing ion, a metal-containing compound, or a metal colloid is adsorbed on the formed anion-exchange group pattern.

Metal-containing ions Anions are used as metal-containing ions. The anion forms a salt with the anion exchange group and is adsorbed as a counter ion of the anion exchange group.

Metal-containing compound As the metal-containing compound, a compound having a binding group capable of binding to an anion exchange group is used. This bonding group is bonded to and absorbed by the anion exchange group.

Metal colloid As the metal colloid, for example, a metal colloid that is negatively charged is used. The charged metal colloid is electrostatically adsorbed on the ionized anion exchange group.

Metallization These metal-containing ions, metal-containing compounds or metal colloids serve as catalysts in the next step of electroless plating. When a metal-containing ion or a metal-containing compound is adsorbed, the metal ion is metallized by a reduction treatment as necessary. The metallization improves the catalytic ability of electroless plating.

  The adsorption is generally carried out, for example, by immersing a substrate on which a pattern of anion-exchange groups is formed in a solution of the metal-containing ion, metal-containing compound or metal colloid. The immersion time is generally set between about 10 seconds and about 5 hours. The swellable photosensitive layer is swollen by the plating nucleus solution, and the solution penetrates into the photosensitive layer. Therefore, plating nuclei can be adsorbed not only on the surface layer of the photosensitive layer but also on the anion-exchange group present inside the layer. Therefore, the amount of plating nuclei adsorbed can be increased, so that the plating time can be shortened and the conductivity of the formed conductive pattern can be increased.

(D) Plating Step Electroless plating of copper or the like is performed using the adsorbed metal-containing ion, metal-containing compound, or metal colloid as a catalyst core to form a conductive pattern.

  If a photosensitive material containing a compound that loses an ion-exchange group upon exposure is used, a negative pattern in which the ion-exchange group remains in the unirradiated portion in the above-mentioned "energy beam irradiation step" is formed.

  Further, the anion exchange group generated in the irradiated portion by the pattern irradiation is selectively reacted with a fluorine compound or the like to lose the anion exchange ability, and thereafter, the entire surface is exposed or heated, etc. An anion-exchange group may be formed in a non-irradiated portion, and a metal-containing ion, a metal-containing compound, or a metal colloid may be adsorbed on the anion-exchange group to perform plating.

  According to this method, two exposure operations and two heating operations are required. For this reason, the method of plating by directly adsorbing a metal-containing ion, a metal-containing compound, or a metal colloid on the pattern of the anion-exchangeable group formed by the pattern irradiation is simpler and has been manufactured. It is also excellent in dimensional stability of composite members.

  For example, an electroless plating solution of copper, which is particularly important as a wiring material, is often strongly alkaline. Therefore, when the cation exchange group is used, the photosensitive layer is easily dissolved or peeled off in a strongly alkaline plating solution. On the other hand, an anion-exchange group is excellent in resistance to a plating solution or the like, so that plating without defects can be performed.

  The method for manufacturing a composite member according to the first aspect is also very effective when quartz, glass, carbon, or the like is used as a base material.

  Usually, quartz or glass has a silanol group on the surface of the substrate. In addition, a carboxyl group usually exists on the surface of the carbon substrate. Silanol groups and carboxyl groups function as cation exchange groups and adsorb metal cations, metal colloids, etc., which are plating catalysts or their precursors.

  For this reason, in the conventional method of performing plating by adsorbing a plating catalyst (metal cation or the like) on a cation exchange group, the plating catalyst also adsorbs on a silanol group or a carboxyl group on the substrate surface. Therefore, plating was likely to be abnormally deposited on the surface of the base material where plating was not desired.

  On the other hand, the plating catalyst adsorbed on the anion exchange group is hardly adsorbed on the silanol group or the carboxyl group. Therefore, abnormal deposition of plating can be prevented. Not only quartz, glass, and carbon but also a cation-exchange group formed by oxidizing the substrate on the surface of the substrate in many cases.

  In particular, when oxygen plasma treatment is performed to improve wettability, a large amount of cation exchange groups are generated on the substrate surface. For example, in the case of a carbon-based polymer substrate, a carboxyl group is generated. The use of an anion-exchange group as a group for adsorbing a plating catalyst is very effective in preventing abnormal deposition of plating.

  Further, an amino group or the like, which is an anion exchange group, does not easily corrode the formed conductive portion made of a metal such as copper or nickel. The base for adsorbing the plating catalyst remains between the substrate and the deposited plating. Therefore, when the acidic cation exchange group remains, the conductive portion is easily corroded. An anion-exchange group does not have such a possibility. The use of an anion-exchange group is very effective when forming a conductive portion made of a metal.

  Further, the amino group or the like can cure a curable resin such as an epoxy resin. After the deposition of the plating or after the adsorption of the plating catalyst, if an amino group is generated in a portion other than the portion where the plating is deposited, the curable resin impregnated in the porous body has good adhesion to the substrate surface. Can be cured. Yabe et al. Also discloses a method of forming an amino group pattern on the surface of a base material, adsorbing a plating catalyst to the pattern, and performing electroless plating (Nihon Keizai Shimbun, published February 19, 1993, morning edition). . In this method, a polytetrafluoroethylene substrate is used as a substrate, and an excimer laser is irradiated in a hydrazine gas atmosphere. Amino groups are generated by the reaction of irradiated polytetrafluoroethylene with hydrazine. In this method, it is necessary to irradiate a high energy excimer laser in order to react a non-photosensitive substrate. In addition, since irradiation is performed in a hydrazine gas atmosphere, the substrate needs to be housed in a chamber filled with hydrazine gas, so that the irradiation apparatus becomes expensive and throughput cannot be increased. A method in which a substrate is irradiated with an excimer laser in a state of being in contact with an aqueous solution to generate a hydrophilic group on the substrate surface has also been proposed, but there is a similar problem because a liquid material is handled in an exposure apparatus. . In addition, since short-wavelength light such as excimer laser is absorbed by most resins, for example, if a porous body is used as the base material and the inside of the porous body is to be plated, the light applied to the base material is absorbed. Therefore, it is difficult to efficiently irradiate the inside of the porous body.

  On the other hand, in the present invention, since the photosensitive layer that absorbs energy rays is formed only thinly on the surface of the substrate, even when the substrate is a porous body, the inside can be satisfactorily irradiated.

  The conditions for the electroless plating are not particularly limited, but generally, the temperature of the plating solution is set between 20 and 60 ° C., and the plating time is set between 30 minutes and 10 hours.

(2) Detailed Description of Each Step Next, the details of each step of the first aspect of the method for manufacturing a composite member will be specifically described below.

  In the following description, metal-containing ions, metal-containing compounds, and metal colloids may be collectively referred to as plating nuclei.

(A) Base Material (a) Material Constituting the Base Material The base material on which the conductive portion is formed is not particularly limited, and those formed of various inorganic materials or organic materials are used. For example, polymers, ceramics, carbon, metals and the like.

  In order to form a composite member such as a wiring board in which wirings, vias, and the like are formed as conductive portions, the base material is preferably an insulator. The insulating substrate on which the conductive portion is formed may be made of any insulating material, and specific examples thereof include polymers and ceramics.

Polymer Examples of the polymer include, for example, epoxy resins, bismaleimide-triazine resins, PEEK resins, resins conventionally used as insulators of printed wiring boards such as butadiene resins, and other polyolefins such as polyethylene and polypropylene, polybutadiene, and the like. Polyisoprenes, polydienes such as polyvinylethylene, polymethyl acrylate, acrylic resins such as polymethyl methacrylate, polystyrene derivatives, polyacrylonitrile, polyacrylonitrile derivatives such as polymethacrylonitrile, polyacetals such as polyoxymethylene, polyethylene terephthalate, Polyesters such as polybutylene terephthalate and aromatic polyesters, polyarylates, aromatic polyamides such as aramid resin, nylon, etc. Aromatic polyethers such as polyamides, polyimides, epoxy resins, poly p-phenylene ether, polyether sulfones, polysulfones, polysulfides, fluorine-based polymers such as polytetrafluoroethylene (PTFE), and polybenzo Oxazoles, polybenzothiazoles, polyphenylenes such as polyparaphenylene, polyparaphenylenevinylene derivatives, polysiloxane derivatives, novolak resins, melamine resins, urethane resins, polycarbodiimide resins, and the like.

Ceramics Examples of the ceramics include metal oxides such as silica, alumina, titania, and potassium titanate, silicon carbide, silicon nitride, and aluminum nitride.

  Among these insulating substrates, polymers are preferable because of their low dielectric constant, and liquid crystal polymers such as polyimides and aromatic polyamides, and fluorine-based polymers such as polytetrafluoroethylene are particularly preferable because of their excellent heat resistance. It is preferable to use a class or the like.

(B) Shape of the base material In particular, when the conductive portion is formed three-dimensionally in the present invention, that is, for example, when the conductive portion is formed not only in the plane direction but also in the thickness direction on the sheet-shaped insulator, the insulating portion is formed. By using a porous body having continuous pores made of the insulator material as the body, a highly accurate conductive portion can be easily formed.

  Using the porous body, plating is deposited in the pores of the porous body. Then, a three-dimensional conductive portion formed of a region in which the porous body is impregnated with the precipitate can be formed. When the continuous pores are three-dimensionally continuous, the conductive portion is an isotropically conductive composite in which the insulating material and the precipitate constituting the porous body interpenetrate. The three-dimensionally-shaped conductive portion made of such a composite can be used as a three-dimensional wiring, a multilayer wiring, a via for interlayer connection of the multilayer wiring, or the like.

Porous body Specific examples of the porous body include a porous sheet in which three-dimensional continuous pores are formed in a sheet of a polymer material or the like, and a cloth or nonwoven fabric in which polymer fibers or ceramic fibers are entangled in a three-dimensional network. Is used.

  Specifically, for example, a sheet produced by stretching a sheet of a crystalline polymer such as polypropylene or polytetrafluoroethylene, or a polyimide formed by utilizing phase separation phenomena such as spinodal decomposition of a polymer or microphase separation, etc. May be used.

  As the cloth and the nonwoven fabric, those manufactured from ceramic fibers or polymer fibers are used.

  As the ceramic fiber, for example, silica glass fiber, alumina fiber, silicon carbide fiber, potassium titanate fiber or the like is used.

  Examples of the polymer fiber include a liquid crystalline polymer such as an aromatic polyamide fiber and an aromatic polyester fiber, a high Tg polymer fiber, a fluorine-based polymer fiber such as a PTFE fiber, a polyparaphenylene sulfide fiber, an aromatic polyimide fiber, and a polybenzo fiber. Oxazole derivative fibers and the like are used.

The above ceramic fiber and polymer fiber may be mixed, or a composite fiber of ceramic and polymer may be used.
A nonwoven fabric is more preferable than a cloth because the fibers are three-dimensionally entangled and the pore diameter is uniform. Further, as the nonwoven fabric, for example, a nonwoven fabric of a polymer fiber manufactured by a melt blow method or a fine fiber having a diameter of about 0.1 to 0.3 μm obtained by finely pulverizing a fiber of a liquid crystalline polymer such as an aromatic polyamide is used. Woven nonwoven fabrics are preferred because the fiber diameter is fine and the pore diameter is uniform. In order to improve the dimensional stability of these nonwoven fabrics, it is preferable that the fibers are welded to each other or coated with a polymer to prevent the fibers from shifting.

  Among these porous bodies, a porous body formed by stretching polytetrafluoroethylene, a porous body such as polyimide formed by using a phase separation phenomenon, and a non-woven fabric of fine fibers of a liquid crystalline polymer are three-dimensionally. It is preferable because it has a uniform porous structure with little anisotropy and a uniform pore diameter.

  The average pore diameter of the continuous pores is preferably set in the range of 0.05 to 5 μm, and more preferably in the range of 0.1 to 0.5 μm. If the pore diameter is too small, the plating solution or the like does not sufficiently penetrate into the porous interior, and the porous interior cannot be plated uniformly. If the pore diameter is too large, it is difficult to form a fine plated metal pattern, and when exposure is performed with ultraviolet light or visible light, the exposure light is scattered by the porous structure and pattern exposure with good contrast can be performed. difficult. In order to prevent the exposure light from being excessively scattered and to allow the plated metal to grow uniformly in the pores, the pore diameter is preferably uniform. The porosity is preferably set in the range of 20 to 95%, and more preferably in the range of 45 to 90%. If the porosity is too small, the plating solution or the like may not sufficiently penetrate, or the conductivity of the formed plated metal pattern may be low. If the porosity is too large, the strength of the porous body will not be sufficient and the dimensional stability will be poor.

(C) Hydrophilic treatment The surface of the base material is preferably subjected to a hydrophilic treatment in order to improve wettability with a plating solution or the like. In particular, when a porous body is used as a base material and plating is performed to the inside of the porous body, hydrophilic treatment is important in order to allow the plating solution to penetrate into the inside of the porous body.

  The method for performing the hydrophilic treatment is not particularly limited, and a widely known method can be used. For example, a method of applying a hydrophilic substance such as a hydrophilic polymer such as polyvinyl alcohol, a method of modifying the surface by optical, thermal, or chemical treatment, and the like are used.

  Specifically, the surface of the base material is oxidized by irradiating ultraviolet rays under an oxygen stream or an ozone stream, or by exposing to an ozone atmosphere or an ozone solution. Further, for example, there is a method of oxidizing the surface of a base material by plasma treatment with oxygen or the like in the air or in a vacuum. Moreover, you may process with an acid or an alkali. Further, the hydrophilicity may be increased by an oxidation method as disclosed in JP-A-2000-290413.

  When an oxidation treatment is performed on a polymer, glass, or the like, an acidic group capable of adsorbing a metal cation such as a carboxyl group or a silanol group is generated. However, as described above, according to the method of the present invention using an anion-exchange group, even if these acidic groups are present, there is no possibility that plating will abnormally precipitate.

  Among these hydrophilic treatments, plasma treatment in the air is preferred because the process is simple.

(B) Photosensitive layer (a) Anion-exchange group The anion-exchange group in the present invention is a group capable of adsorbing an anion, such as a cationic group or a basic group. Say that.

Cationic group Specifically, examples of the cationic group include aliphatic amines such as ammonium groups, quaternary ammonium salt derivative groups of aromatic amines, and pyridinium groups and imidazolium. And a quaternary ammonium salt derivative group of a nitrogen-containing heterocyclic ring such as a group.

Basic Group Examples of the basic group include an aliphatic or aromatic amino group, and a nitrogen-containing heterocyclic derivative group such as a pyridine residue or an imidazole residue.

(B) Swellability The photosensitive layer in the present embodiment is a layer having swellability. The swelling property refers to a property of having affinity with a solution used for adsorption of plating nuclei when a plating nucleus is adsorbed on a substrate in a later step, and taking the solution into a layer to cause volume expansion. As a result, in the plating nucleus adsorption step, the plating nucleus sufficiently penetrates into the inside of the photosensitive layer, and the plating nucleus is adsorbed on the photosensitive layer at a high density, so that a sufficient amount of the electroless plating layer can be formed in a short time. Can be.

(C) Formation of Photosensitive Layer Photosensitive Layer In the present invention, the photosensitive layer that generates or disappears an anion exchange group by irradiation with energy rays is a layer formed on the surface of the base material, This is a layer having a photosensitive group that generates or loses an anion exchangeable group upon irradiation.

  The photosensitive layer can be composed of only a photosensitive compound having a photosensitive group, but may be a mixture with another compound. By irradiating the photosensitive layer containing such a photosensitive group with an energy beam in a desired pattern, an ion-exchange group is generated or eliminated at the irradiated site. For example, when a composite member is used as a wiring board or the like, the base material is required to have electrical characteristics, heat resistance, mechanical strength, and the like. In the case of imparting photosensitivity to the base material itself, it is difficult to achieve compatibility with these required characteristics. Therefore, it is preferable to form a photosensitive layer on the non-photosensitive substrate surface. In particular, when a porous body is used as a base material and a conductive portion is formed up to the inside of the porous body, a photosensitive layer is preferably formed separately from the base material. When the porous body itself is photosensitive, it is difficult to sufficiently expose the inside of the porous body because it strongly absorbs the irradiated energy rays. It is preferable that a thin photosensitive layer is formed on the surface of a porous body that is made of a material that does not absorb or has low absorption of energy rays to be irradiated. The layer thickness of the photosensitive layer formed on the inner surface of the pores of the porous body is preferably set in the range of 1 to 100 nm, more preferably 20 to 50 nm. If the thickness is too small, the amount of anion-exchange groups is insufficient, and a sufficient amount of plating catalyst cannot be adsorbed. On the other hand, if the thickness is too large, the holes may be closed. In addition, the irradiated energy rays are all absorbed near the surface, and the photosensitive layer inside the porous body cannot be sufficiently exposed to light. Needless to say, the layer thickness of the photosensitive layer is sufficiently smaller than the hole diameter so as not to block the holes. The thickness of the photosensitive layer is 20% or less, preferably 10% or less of the pore diameter.

Formation of photosensitive layer The photosensitive layer may be formed by coating a photosensitive compound having a photosensitive group and a crosslinkable group or a photosensitive composition containing a compound having a photosensitive group on the substrate surface. it can. Alternatively, a photosensitive layer may be formed by bonding a molecule having both a group capable of binding to a functional group present on the substrate surface and a photosensitive group to the substrate surface.

JP-A-6-202343 discloses a method for selective plating using a silane coupling agent having a group generating a carboxyl group for adsorbing metal ions and a trialkoxysilyl group capable of binding to the surface of a glass substrate. Is disclosed.
However, in this method, metal ions are also adsorbed to the silanol groups generated from the trialkoxy groups, and there is a possibility that the plating is randomly deposited. However, since the anion exchange group and the silanol group have opposite polarities of charge, such disordered plating hardly occurs. There is also known a method of performing selective plating using a silane coupling agent having both an amino group which is an anion exchange group for adsorbing metal ions and a trialkoxysilyl group capable of binding to the surface of a glass substrate. Irradiation with ultraviolet light having a short wavelength of 200 nm or less cleaves a covalent bond between carbon atoms to eliminate an amino group in an irradiated portion to form a latent image. A palladium colloid is adsorbed on the latent image. However, even with this method, it is difficult to form a photosensitive layer having a sufficient film thickness with a silane coupling agent, and cross-linking occurs at a high density, so that the photosensitive layer does not swell in the plating nucleus solution. Therefore, the palladium colloid adheres only to the surface of the photosensitive layer, and the amount of plating nuclei adsorbed is not sufficient. Further, since the method is a method in which a covalent bond between carbon and carbon is directly cut with ultraviolet light having a short wavelength, sensitivity at the time of exposure is low. When the substrate is a porous body, it is difficult to expose the inside of the substrate. However, a photosensitive layer made of a polymer or a polymer compound having a photosensitive group can easily swell and can adsorb a sufficient amount of plating nuclei. A latent image can be formed with high sensitivity by using a photosensitive group, particularly an acyl oxime derivative group or an azide derivative group, as described in the present invention. Further, the wavelength can be selected in a wide range, which is excellent when a plating pattern is formed even inside the porous body.

Further, the photosensitive layer can be formed by modifying the surface of the base material by a chemical reaction.
For example, a photosensitive graft polymer chain having a photosensitive group may be grown from a growth point formed on the substrate surface by an interface graft polymerization method, and the substrate surface may be covered with the photosensitive graft polymer chain. Furthermore, a photosensitive group may be formed by introducing a functional group into the surface of a base material such as a porous sheet of a polymer having an aromatic ring such as a polyimide porous sheet and chemically modifying the introduced functional group. To introduce a functional group, a sulfonic acid group or the like may be introduced by a Friedel-Crafts reaction or the like, or a hydroxyl group or a carboxyl group may be introduced by an oxidation method disclosed in JP-A-2000-290413. good. Forming a photosensitive layer by coating a photosensitive material made of a photosensitive compound or a photosensitive composition on the surface of the base material because the material selection range of the base material is wide and the photosensitive layer can be easily formed. Is most preferred.

(D) Photosensitive group A photosensitive group is a substance that generates an anion-exchangeable group by a chemical reaction alone by absorbing irradiated energy rays, or a kind of anion that generates a chemical reaction by irradiation. A precursor of an exchangeable group, and the precursor further reacts with a substance present in the surroundings to form an anion exchangeable group, and acts with a base or the like generated from a base generator by irradiation with energy rays. To produce an anion-exchangeable group as a result, and further, to eliminate the anion-exchangeable group by irradiation with energy rays. Among them, a photosensitive group which generates or disappears an anion exchange group by a chemical reaction alone is most preferable. Because it reacts alone, it is less susceptible to the surrounding atmosphere such as humidity, and also tends to occur when forming a photosensitive layer by applying a composition containing a compound having a photosensitive group. This is because it is possible to prevent a variation in reactivity due to the bias. In addition, when the precursor generated by irradiation chemically reacts with surrounding substances to generate anion-exchange groups, the surrounding substances are naturally contained in the atmosphere as moisture, such as water, or may be contained in the photosensitive layer. It is excellent to use a substance that has been previously mixed and contained in the mixture because the process is simple. Further, a photosensitive group to be formed is better than a photosensitive group to eliminate an anion exchange group. Since the plating reaction is an amplification reaction, a certain amount of plating can be grown from a small amount of plating nucleus. Therefore, when the anion exchange group is lost, if it is not completely removed, plating may be abnormally deposited from a portion that is not desired to be plated (in this case, an irradiated portion), which may cause insulation failure. Become. On the other hand, when an anion-exchange group is formed, even if the reaction rate is not so high, there is no fear that plating is abnormally deposited at least on a portion not to be plated (in this case, that is, a non-irradiated portion).

  Examples of the photosensitive group that alone generates an anion exchange group by absorbing energy rays include carbamoyl oxime derivative groups such as carbamoyloxy imino groups that generate basic groups such as amines, carbamic acid derivative groups, and formamide derivatives. And the like. A carbamic acid derivative of a piperidine derivative is thermally catalyzed by a base to produce a piperidine derivative which is an amine. For this reason, it is possible to generate a large amount of a basic group with a small exposure amount by combining with a photosensitive group or a photobase generator that generates another basic group.

  A chemical reaction by energy beam irradiation produces a precursor of some anion-exchangeable group, and the precursor further generates an anion-exchangeable group by further producing a chemical reaction. Examples of the photosensitive group that generates an anion exchange group by a multi-step reaction include an acyl oxime derivative group and an azide derivative group.

  Examples of the photosensitive group that generates an anion exchange group by acting with a base or the like generated from a base generator by irradiation with energy rays include a carbamic acid derivative group of a piperidine derivative.

Photo-base generator Add a photo-base generator that generates a base by irradiation with energy rays when using a photosensitive group that generates an anion exchange group by acting with a base generated from the base generator by irradiation with energy rays. I do. Upon irradiation with energy rays, a base is generated from the photobase generator, and the protective group is decomposed by the generated base to form an anion exchangeable group.

  As the photobase generator, for example, carbamates such as cobalt amine complexes, ketone oxime esters, o-nitrobenzyl carbamates, and formamides are used, and specifically, for example, NBC-101 (manufactured by Midori Kagaku) Carbamates such as CAS No. [119137-03-0]) and triarylsulfonium salts such as TPS-OH manufactured by Midori Kagaku (CAS No. 58621-56-0) are used.

  Instead of using a photobase generator, a photoacid generator and a basic compound may be combined. That is, at the energy beam irradiation site, an acid is generated from the photoacid generator to neutralize the basic compound.

  On the other hand, at the unirradiated site, a basic compound acts to generate an anion exchangeable group. This makes it possible to selectively dispose an anion-exchange group only in a non-irradiated part.

Photoacid Generator As the photoacid generator, onium salts, diazonium salts, phosphonium salts, iodonium salts and the like having CF ₃ SO ₃ ⁻ , p-CH ₃ PhSO ₃ ⁻ , p-NO ₂ PhSO ₃ ⁻ etc. as counter anions , Triazines, organic halogen compounds, 2-nitrobenzylsulfonic acid esters, iminosulfonates, N-sulfonyloxyimides, aromatic sulfones, quinonediazidesulfonic acid esters, and the like.

  Specifically, as the photoacid generator, for example, triphenylsulfonium triflate, diphenyliodonium triflate, 2,3,4,4-tetrahydroxybenzophenone-4-naphthoquinonediazidosulfonate, 4-N- Phenylamino-2-methoxyphenyldiazonium sulfate, diphenylsulfonylmethane, diphenylsulfonyldiazomethane, diphenyldisulfone, α-methylbenzoin tosylate, pyrogallol trimesylate, benzoin tosylate, naphthalimidyl trifluoromethanesulfonate, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl -S-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylaminoethyl) amino] -4,6-bis (trichloromethyl) -s-triazine dimethyl sulfate, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, -(4-dimethoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, and 2,4,6-tris ( Trichloromethyl) -s-triazine and the like.

  These photoacid generators may be used in combination with an acid multiplying agent that newly generates an acid autocatalytically with an acid. In addition, the photoacid-generating acid multiplying agent may be used alone. Examples of the acid proliferating agent include t-butyl 2-methyl-2- (p-toluenesulfonyloxymethyl) acetoacetate and derivatives thereof, cis-1-phenyl-2- (p-toluenesulfonyloxy) -1 -Cyclohexanol and its derivatives, 3-nitro-4- (t-butoxycarbonyloxy) benzyl tosylate and its derivatives, 3-phenyl-3,3 such as 3-phenyl-3,3-ethylenedioxypropyl tosylate -Ethylenedioxypropylsulfonate derivatives, 2-hydroxybicycloalkane-1-sulfonate derivatives such as cis-3- (p-toluenesulfonyloxy) -2-pinanol, 1,4-bis (p-toluenesulfonyloxy) cyclohexane and the like 1,4-cyclohexanediol sulfonate derivative of 2, 4,6-tris [2-(p-toluenesulfonyloxy) ethyl] etc. trioxane derivatives such as 1,3,5-trioxane and the like. Examples of the photoacid-generating acid proliferating agent include 3-phenyl-3,3-ethylenedioxypropylsulfonate derivatives such as 3-phenyl-3,3-o-nitrophenylethylenedioxypropyl tosylate.

Basic compounds A basic compound used in combination with a photoacid generator is neutralized by an acid released from the photoacid generator and acts as a catalyst for the reaction for forming an anion exchange group. Any compound can be used, and either an organic compound or an inorganic compound may be used. Preferably, ammonia, primary amines, secondary amines, tertiary amines and the like are used.

  A photosensitive group that loses an anion-exchange group by irradiation with an energy beam means that the group has an anion-exchange group before irradiation, and this anion-exchange group is released by the energy beam irradiation or becomes hydrophobic. It is a group that changes to a group.

Specifically, for example, Cl ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , BF ₄ ⁻ , ClO ₄ ⁻ , CF ₃ SO ₃ ⁻ , HSO ₄ ⁻ , FSO ₃ ⁻ , F ₂ PO ₂ ⁻ , _{p-CH 3 -C 6 H 4} -SO 3 -, p-NO 2 -C 6 H 4 -SO 3 - diazonium salt and a counter anion anion such as, phosphonium salts, iodonium salts, sulfonium salts and arsonium salts And other groups having a structure such as an onium salt. These can adsorb metal-containing ions and metal-containing compounds by an anion exchange reaction. Since it is charged to a positive charge, metal colloids can be adsorbed. Further, it is decomposed by energy beam irradiation and becomes nonionic, so that it becomes difficult to adsorb plating nuclei.

(E) Polymer or polymer compound to which the photosensitive group is bonded The photosensitive layer is exposed to an alkali or acidic aqueous solution at the time of adsorbing plating nuclei or at the time of plating, so that it is hardly dissolved in them. It is preferable that a photosensitive group that generates or disappears an anion exchange group is bonded to a polymer, a polymer compound, or the like. When the photosensitive group is bonded to a polymer or a polymer compound, it can be swollen by these solutions without being dissolved in a plating nucleus solution or a plating solution. Then, the solution permeates into the inside of the photosensitive layer, so that the adsorption amount of plating nuclei and the deposition amount of plating can be increased. It is particularly important to swell in the plating solution because the amount of plating nuclei adsorbed greatly affects the conductivity of the conductive part. In order to swell without dissolving in a solution, it is preferable that the polymer or the polymer compound is not crosslinked at a high density and has an appropriate affinity for the solution.

  Such polymers include phenolic novolak resins, xylenol novolak resins, pyrogallol resins, vinylphenol resins, phenolic resins such as cresol novolak resins, polyamide resins, polyimide resins, polyester resins, polyolefin resins, polyacrylic acid ester derivatives and polyacrylates. Examples of the resin include an acrylic resin-based resin such as a methacrylate derivative, a polysiloxane derivative, and a resin rich in a long linear portion having few cross-linking points in a resin molecule. Among them, it is preferable to use a phenol resin or an acrylic resin from the viewpoint of applicability and the like.

As the polymer compound, a polymer compound having an aromatic ring and a carbon chain, preferably a branched one is preferable.
The molecular weight of the polymer or polymer compound is not particularly limited, but the molecular weight (weight average molecular weight in the case of a polymer) is preferably 1,000 to 5,000,000, and more preferably 2000 to 50,000.

  When the molecular weight of the polymer or the high molecular compound is too small, the film-forming property is poor, and the solvent resistance to a plating solution or the like may be reduced. That is, it is easily dissolved in a plating solution or the like. Also, it is difficult to impart swelling properties to the polymer or polymer compound without impairing the resistance to solvents. On the other hand, when the molecular weight is excessively large, the solubility in the solvent for coating is reduced, and the coatability is also deteriorated.

  If the amount of the photosensitive group in the polymer or polymer compound is too small, the plating nucleus cannot be sufficiently adsorbed. If the amount is too large, the plating nucleus is easily dissolved in a plating solution or the like, and the produced composite member easily absorbs moisture. This causes problems such as insulation failure.

  The introduction ratio of the photosensitive group that generates or disappears the anion exchange group into the polymer or polymer compound is preferably 5 to 300%, more preferably 30 to 70%. Is good. Here, the introduction ratio is represented by the following formula.

Introduction ratio of photosensitive group to polymer (%) = (number of groups generating or eliminating anion-exchange groups) / (number of monomer units of polymer) × 100
Introduction rate (%) of photosensitive group into polymer compound = (number of groups generating or disappearing anion exchange group) / (molecular weight of polymer compound / 100) × 100
In order to increase the solvent resistance and make it difficult to dissolve in a plating solution or the like, it is preferable to crosslink a polymer or a polymer compound. In order to crosslink a polymer or a polymer compound, a radical generator such as an organic peroxide may be added to form a carbon-carbon bond between polymer molecules by a hydrogen abstraction reaction in the polymer. Further, a crosslinkable group may be introduced into the main chain or side chain of the polymer or into the polymer compound.

Crosslinkable Group As the crosslinkable group, the crosslinkable groups may be cross-linked by self-polymerization, or may be cross-linked by forming a bond with another substance in the photosensitive layer.
Specific examples of the crosslinkable group capable of self-polymerization include, for example, an epoxy group such as a glycidyl group, a vinyl ether group, a chloromethylphenyl group, a methylol group, a benzocyclobutene group, a vinyl group, an acryloyl group, a methacryloyl group, a maleimidyl group, Examples thereof include an alkoxysilyl group, an acetoxysilyl group, an enoxysilyl group, an oximesilyl group, and derivatives thereof.

  These crosslinkable groups are crosslinked as required by light irradiation, heating, or by the action of a catalyst.

  As a catalyst, an acid group or a base catalyst is used for an epoxy group, a methylol group, a vinyl ether group, an alkoxysilyl group, an acetoxysilyl group, an enoxysilyl group, and an oximesilyl group, and a vinyl group, an acryloyl group, a methacryloyl group, and maleimidyl are used. A radical generator is used for a radical polymerizable group such as a group having a multiple bond such as a group. The crosslinkable group which is crosslinked by a radical reaction is preferable because the bond formed by the crosslinking is excellent in resistance to a strong alkaline solution such as a plating solution or a strongly acidic solution.

  In addition, since the radical reaction proceeds quickly even at room temperature, heat treatment is usually unnecessary. For this reason, it is possible to prevent a decrease in dimensional stability and a thermal deterioration due to the heat treatment of the base material.

  Examples of the crosslinkable group in the case of forming a bond with another substance in the photosensitive layer to form a crosslink include a hydroxyl group, an isocyanate group, a carboxylic anhydride group, a maleimidyl group, an aldehyde group, and an alkoxysilyl group.

Crosslinking Aid At this time, a crosslinking aid having a plurality of groups capable of binding to the crosslinkable group in one molecule is used in order to bond with these crosslinkable groups to form a crosslink bond.

  As the crosslinking aid, for example, alkoxysilanes, aluminum alkoxides, carboxylic anhydrides, bismaleimide derivatives, isocyanate compounds, polyvalent methylol compounds, epoxy compounds, etc. are used for the hydroxyl groups. Polyhydric alcohols and the like are used for the isocyanate group, carboxylic anhydride group and alkoxysilyl group.

  What crosslinks by reacting with an anion exchange group may be used. For example, an epoxy group, a chloromethylphenyl group, a methylol group, an alkoxysilyl group, a maleimidyl group, an isocyanate group, a carboxylic anhydride group, an aldehyde group and the like react with an amino group and crosslink. In particular, the epoxy group is excellent because the property of adsorbing plating nuclei can be maintained well even after the amino group has reacted.

  Alternatively, a cross-linking aid having a plurality of these groups in one molecule may be simply added to cross-link the polymers into which the anion exchange groups have been introduced. In these cases, a catalyst such as an acid catalyst may be appropriately added.

  As the crosslinkable group, the following groups that can be dimerized by irradiation with energy rays can also be used. Such a group is excellent in that it absorbs a part of the energy ray but can selectively crosslink only the irradiated part. For example, cinnamoyl group, cinnamylidene group, chalcone residue, isocoumarin residue, 2,5-dimethoxystilbene residue, styrylpyridinium residue, thymine residue, α-phenylmaleimidyl group, anthracene residue, and 2-pyrone Residue.

  The rate of introduction of the crosslinkable group into the polymer or polymer compound is preferably in the range of 1 to 100%, and more preferably in the range of 10 to 50%. Here, the introduction ratio is represented by the following equation.

  Introduction rate of crosslinkable groups into polymer (%) = (number of crosslinkable groups) ÷ (number of monomer units of polymer) × 100 Introduction rate of crosslinkable groups into polymer compound (%) = (anion exchange (The number of groups that form or eliminate a functional group) ÷ (molecular weight of polymer compound ÷ 100) × 100 When the amount of the crosslinkable group introduced into the polymer or polymer compound is too small, it is difficult to sufficiently crosslink. Therefore, it becomes easy to dissolve in a plating solution or the like. On the other hand, if the crosslinkable group is introduced excessively, when crosslinked, it becomes difficult to swell in plating nucleus solution and the like, and the photosensitive layer cures and contracts, and the base material is deformed or the photosensitive layer May be peeled off.

  The crosslinking reaction is preferably performed after forming the photosensitive layer. If cross-linking occurs before the formation of the photosensitive layer, the solubility of the polymer or polymer compound in the solvent decreases, and it becomes difficult to apply the polymer or polymer compound to the insulating substrate. After the formation of the photosensitive layer, the crosslinking reaction is preferably advanced by stimulation such as heating, irradiation with energy rays, and moisture in the air.

  Energy beam irradiation is preferably performed by energy beam irradiation when generating or eliminating anion exchange groups. For example, a photoacid generator, a photobase generator, or a radical generator is used as a catalyst activated by energy beam irradiation. Irradiation energy rays are not particularly limited, such as ultraviolet rays, visible rays, infrared rays, and the like, X-rays, electron rays, α-rays, γ-rays, heavy particle rays, and the like. Usually, ultraviolet rays, visible rays, electron beams and the like are most often used.

  As described above, the crosslinking reaction is most preferably a radical reaction, and it is preferable to use a radical generator in combination with a radical polymerizable crosslinking compound or a crosslinking group.

Radical generator As the radical generator, for example, the following organic peroxides can be used.

  For example, ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, and acetylacetone peroxide; 1,1-bis (t-hexylperoxy) -3,3,5- Trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, di-t-butylperoxy-2-methyl Cyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 2,2-bis (t-butylperoxy) butane, n-butyl-4 , 4-bis (t-butylperoxy) valerate, Peroxyketals such as 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl Hydroperoxides such as hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide; 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butyl Dialkyl peroxides such as peroxy) hexyne, isobutyryl Oxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide, m-toluoyl and benzoyl peroxide, diacyl peroxide such as benzoyl peroxide , Di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethylperoxydicarbonate, di-2-ethylhexylperoxy Peroxycarbonates such as dicarbonate, di-3-methoxybutylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, α, α′-bi (Neodecanoyl peroxy) diisopropylbenzene, cumyl peroxy neodecanoate, 1,1,3,3-tetramethylbutylperoxy neododecanoate, 1-cyclohexyl-1-methylethyl peroxy neodecanoate , T-hexylperoxy neodecanoate, t-butyl peroxy neodecanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexyl Peroxy 2-ethylhexanoate, t-butylperoxy 2-ethylhexa Ethate, t-butylperoxyisobutyrate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymelamine acid, t-butylperoxy 3,5,5-trimethylhexanoate, t-butylperoxy Laurate, 2,5-dimethyl-2,5-bis (m-toluylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxy-m-toluylbenzoate, t-butylperoxybenzoate, bis (t-butylperoxy) ) Peroxy such as isophthalate Esters, t-butylperoxyallyl monocarbonate, t-butyltrimethylsilyl peroxide, 3,3 ′, 4,4′-tetrakis (t-butylperoxycarbonyl) benzophenone, and 2,3-dimethyl-2, 3-diphenylbutane and the like. In particular, polyfunctional radicals such as 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane and 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone The generator is preferable because it acts also as a crosslinking aid. Azonitriles such as azobisisobutyronitrile other than peroxides can also be used.

Sensitizer Various sensitizers may be added to the photosensitive layer. By adding a sensitizer, the sensitivity can be improved, and the photosensitive wavelength can be variously changed according to the light source used.

  In the case where the inside of the porous substrate is to be exposed to light, it is preferable to expose the inside of the porous substrate to energy rays that easily transmit through the substrate such as light having a wavelength other than the absorption wavelength of the substrate.

  For example, a polyimide porous substrate or the like often absorbs light having a wavelength of about 500 nm or less. Therefore, for example, it is difficult to expose the inside of the porous material by g-line or i-line. Even in such a case, by using a visible light sensitizer having an absorption band in a wavelength region of 500 nm or more, it is possible to satisfactorily expose the inside of the porous material.

  Specific examples of the sensitizer include, for example, aromatic hydrocarbons and derivatives thereof, benzophenone and derivatives thereof, o-benzoyl benzoate and its derivatives, acetophenone and its derivatives, benzoin and benzoin ether and its derivatives, xanthone and its derivatives Derivatives, thioxanthone and its derivatives disulfide compounds, quinone compounds, halogenated hydrocarbon-containing compounds and amines, 3-ethyl-5-[(3-ethyl-2 (3H) -benzothiazolylidene) ethylidene] -2- Merocyanine compounds such as thioxo-4-oxoazolidinone, 5-[(1,3-dihydro-1,3,3-trimethyl-2H-indole-2-ylidene) ethylidene] -3-ethyl-2-thioxo-4-oxazolidinone Dye, 3-butyl-1,1-dimethyl-2 [2 [2-diphenylamino-3-[(3-butyl-1,3-dihydro-1,1-dimethyl-2H-benz [e] indole-2-ylidene) ethylidene] -1-cyclopenten-1-yl ] Ethienyl] -1H-benz [e] indolium percolate, 2- [2- [2-chloro-3-[(3-ethyl-1,3-dihydro-1,1-dimethyl-2H-benz [e] Indole-2-ylidene) ethylidene] -1-cyclohexen-1-yl] ethenyl] -1,1-dimethyl-3-ethyl-1H-benz [e] indolium tetrafluoroborate, 2- [2- [2- Chloro-3-[(3-ethyl-1,3-dihydro-1,1-dimethyl-2H-benz [e] indole-2-ylidene) ethylidene] -1-cyclopenten-1-yl] [Enyl] -1,1-dimethyl-3-ethyl-1H-benz [e] cyanine dyes such as indolium iodide, squarium cyanine dyes, 2- [p- (dimethylamino) styryl] benzothiazole, 2- [ Styryl dyes such as p- (dimethylamino) styryl] naphtho [1,2-d] thiazole and 2-[(m-hydroxy-p-methoxy) styryl] benzothiazole; eosin B (CI No. 45400) ), Eosin J (CI No. 45380), cyanosine (CI No. 45410), bengal rose, erythrosine (CI No. 45430), 2,3,7-trihydroxy-9- Xanthene dyes such as phenylxanthene-6-one and rhodamine 6G, thionine (CI No. 52000), Azure A (C . I. No. 52005), thiazine dyes such as Azure C (CI No. 52002), pyronin B such as pyronin B (CI No. 45005), and pyronin GY (CI No. 45005); 3-acetyl Coumarin, 3-acetyl-7-diethylaminocoumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (dibutylamino) coumarin, 3- (2-benzimidazolyl) -7- (Diethylamino) coumarin, 10- (2-benzothiazolyl) -2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H, 11H- [1] benzopyrano [6, 7,8-ij] quinolizin-11-one, 3- (2-benzothiazolyl) -7- (dioctylamino) coumarin, 3-carbet Xy-7- (diethylamino) coumarin, 10- [3- [4- (dimethylamino) phenyl] -1-oxo-2-propenyl] -2,3,6,7-tetrahydro-1,1,7,7 Coumarin dyes such as -tetramethyl-1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolizin-11-one; 3,3′-carbonylbis (7-diethylaminocoumarin); Ketocoumarin dyes such as 3'-carbonyl-7-diethylaminocoumarin-7'-bis (butoxyethyl) aminocoumarin, 3,3'-carbonylbis (7-dibutylaminocoumarin), 4- (dicyanomethylene) -2- Methyl-6- (p-dimethylaminostyryl) -4H-pyran, 4- (dicyanomethylene) -2-methyl-6- (p-dibutylaminostyryl) There is a DCM-based dyes such as 4H- pyran.

  The compounding ratio of such a sensitizer is usually from 0.001 to 10% by weight, preferably from 0.01 to 5% by weight, based on the amount of the compound capable of producing or eliminating an anion exchange group upon exposure. .

  The sensitizer may be introduced not only into the photosensitive layer but also into, for example, a side chain of a polymer having a photosensitive group. When the photosensitive layer is sufficiently thin, a layer containing a sensitizer may be laminated on the photosensitive layer.

  In the present invention, in the formation of the above-mentioned photosensitive layer, a photosensitive material containing a later-described photosensitive compound for forming a composite member or a photosensitive composition for forming a composite member can be used.

(C) Irradiation energy rays Irradiation energy rays are not particularly limited, such as ultraviolet rays, visible rays, infrared rays, etc., X-rays, electron rays, α-rays, γ-rays, and heavy ion beams. Usually, ultraviolet rays, visible rays, electron beams and the like are most often used. Particularly, ultraviolet light and visible light having a wavelength of 280 nm or more, preferably 350 nm or more are good. For example, i-line (wavelength = 365 nm), g-line (wavelength = 435 nm), argon ion laser light (for example, wavelength = 488 nm), various semiconductor laser lights (for example, wavelength = 405 nm) using a high-pressure mercury lamp as a light source are used. These energy rays are relatively simple to irradiate, and can irradiate a large area in the atmosphere. When a mask is used, a general polymer film mask or a glass mask can be used as the mask. If the wavelength is too short, it is absorbed by the glass of the mask or the polymer film itself. Further, as described above, when plating the inside of a porous base material, it is necessary to transmit the energy beam to be transmitted through the porous base material. In the case of a porous substrate made of a heat-resistant aromatic polymer, for example, there is strong absorption such as a benzene ring having a peak around 250 to 260 nm. Therefore, it is difficult to obtain a sufficient transmittance below 280 nm.

(D) Adsorption The plating nucleus is adsorbed to the anion-exchange group by bringing the substrate on which the photosensitive layer is formed into contact with the plating nucleus solution.

  The method of contact is best to immerse the substrate in the solution, but it may also be applied by spraying the solution onto the substrate.

  Metal-containing ions, metal-containing compounds, and metal colloids are used as plating nuclei.

(A) Metal-containing ions As metal-containing ions, organic or inorganic acids or organic salts such as gold, platinum, palladium, copper, silver, nickel, ruthenium, and rhodium, which serve as catalysts for electroless plating by reduction or the like. And inorganic salts.

  The metal-containing ion is adsorbed to the anion-exchange group as a counter ion, and is therefore desirably an anion.

Specific examples of the anion include (AuCl ₄ ⁻ , PtCl ₄ ²⁻ , PtCl ₆ ²⁻ , PdCl ₄ ²⁻ , PdCl ₆ ²⁻ , and CuCl ₄ ²⁻ . The ions are used in the form of an organic or inorganic acid, or an inorganic salt such as a sodium salt or a potassium salt, an organic salt such as an ammonium salt, or the like, dissolved in water, an alcohol, or the like. When a basic group such as is used, it is preferable to adsorb an anion after ionization by the action of an acid or the like.

  It is preferable to use a strong acid such as hydrochloric acid or sulfuric acid to generate a salt of a basic group with a strong acid. At this time, when a sodium salt or potassium salt which is a salt of a strong base is used as a metal salt, a salt of a strong acid (such as hydrochloric acid or sulfuric acid) and a salt of a strong base (such as sodium hydroxide or potassium hydroxide) can be used to form a strong acid. By the reaction of rapidly generating a salt with a strong base, the metal-containing ion can be adsorbed on the anion exchange group as a counter ion with good reactivity.

  Since ionization and adsorption can be performed simultaneously, it is preferable to use an organic acid or an inorganic acid capable of generating a metal-containing ion.

Organic acids and inorganic acids Examples of organic acids and inorganic acids capable of generating these metal-containing anions include tetrachloroauric (III) acid, hexachloroplatinic (IV) acid, and tetrachloropalladium (II) acid.

Organic Salts and Inorganic Salts Organic salts and inorganic salts include chloroaurates such as potassium tetrachloroaurate (III) and sodium tetrachloroaurate (III), potassium tetrachloroplatinate (II), and tetrachloroplatinum ( II) Chloroplatinates such as sodium acid, potassium hexachloroplatinate (IV), sodium hexachloroplatinate (IV), ammonium hexachloroplatinate (IV), ammonium tetrachloroplatinate (II), and tetrachloropalladium (II) Palladium chlorides such as potassium citrate, sodium tetrachloropalladate (II), potassium hexachloropalladium (IV), sodium hexachloropalladium (IV), ammonium tetrachloropalladium (II), ammonium hexachloropalladium (IV) , Tetraclo Examples thereof include cuprates such as potassium potassium cuprate (II), sodium tetrachlorocuprate (II), and ammonium tetrachlorocuprate (II), and silver salts such as potassium dicyanosilverate.

(B) Metal-containing compound Examples of the metal-containing compound include an organometallic complex having a binding group capable of adsorbing or binding to an anion-exchange group.

  Specifically, for example, those obtained by introducing a binding group into an organometallic complex including a ligand such as a β-diketone derivative, a bipyridine derivative, a biquinoline derivative, a phenanthrolen derivative, and a porphyrin derivative are used.

  Examples of the binding group include an acidic hydroxyl group such as a hydroxyl group or a mercapto group bonded to a fluorine-substituted alkyl group, a phenolic hydroxyl group, a thiophenolic hydroxyl group, a mercapto group, a carboxyl group, a sulfo group (sulfonic acid group), and a phosphono group. Acidic groups such as a group (phosphate group) and salts thereof. These acidic groups and salts are adsorbed as a counter ion of the anion-exchange group, or form an ester bond or the like to be bonded.

  Further, those which react with and bond to an amino group which is an anion-exchangeable group such as an aldehyde group, an epoxy group, an active ester group, an acid anhydride derivative group, and a maleimide derivative group can also be used. Further, a metal alkoxide derivative group such as an alkoxysilyl group or a nitroaryl halide derivative group may be used. Examples of the active ester group include a 4-nitrophenyloxycarbonyl group derivative, an active ester group between a carboxyl group and N-hydroxysuccinimide or N-hydroxybenzimide, and an imide ester derivative group. Examples of the alkoxysilyl group include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, and a methoxydimethylsilyl group.

  Usually, these metal-containing ions and metal-containing compounds are used as a solution such as an aqueous solution or an alcohol solution. The substrate on which the pattern of the anion-exchange groups is formed is brought into contact with the solution by dipping or coating, for example, to perform adsorption on the anion-exchange groups. The solution is preferably an aqueous solution because it is easy to handle and safe.

  When the binding group is an acidic group such as a carboxyl group, the metal-containing compound is preferably added with water solubility as a salt with a strong base, that is, a sodium salt or a potassium salt. In this case, the anion exchange group is preferably a salt with a strong acid. An anion exchange group such as an amino group is treated with hydrochloric acid or sulfuric acid to form a strong acid salt such as hydrochloride or sulfate. When a metal-containing compound such as a sodium salt or a potassium salt is allowed to act on this, a strong acid + strong base salt and a weak acid + weak base salt are generated from a strong acid + weak base salt and a weak acid + strong base salt. The metal-containing compound can be efficiently adsorbed on the anion exchange group.

  The adsorbed metal-containing ion or metal-containing compound is used as it is or as a catalyst for electroless plating by being reduced and metallized.

  Metal ions having a smaller ionization tendency than the metal to be plated are reduced by the plating metal ions in the plating solution without being reduced.

  For example, in the case of copper plating, ions such as gold, platinum, palladium, and silver can be used as they are. Copper ions are reduced to fine copper particles and then used as a catalyst for electroless plating.

  As the reducing agent, known reducing agents such as formaldehyde, sodium borohydride, dimethylamine borane, trimethylamine borane, hydrazine, and hypophosphite such as sodium hypophosphite can be used. The reducing agent is generally reduced as a solution such as an aqueous solution by dipping the substrate in the solution. Before reduction, it is preferable to wash the base material with water or the like to remove excess metal-containing ions and metal-containing compounds.

(C) Metal colloid As the metal colloid solution, an aqueous solution of a colloid such as gold, silver, platinum, palladium, copper or nickel, or a solution of an organic solvent such as alcohol is used. It is desirable to use a protective colloid protected by a protective substance such as a surfactant or a polymer from the viewpoint of storage stability of the metal colloid solution. Metal colloids are often positively or negatively charged, and the polarity of the charge can be changed by a protective substance.

  In many cases, the anion exchange group is also charged in the liquid, so that the metal colloid is adsorbed by electrostatic attraction with the anion exchange group. It is preferable to use a negatively charged metal colloid.

  This binding group may be bound to the anion exchange group using a metal colloid having a binding group on the surface. Examples of the binding group include an acidic hydroxyl group such as a phenolic hydroxyl group, a thiophenolic hydroxyl group, a hydroxyl group and a mercapto group bonded to a fluorine-substituted alkyl group, a mercapto group, a carboxyl group, a sulfo group (sulfonic acid group), and a phosphono group. Examples include acidic groups such as a group (phosphate group) and salts thereof. These acidic groups are adsorbed as a counter ion of the anion-exchange group, or form an ester bond or the like to be bonded. In addition, an anion exchange group such as an aldehyde group, an epoxy group, a metal alkoxide derivative group, an active ester group, a metal alkoxide derivative group such as an alkoxysilyl group, an acid anhydride derivative group, a maleimide derivative group, and a nitroaryl halide derivative group. Those which react with and bind to a certain amino group or the like can also be used. Examples of the active ester group include a 4-nitrophenyloxycarbonyl group derivative, an active ester group of a carboxyl group and N-hydroxysuccinimide, an N-hydroxybenzimide, an imide ester derivative group, and the like. Examples of the alkoxysilyl group include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, and a methoxydimethylsilyl group.

  The metal colloid does not need to be reduced and can be used as it is as a catalyst for electroless plating. In the case of a protective colloid, the activity as a catalyst is improved by removing the protective substance by etching or the like using an acid, alkali solution, oxidizing agent solution or the like.

  Specific examples of the metal colloid solution include palladium hydrosol. The palladium hydrosol is prepared, for example, by adding an aqueous solution of a surfactant to an aqueous solution of palladium (II) chloride and sodium chloride with vigorous stirring, and then adding an aqueous solution of sodium borohydride as a reducing agent.

  The surfactant is not particularly limited, and widely known surfactants can be used. For example, cationic surfactants such as stearyltrimethylammonium chloride, anionic surfactants such as sodium dodecylbenzenesulfonate, nonionic surfactants such as polyethylene glycol mono-p-nonylphenyl ether, and zwitterionic surfactants An activator or the like is used. To adjust the negatively charged metal colloid, an anionic surfactant such as sodium dodecylbenzenesulfonate may be used.

  Although the particle diameter of the metal colloid is not particularly limited, it is generally 1 to 100 nm, preferably 1 to 20 nm in order to uniformly and densely adsorb the fine pattern of the anion exchange group. . In particular, when the metal colloid is adsorbed to the inside of the porous body, the particle diameter is preferably 1 to 10 nm.

  The concentration of the plating nucleus solution is preferably set in the range of 0.1 to 30% by weight, more preferably 1 to 15%. If the concentration is too low, a sufficient amount of plating nuclei will not be adsorbed on the anion exchange group, or the adsorption speed will be slow, and it will take time to adsorb. If the concentration is too high, the plating nuclei may be randomly adsorbed to regions other than the region where the anion exchange group is present, and it is difficult to form a good composite member. The time for which the base material is brought into contact with the solution by dipping the base material in the plating nucleus solution or the like is not particularly limited, but is generally from about 10 seconds to about 5 hours.

  It is preferable to add a surfactant or the like to the plating nucleus solution in order to improve the wettability to the substrate surface. In particular, when a porous substrate is used as the substrate, it is preferable to add a surfactant so that the solution permeates sufficiently into the inside of the porous material. As the surfactant, a nonionic surfactant is preferably used to inhibit adsorption of plating nuclei or prevent abnormal adsorption. Further, a fluorine-based surfactant which is hardly chemically changed is preferable. A supercritical fluid solution of plating nuclei may be used. Supercritical fluids are excellent because they can penetrate well into fine structures such as porous ones.

  When electroless plating is performed to the inside of the porous substrate, better results can be obtained by using a metal-containing ion solution or a metal-containing compound solution. The metal colloid has a low diffusion rate in a solution, and is difficult to diffuse into a porous body. Therefore, it is suitable for plating only near the surface of the porous substrate.

  On the other hand, metal-containing ions and metal-containing compounds have a high diffusion rate and can be sufficiently adsorbed inside the porous material. Therefore, it is suitable when it is necessary to plate the inside of the porous material, such as when forming a via. In addition, even if it is not a porous substrate, when there are fine irregularities on the surface of the substrate, it is better to use a metal-containing ionic solution or a metal-containing compound solution to follow the fine irregularities and plate with good adhesion. I can do it.

  After the substrate is brought into contact with a plating nucleus solution, it is preferable to wash the substrate to remove excess plating nuclei. For example, it is preferable to wash with the same solvent as the plating nucleus solution, such as water. By washing, the plating nuclei attached to the area other than the area where the anion exchange group is present can be removed, and the plating can be prevented from being disordered outside the area where the anion exchange group exists.

  Washing is particularly important when a porous substrate is used as the substrate. For cleaning, the base material is immersed in a cleaning tank containing a cleaning liquid such as water, or the cleaning liquid is sprayed with a spray or the like. In the case of using a base material such as a flat plate as a base material, which has few irregularities and hardly accumulates a solution, an air knife, an ultrasonic vibration air, or the like may be used to blow off an excess plating nucleus solution with a gas flow of air or nitrogen. good. Furthermore, the solution may be shaken by applying vibration, centrifugation or the like.

Adapter Molecule Normally, the plating nucleus is directly adsorbed to the anion-exchange group, but an adapter molecule may be used in order to cope with a wider range of plating conditions or to improve the adsorption ability. Here, the adapter molecule refers to a molecule that binds the anion exchange group and the plating nucleus. The adapter molecule has both a binding group for binding to an anion exchange group and an adsorptive group for adsorbing plating nuclei in the molecule. First, an adapter molecule is bound to the anion exchange group. Thereafter, the plating nucleus is adsorbed to the bound adapter molecule.

  The use of such an adapter molecule has the following two main advantages.

  The first advantage is that the types of plating nuclei and adsorption conditions, the type of plating solution and plating conditions can be selected in a wide range.

  For example, if an adapter molecule having a cation exchange group as the adsorptive group is used, a metal cation or a positively charged metal colloid can be adsorbed. In addition, if various ligands are used as the adsorptive group, various metal-containing ions can be adsorbed with high adsorptivity and selectivity. In addition, it is possible to cope with a change in plating nuclei to be used and various adsorption conditions. Similarly, in the plating process, it is possible to correspond to various compositions and properties of plating solutions and plating conditions.

  Of course, it is possible to apply a similar adapter molecule to a conventional cation exchange group. However, an amino group that is an anion exchange group has higher reactivity to the binding reaction. Therefore, it is possible to form a strong bond with the binding group even under mild reaction conditions.

  The second advantage is that the adsorption amount of plating nuclei can be increased. When an adapter molecule having a large number of adsorptive groups in one molecule is used, a large number of plating nuclei can be adsorbed per anion-exchange group as a result.

  Examples of the binding group of the adapter molecule include a phenolic hydroxyl group, a thiophenolic hydroxyl group, an acidic hydroxyl group such as a hydroxyl group or a mercapto group bonded to a fluorine-substituted alkyl group, a mercapto group, a carboxyl group, a sulfo group (sulfonic acid group), An acidic group such as a phosphono group (phosphate group) or a salt thereof can be used.

  These acidic groups bind as a counter ion of the anion exchange group or form an ester bond or the like. However, when bound as a counter ion, it is easily dissociated under acidic or alkaline conditions. Therefore, aldehyde groups, epoxy groups, metal alkoxide derivative groups, active ester groups, metal alkoxide derivative groups such as alkoxysilyl groups, acid anhydride derivative groups, maleimide derivative groups, nitroaryl halides, which can form stronger covalent bonds. Those which react with and bond to an amino group which is an anion exchange group such as a derivative group are preferable. Examples of the active ester group include a 4-nitrophenyloxycarbonyl group derivative, an active ester group between a carboxyl group and N-hydroxysuccinimide or N-hydroxybenzimide, and an imide ester derivative group. Examples of the alkoxysilyl group include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, and a methoxydimethylsilyl group.

  Examples of the adsorptive group of the adapter molecule include a phenolic hydroxyl group, a thiophenolic hydroxyl group, an acidic hydroxyl group such as a hydroxyl group and a mercapto group bonded to a fluorine-substituted alkyl group, a mercapto group, a carboxyl group, a sulfo group (sulfonic acid group), Acidic groups such as phosphono groups (phosphate groups) and salts thereof, or crown ether derivatives, ethylene oxide derivatives such as oligoethylene oxide and polyethylene oxide, β-diketone derivatives, bipyridine derivatives, biquinoline derivatives, phenanthrolen derivatives, porphyrin derivatives, etc. Derivatives of metal ligands and the like can be mentioned. In order to increase the adsorption amount of plating nuclei, it is preferable to have a plurality of these adsorptive groups in one molecule. Those in which these adsorptive groups are introduced into the main chain or side chain of a polymer adapter molecule can also be used.

  A substrate on which a pattern of anion-exchange groups is formed is immersed in a solution of these adapter molecules to contact the adapter molecules with the anion-exchange groups. Thereafter, the plating nuclei are adsorbed as before.

(E) Electroless plating Next, electroless plating is performed using the adsorbed plating nucleus or its reduced body as a plating catalyst to form a conductive pattern.

  The electroless plating is performed by immersing a base material having a plating nucleus or a reduced body thereof adsorbed in an electroless plating solution or the like and bringing the base into contact.

  The electroless plating solution is not particularly limited, and a widely known plating solution such as copper, nickel, gold, silver, and platinum can be used. In electroless plating, plating proceeds using a plating nucleus or a reduced form thereof adsorbed on an anion exchange group as a catalyst. As a result, it is possible to selectively perform plating only in a region where an anion exchange group exists. .

  The pattern of the anion-exchange group that adsorbs the plating nucleus uses the pattern of the anion-exchange group formed by pattern exposure on the photosensitive layer that generates or disappears the anion-exchange group. It is preferable because it is completed. However, in order to perform plating on a pattern that is the reverse of the exposure pattern, there is a method in which exposure is performed two or more times, in addition to using a photosensitive layer that loses an anion exchangeable group.

  Using a photosensitive layer that generates an anion exchange group, pattern exposure is performed to form a pattern of the anion exchange group. Next, the resulting anion-exchange group is capped with a protecting group to prevent the plating nucleus from adsorbing. Next, the entire surface is exposed to form an anion-exchangeable group other than the portion subjected to the pattern exposure. Then, a plating nucleus is adsorbed on the resultant and plated to form a conductive portion having a pattern inverted from the exposure pattern.

  A similar method using a carboxyl group which is a cation exchange group is disclosed in JP-A-6-202343.

  However, since the carboxyl group has insufficient reactivity, it is difficult to cap a protective group having high resistance to a strongly alkaline plating solution or the like. If an attempt is made to cap a protective group having high resistance, the process tends to be complicated due to the necessity of heating or a special reagent.

  On the other hand, since an anion exchange group such as an amino group has a high reactivity, it is possible to cap a protective group having high resistance under mild conditions such as room temperature.

Protecting Group As a compound to be capped as a protecting group, a compound having both a cap site that does not adsorb plating nuclei and a binding group that can bind to an anion exchange group is preferable.

  Examples of the capping site include a substituted or unsubstituted alkyl group, aryl group, aralkyl group, and the like, and a fluorine-substituted group, a siloxane derivative group, and the like can also be used. However, if the cap portion is too hydrophobic, the plating solution is repelled too much, and poor plating is likely to occur when the pattern is fine or when a porous substrate is used. Therefore, it is preferable to have an appropriate affinity for the plating solution, and it is preferable that polar groups such as a hydroxyl group, a silanol group, an alkoxy group, an ester group, and an amide group, and these polar groups are substituted.

  Examples of the binding group include an acidic hydroxyl group such as a phenolic hydroxyl group, a thiophenolic hydroxyl group, a hydroxyl group and a mercapto group bonded to a fluorine-substituted alkyl group, a mercapto group, a carboxyl group, a sulfo group (sulfonic acid group), and a phosphono group. Examples include acidic groups such as a group (phosphate group) and salts thereof. These acidic groups are adsorbed as a counter ion of the anion-exchange group, or form an ester bond or the like to be bonded. Further, an aldehyde group, an epoxy group, an active ester group, an acid anhydride derivative group, a maleimide derivative group, an amino group which is an anion-exchange group such as an alkoxysilyl group, and the like, which reacts and binds can be used. An aldehyde group, an epoxy group, an active ester group, an acid anhydride derivative group, a maleimide derivative group, an alkoxysilyl group, or the like is preferably used because a bond having high resistance to a plating solution or the like can be formed.

[II] Manufacturing method of composite member (second embodiment)
Next, each step of the second aspect of the method for manufacturing a composite member will be described. The second embodiment is different from the first embodiment in the material for forming the photosensitive layer. That is, in the first embodiment, as the photosensitive layer, a swellable photosensitive layer in which an anion exchange group is generated or disappears by irradiating the surface of the base material with energy rays is used. The embodiment is characterized in that a photosensitive layer having at least an acyl oxime derivative group-containing compound or an azide derivative group-containing compound that generates an anion exchange group by irradiating an energy ray to the surface of the substrate is characterized. Therefore, in the description of this embodiment, only the photosensitive layer having at least an acyl oxime derivative group-containing compound or an azide derivative group-containing compound in which an anion exchange group is generated by irradiating the substrate surface with energy rays. Explanations are omitted, and others are omitted.

  The acyl oxime derivative group or azide derivative group used in this embodiment is exposed to energy rays in a long wavelength region of about 280 to 800 nm by using a sensitizer or the like as necessary. And since the energy rays in this region can irradiate the photosensitive layer inside the porous substrate without being absorbed by the material serving as the substrate, in the adsorption step after the energy ray irradiation step, Plating nuclei can be sufficiently adsorbed to the inside of the base material, and a sufficient amount of plating layer can be formed. In addition, these groups do not have an amide bond or the like which tends to abnormally adsorb plating nuclei before exposure. Therefore, high-contrast plating can be performed in the irradiation area and the non-irradiation area. Further, unlike the onium salts, there is no possibility that an acid is generated after plating from the remaining photosensitive group, thereby corroding the conductive patterns or reducing the insulation between the conductive patterns. Therefore, it is possible to form a composite member having excellent electrical characteristics and reliability. Further, the acyl oxime derivative group can crosslink the photosensitive portion by acting a cross-linking aid such as benzoquinone. Further, the azide derivative group also acts as a crosslinking group by a hydrogen abstraction reaction of nitrene. A phenol novolak resin or the like may be added as a crosslinking aid. In addition, since the photosensitive wavelength of these photosensitive groups can be easily controlled by a sensitizer, it is possible to sufficiently plate the inside of the substrate.

なお、式中、Ｒ１、Ｒ２はそれぞれ独立に炭素数１〜２０の置換または非置換のアルキル基、アリール基、アラルキル基を示す。 As the acyl oxime derivative group used in this embodiment, for example, the following groups are used.

In the formula, R1 and R2 each independently represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group.

なお、式中、Ｒは炭素数１から２０の置換または非置換の２価の芳香環構造。具体的には例えばフェニレンなどを示す。 As the azide derivative group, for example, the following groups are used.

In the formula, R is a substituted or unsubstituted divalent aromatic ring structure having 1 to 20 carbon atoms. Specifically, for example, phenylene is shown.

  As the compound containing these photosensitive groups, specifically, a polymer having these groups in a side chain or a main chain, or a polymer compound having a plurality of these groups is preferable. As the polymer or polymer compound, the polymer or polymer compound described in the first embodiment can be used.

  As a more preferable material of the photosensitive layer, a polymer which is a binary copolymer of an acrylate or methacrylate having these photosensitive groups and an acrylate or methacrylate having the crosslinkable group, or A terpolymer obtained by copolymerizing an acrylate or methacrylate having a group having a sensitizing effect with the terpolymer, and an acrylate or methacrylic acid having a hydrophobic group for controlling solubility. A quaternary copolymer obtained by copolymerizing an ester is exemplified. Further, instead of the acrylate or methacrylate, a styrene derivative, a norbornene derivative, an N-substituted maleimide derivative, a vinyl alcohol derivative, or the like may be used. Examples of the crosslinkable group include an epoxy group such as a glycidyl group, and a radical polymerizable group such as a vinyl group, an acryloyl group, and a methacryloyl group. The molecular weight of the polymer is preferably about 2,000 to 50,000.

なお、式中、Ｒ１は水素、メチル基。Ｒ２、Ｒ３はそれぞれ独立に炭素数１〜２０の置換または非置換のアルキル基、アリール基、アラルキル基を示す。Ｒ２，Ｒ３の具体例としては、メチル基、フェニル基、ナフチル基、アンスリル基などが挙げられる。 Examples of an acrylate or methacrylate having an acyl oxime derivative group as a photosensitive group include the following.

In the formula, R1 is hydrogen or a methyl group. R2 and R3 each independently represent a substituted or unsubstituted alkyl group, aryl group or aralkyl group having 1 to 20 carbon atoms. Specific examples of R2 and R3 include a methyl group, a phenyl group, a naphthyl group, and an anthryl group.

Examples of monomer units having an azide derivative group as a photosensitive group include the following.

  In the formula, R1 represents hydrogen or a methyl group. R2 represents a hydrocarbon chain having 1 to 10 carbon atoms. Specific examples of R2 include methylene and ethylene.

  Further, the photosensitive layer of the present embodiment more preferably has swellability. Thereby, as described above, not only the inside of the photosensitive layer, which preferably has a thickness of 20 to 50 nm, can be impregnated with the plating nucleus forming composition, but also the photosensitive layer existing inside the base material. This is because, since sufficient exposure can be performed, a plating nucleus can be sufficiently formed, and as a result, a thick plating layer can be formed.

[III] Manufacturing method of composite member (third embodiment)
Next, each step of the third aspect of the method for manufacturing a composite member will be described.

  In the following description, a case where a porous sheet that is a sheet-like porous body is used will be described as an example to facilitate understanding. Needless to say, it is not limited.

(1) Manufacturing process (A) Electrode installation process As shown in FIG. 1, the electrode 2 is installed on one surface of the insulating porous sheet 1. As the porous sheet, a honeycomb sheet or a three-dimensional mesh sheet having holes penetrating on the front and back of the sheet is used. It is preferable to form a photosensitive layer whose surface energy changes upon irradiation with energy rays on the inner surface of the pores of the porous sheet.

  The method for forming the photosensitive layer on the substrate is not particularly limited, but is generally formed by applying a solution of a photosensitive agent to the substrate. The layer thickness of the photosensitive layer to be applied is not particularly limited, but is generally set to about 0.5 to 1000 nm, preferably 1 to 100 nm, more preferably 20 to 50 nm. good.

  Further, the electrode is placed in close contact with the porous sheet. At this time, it is important that the electrode surface that is in close contact with the porous sheet communicates with the opposite side of the porous sheet by holes that penetrate the front and back of the porous sheet. In a later step, the plating solution is made to penetrate into the electrode surface through the penetrated holes to deposit the plating metal. The electrodes may be installed after the irradiation with the energy rays.

(B) Partial surface modification step Next, a part of the porous body is modified to change its surface energy, so that the affinity of the modified part for water is equal to the affinity of the non-modified part for water. A pattern of a different region is formed. As a result, the permeability of the plating solution to the porous sheet changes, and the plating solution easily permeates the hydrophilic portion. In this surface modification step, a method using energy beam irradiation, a method using a chemical, a method using partial heating, a method using a mechanical means to partially modify the surface, or the like is used as the modification means. Can be. As a method of modifying with a drug, the modification can be performed by applying a hydrophilic substance or a hydrophobic substance and forming a hydrophilic layer or a hydrophobic layer on the surface. In addition, it is possible to modify the surface by applying a reagent such as an oxidizing agent, a reducing agent, a hydrophilic group-introducing reaction initiator, a lipophilic group-introducing reaction initiator to a part of the base material to cause a required reaction. . When applying these agents, the agents may be applied only to the necessary portions of the base material by ejecting the agents by inkjet, or a masking agent such as wax may be applied to the unnecessary portions and the entire surface of the agent may be applied. You may. In the method based on partial heating, the surface energy can be changed by partially heating in an oxidizing atmosphere and partially oxidizing the surface. Further, the modification by mechanical means can also change the surface energy by rubbing a part of the surface of the base material to roughen it. However, in comparison with these methods, from the viewpoints of workability, reforming efficiency, and the like, the following method using energy ray irradiation is the most efficient and preferable.

  This energy ray irradiation irradiates the porous sheet with energy rays in a pattern, changes the surface energy of the inner surface of the pores of the irradiated part, and forms a pattern in which the irradiated part or the non-irradiated part is selectively hydrophilic. . As a result, the permeability of the plating solution to the porous sheet changes, and the plating solution easily permeates the hydrophilic portion. When a photosensitive layer is formed on the inner surface of the pore, the photosensitive layer is exposed to light and the surface energy changes. FIG. 1 shows, by way of example, a case where the surface energy of the irradiation unit changes and the plating solution changes to a state where it easily penetrates. In this case, the photosensitive layer before irradiation is made of a material that repels a plating solution so that the plating solution does not penetrate into unirradiated portions. By the irradiation, the plating solution is selectively permeated into the insulating region 3 in the porous body selected in contact with the electrode surface. The method of changing the surface energy is not particularly limited. However, since a change in surface energy before and after irradiation can be increased, it is best to use a photosensitive group that generates or loses an ion-exchange group by irradiation with energy rays. For example, copper electroplating solutions are generally acidic. Therefore, when a basic amino group or the like is generated in the region 3, an ammonium salt is generated to make the region hydrophilic. Therefore, a region 3 where the plating solution easily permeates is formed. As described above, the method of forming a region into which the plating solution selectively penetrates by changing the surface energy can simplify the process and form a fine pattern. For example, in a method of filling a hole or the like in a region where the plating solution is not desired to be penetrated with wax or resist, it is difficult to form a fine pattern and it is difficult to remove the wax or resist after plating. According to the method of the present invention, since the porous body remains porous from beginning to end, it is easy to impregnate a curable resin or the like after forming the conductive pattern.

The condition for irradiating the energy rays is generally performed by, for example, using a high-pressure mercury lamp or the like as a light source and exposing with an exposure amount of about 0.1 to 10000 mJ / cm ² through a mask according to a pattern. For the exposure, a mask may be used, scanning with a laser beam may be performed, or light from a light source may be modulated by a micromirror array in which a large number of minute mirrors are arranged in a matrix.

(C) Plating solution infiltration step By dipping the porous sheet with electrodes in which the region 3 has been formed in the electrolytic plating solution or the like, the plating solution selectively penetrates into the region 3. Since the region 3 is in contact with the electrode surface, the plating solution penetrates to the electrode surface and the electrolytic plating can be performed. In addition, since the inner surface of the hole in the region 3 is insulative, the deposition of plating proceeds only from the electrode surface, and the inside of the hole can be sequentially filled at a high filling rate. If the inner surface of the hole in the region 3 is conductive, plating is also deposited from the inner surface of the hole, and the hole in the outer peripheral portion of the region 3 is likely to be closed first. For this reason, the plating solution is not sufficiently supplied to the central portion of the region 3, and it becomes difficult to perform plating at a high filling rate.

  In general, the step of infiltrating the plating solution is completed by immersing the base material in the electrolytic plating tank for electrolytic plating so that the electrolytic plating solution immediately penetrates.

(D) Electroplating Step After the plating solution has penetrated, the electrodes are energized to perform electrolytic plating. Then, the electroplating selectively proceeds only in the region 3 to form the conductive portion 4. The plating deposition starts from the electrode surface and fills the region 3 sequentially. Since the deposition of plating proceeds sequentially from the electrode surface, it becomes possible to fill the pores in the porous body at a very high filling rate. Further, if the energization time is adjusted, the porous sheet 1 can be stopped in the middle of the porous sheet 1 as in the conductive section 4, and plating can be continued to penetrate the porous sheet 1 as in the conductive section 5. I can do it. Furthermore, it can be made to protrude from the upper surface of the porous sheet 1 like the conductive portion 6. In addition, in electroplating, the deposition rate of plating can be increased as compared with electroless plating, so that formation of a conductive portion can be performed in a short time and with high throughput.

  The plating conditions at the time of the electrolytic plating step are not particularly limited, and generally, the same conditions as those of known general electrolytic plating can be applied.

(3) Detailed Description of Each Step Next, the details of each step of the third aspect of the method for producing a composite member of the present invention will be specifically described below.

(A) Base material (a) Insulating material constituting the base material The insulating material forming the porous body may be an organic material or an inorganic material, or a composite material of an organic material and an inorganic material. It may be.

Organic Material As the organic material, a polymer material is generally used.

  Examples of polymer materials include polyolefins such as polyethylene and polypropylene, polybutadienes, polyisoprenes, polydienes such as polyvinylethylene, acrylic resins such as polymethyl acrylate and polymethyl methacrylate, polystyrene derivatives, polyacrylonitrile, and polymethacrylonitrile. Polyacrylonitrile derivatives, polyacetals such as polyoxymethylene, polyethylene terephthalate, polyesters including aromatic polyesters such as polybutylene terephthalate, polyarylates, polyamides such as aromatic polyamides and nylons such as aramid resin, polyimides, polyimides, Epoxy resins, aromatic polyethers, polyether sulfones, polysulfones, polysulfides, and polytetrafluoroethylene. System polymers, polybenzoxazoles, poly benzothiazoles, polyphenylene such as polyparaphenylene, polyparaphenylene vinylene derivatives, polysiloxane derivatives, novolak resins, melamine resins, and urethane resins and the like.

Inorganic Material As the inorganic material, a ceramic material is generally used.

  Examples of the ceramic material include metal oxides such as silica, alumina, titania, and potassium titanate, silicon carbide, silicon nitride, and aluminum nitride.

  Among these insulating substrates, polymers are preferable because of their low dielectric constant, and liquid crystal polymers such as polyimides and aromatic polyamides, and fluorine-based polymers such as polytetrafluoroethylene are particularly preferable because of their excellent heat resistance. It is preferable to use a class or the like.

(B) Shape of Porous Substrate The porous body preferably has continuous pores having openings on the surface of the porous body, and preferably has continuous pores formed in a three-dimensional network. good.

By being formed in a three-dimensional network, the metal plated in the pores is three-dimensionally continuous, and thus has excellent strength and conductivity.

Pores of Porous Substrate The average pore diameter of the continuous pores is preferably set in the range of 0.05 to 5 μm, and more preferably in the range of 0.1 to 0.5 μm. If the pore diameter is too small, the plating solution or the like does not sufficiently penetrate into the porous interior, and if the pore diameter is too large, it is difficult to form a fine plated metal pattern, and when exposing with ultraviolet light or visible light, etc. Exposure rays are scattered by the porous structure, and it is difficult to perform pattern exposure with good contrast. The pore diameter should be uniform. The porosity is preferably set in the range of 20 to 95%, and more preferably in the range of 45 to 90%. If the porosity is too small, the plating solution or the like may not sufficiently penetrate, or the conductivity of the formed plated metal pattern may be low. If the porosity is too large, the strength of the porous body will not be sufficient and the dimensional stability will be poor.

Specific examples of porous body and manufacturing method For the porous body, specifically, a porous sheet in which three-dimensional continuous pores are formed in a sheet of a polymer material or the like, or a polymer fiber or a ceramic fiber entangled in a three-dimensional network. A cloth or a nonwoven fabric is used.

  The method for producing the porous sheet is not particularly limited. For example, a sheet produced by stretching a sheet of a crystalline polymer such as polypropylene or polytetrafluoroethylene is used. Further, it may be formed by utilizing a phase separation phenomenon such as spinodal decomposition or microphase separation of a polymer, or may be formed by an emulsion templating method using a surfactant.

  In addition, Y. A. Vlasov et al. (Adv. Mater. 11, No. 2, 165, 1999) and A. As described by Johnson et al. (Science Vol. 283, 963, 1999), a porous material formed by filling a gap between beads of an aggregate of silica or polymer beads with a polymer or ceramic and then removing the beads is used. It may be a sheet.

  Further, for example, H. Park et al. (Adv. Mater. 10, No. 13, 1045, 1998) and A. As reported by Jenekhe et al. (Science Vol. 283, 372, 1999), the beads may be produced using an aggregate of bubbles or liquid bubbles instead of beads.

  Further, B.I. H. Cumston et al. (Nature, vol. 398, 51, 1999) and M.S. It may be manufactured using a three-dimensional stereolithography as reported by Campbell et al. (Nature, vol. 404, 53, 2000).

  As the cloth and the nonwoven fabric, those manufactured from ceramic fibers or polymer fibers are used.

  As the ceramic fiber, for example, silica glass fiber, alumina fiber, silicon carbide fiber, potassium titanate fiber or the like is used.

  Examples of the polymer fiber include liquid crystalline polymers such as aromatic polyamide fiber and aromatic polyester fiber, high Tg polymer fiber, fluorinated polymer fiber such as PTFE fiber, polyparaphenylene sulfide fiber, aromatic polyimide fiber, Benzoxazole derivative fibers are used.

  Ceramic fibers and polymer fibers may be mixed, or composite fibers of ceramics and polymers may be used. As the nonwoven fabric, a nonwoven fabric of a polymer manufactured by a melt blow method, a nonwoven fabric of fine fibers having a diameter of about 0.1 to 0.3 μm obtained by finely pulverizing fibers of a liquid crystalline polymer such as an aromatic polyamide, or the like is used. It is preferable because the fiber diameter is fine and the pore diameter is uniform.

  In order to improve the dimensional stability of these nonwoven fabrics, it is preferable that the fibers are welded to each other or coated with a polymer to prevent the fibers from shifting. Non-woven fabrics are preferred over cloths because of their low anisotropy and uniform structure.

  Of course, the shape of the porous body is not limited to a sheet shape, and various shapes such as a fibrous shape, a hollow fiber shape, a tubular shape, a spherical shape, and a lump shape are used according to the application.

  As an example of a sheet-like porous body, as a sheet-like porous body used for a flexible wiring board or a multilayer wiring board, for example, the thickness is about 10 to 100 μm, and the pore diameter is 0.1 to 0. A polyimide porous sheet manufactured by spinodal decomposition or microphase separation having a porosity of about 5 μm and a porosity of about 60 to 85%, a porous sheet of polytetrafluoroethylene manufactured by a drawing method, and a nonwoven fabric of fine aramid fiber (aramid paper) ) Etc. can be used.

(C) Wettability of inner surface of pores of porous body When a photosensitive layer as described later is formed on the inner surface of pores of these porous bodies, plating of inner surface of pores before formation of the photosensitive layer is performed. The wettability with the liquid is set according to the characteristics of the photosensitive layer. That is, the method for manufacturing a composite member according to the third aspect of the present invention is characterized in that the inner surface of the pores in a specific region is easily wetted with the plating solution, and the plating solution is selectively penetrated into this region. is there. At this time, it is necessary to prevent the plating solution from permeating by repelling the plating solution on the inner surface of the holes in the other regions. In the case where the photosensitive layer becomes wet with the plating solution by the irradiation of the energy beam, it is better to repel the plating solution by making the inner surface of the pores water repellent. Conversely, when the photosensitive layer repels the plating solution by irradiating the energy beam, it is better to make the inner surface of the pores hydrophilic so that the plating solution can easily penetrate. Of course, the object of the present invention can be achieved if the wettability of the photosensitive layer, which is the outermost layer, with the plating solution before and after the exposure greatly changes. However, it may be difficult to completely cover the inner surface of the pores of the porous body with the photosensitive layer, and in some cases, the inner surface of the pores of the porous body may be exposed. In such a case, the properties of the inner surface of the pores of the porous body are reflected in the permeability of the plating solution. That is, it is preferable that the wettability of the inner surface of the pores with the plating solution is adjusted to the state before the irradiation of the photosensitive layer with energy rays.

(B) Installation of Electrode The electrode is installed at least partially in close contact with the porous body. For example, when the porous body has a sheet shape, a sheet-like electrode may be attached. A sheet-like porous body may be wound around a cylindrical electrode. Further, a wire-shaped or pipe-shaped electrode may be inserted into the hollow portion of the hollow fiber-shaped porous body.

  As long as the electrode and the porous body are in close contact with each other, the electrode and the porous body may be adhered and fixed, or may be fixed in a removable state by adhesion or the like. Alternatively, it may be simply pressed.

  For example, as shown in FIG. 2, a sheet-shaped porous body 8 may be supplied to a rotating roll-shaped electrode 7 by a reel-to-reel and plated continuously. The porous body 8 tightly wound around the electrode 7 enters the plating solution tank 11 as it is, and after plating a conductive part such as a via, for example, 13, exits from the plating solution tank 11 and moves away from the electrode. . The roll-shaped electrode 7 is preferably made of stainless steel without corrosion.

  The smoother the electrode surface, the easier it is for the conductive portion to peel off from the electrode. Alternatively, the surface of the conductive portion may be made uneven by applying a texture such as unevenness to the electrode surface. By making the end surfaces of the vias uneven, electric conduction with wirings and the like can be improved.

  Further, a conductive substance may be filled in pores of a selected region in the porous body to form an electrode. If the porous body electrode and the porous body do not adhere to each other and there is a gap, plating is deposited in the gap. If the electrode is in close contact with the porous body, the deposition of plating proceeds only in a selected region of the porous body, so that a highly accurate conductive pattern can be formed.

(C) Irradiation of energy rays Irradiation energy rays are not particularly limited, such as light rays such as ultraviolet rays, visible rays, and infrared rays, X rays, electron rays, α rays, γ rays, and heavy ion beams. Usually, ultraviolet rays, visible rays, electron beams and the like are most often used. Particularly, ultraviolet light and visible light having a wavelength of 280 nm or more, preferably 350 nm or more are good. For example, i-line (wavelength = 365 nm), g-line (wavelength = 435 nm), argon ion laser light (for example, wavelength = 488 nm), various semiconductor laser lights (for example, wavelength = 405 nm) using a high-pressure mercury lamp as a light source are used. These energy rays are relatively simple to irradiate, and can irradiate a large area in the atmosphere. When a mask is used, a general polymer film mask or a glass mask can be used as the mask. If the wavelength is too short, it is absorbed by the glass of the mask or the polymer film itself. For example, in the case of a porous substrate made of a heat-resistant aromatic polymer, there is strong absorption such as a benzene ring having a peak around 250 to 260 nm. Therefore, it is difficult to obtain a sufficient transmittance below 280 nm. The method of changing the surface energy by irradiation with energy rays is not particularly limited, and a widely known method can be used. For example, a method of irradiating an excimer laser to a PTFE porous sheet to make it hydrophilic, as disclosed in JP-A-6-293837, may be used. However, in order to allow the energy rays to sufficiently penetrate into the porous body, it is preferable to form a photosensitive layer that is sensitive to a wavelength of 280 nm or more on the inner surface of the pores of the porous body.

(A) Photosensitive layer Since the process is simple and the change in surface energy is large, it is preferable to form a photosensitive layer that generates or loses ion-exchange groups by irradiation with energy rays on the inner surface of the pores. . If the porous body itself is made photosensitive, the porous body absorbs a large amount of energy rays, making it difficult to irradiate the inside of the porous body. In addition, it is difficult to achieve a balance between characteristics required for a porous body, such as electrical characteristics, heat resistance, and mechanical strength, and photosensitivity. On the other hand, if a thin photosensitive layer is formed on the inner surface of the pores of a porous body made of a weak material that does not absorb energy rays or is made of a weak material, the energy rays can be sufficiently transmitted to the inside of the porous body. . In addition, since the material of the porous body itself does not need to be photosensitive, electrical properties, heat resistance, mechanical strength, and the like of the porous body can be easily secured. The process may be simple because the photosensitive layer has a group that generates or loses an ion-exchange group upon irradiation with energy rays.

Ion-exchangeable group The ion-exchangeable group in the present invention is a group capable of adsorbing ions, and refers to an ionic group or an acidic or basic group.

  The ion exchange group is hydrophilic or reacts with the plating solution to become hydrophilic, thereby facilitating the penetration of the plating solution. The polarity of the ionic group and whether to select acidic or basic are determined by the liquidity of the plating solution at the time of electrolytic plating.

  The reason why the ion exchange group is strong and hydrophilic is that it is ionized. Therefore, a plating solution that can be ionized is preferable. For example, a copper sulfate aqueous solution is generally used for electrolytic plating of copper. Copper sulfate aqueous solution is strongly acidic. Therefore, for example, phenolic hydroxyl groups and carboxyl groups, which are weakly acidic groups, cannot be ionized and have insufficient hydrophilicity. Similarly, an anionic group formed by the reaction of these weakly acidic groups with a base also becomes a weakly acidic group in a strongly acidic plating solution and has insufficient hydrophilicity. On the other hand, for example, a basic group such as an amino group or a cationic group such as an ammonium group becomes an ammonium group in a strongly acidic plating solution, and can exhibit strong hydrophilicity. That is, when the plating solution is acidic, it is preferable to use a cationic group or a basic group.

  On the other hand, when the plating solution is alkaline, it is preferable to use an anionic group or an acidic group.

  Examples of the anionic group or acidic group include a hydroxyl group and a mercapto group, a phenolic hydroxyl group, a thiophenolic hydroxyl group, and other acidic hydroxyl groups and mercapto groups, carboxyl groups, sulfo groups (sulfonic acid groups) bonded to a fluorine-substituted alkyl group or the like. ), An acidic group such as a phosphono group (phosphate group) or a salt thereof. Examples of the cationic group or basic group include an amino group, an amide group, a pyridine derivative group, an imidazole derivative group such as an imidazole residue, an oxazole residue, and a thiazole residue, a triazole derivative residue, and a salt thereof.

Groups that generate anionic groups or acidic groups by irradiation with energy rays Examples of groups that generate anionic groups or acidic groups by irradiation with energy rays include, for example, o-nitrobenzyl ester of carboxylic acid, sulfonic acid or silanol Derivatives, p-nitrobenzyl ester sulfonate derivatives and naphthyl or phthalimidotrifluorosulfonate derivatives.

  Furthermore, peroxides such as tert-butyl ester peroxide of carboxylic acid can also be used. In addition, quinonediazide derivatives such as benzoquinonediazide, naphthoquinonediazide, and anthraquinonediazide are also included.

  Further, a group in which a protecting group which can be deprotected by an acid catalyst or the like is introduced into an ion-exchange group such as a carboxyl group, a phenolic hydroxyl group, and a silanol group.

Photoacid Generator In the case of using an ion-exchange group into which a protecting group that can be deprotected by an acid catalyst is introduced, a photoacid generator that generates an acid by irradiation with energy rays is added.

  Irradiation with energy rays generates an acid from the photoacid generator, and the generated acid decomposes the protecting group to generate an ion-exchange group.

  Examples of the carboxyl-protecting group include tert-butyl, tert-butoxycarbonyl, and acetal groups such as tetrahydropyranyl. Examples of the protective group such as a phenolic hydroxyl group and a silanol group include a tert-butoxycarbonyl group and the like, which is used as a tert-butoxycarbonyloxy group.

Suitable photoacid generators for deprotection of such protecting groups include onium salts and diazonium salts having CF ₃ SO ₃ ⁻ , p-CH ₃ PhSO ₃ ⁻ , p-NO ₂ PhSO ₃ ⁻ or the like as a counter anion. , Phosphonium salts, salts such as iodonium salts, triazines, organic halogen compounds, 2-nitrobenzylsulfonic acid esters, iminosulfonates, N-sulfonyloxyimides, aromatic sulfones, quinonediazidesulfonic acid esters and the like. It can be used, and specifically, the photoacid generator as described in the description of the first embodiment of the method for producing a composite member of the present invention can be used. These photoacid generators may be used in combination with an acid multiplying agent that newly generates an acid autocatalytically with an acid. Furthermore, as an acid-producing group, an acid-proliferating group that newly generates an acidic group autocatalytically by an acid such as a 2-hydroxybicycloalkane-1-sulfonate residue introduced into a polymer side chain or the like is used, This may be used in combination with a photoacid generator.

Groups that lose anionic or acidic groups by irradiation with energy rays Examples of groups that lose anionic or acidic groups by irradiation with energy rays include, for example, carboxyl group derivatives that can be decomposed by decarboxylation. No. As the carboxyl group derivative group, a group in which a decarboxylation reaction proceeds with a basic compound is preferable. Examples of such groups include those having an electron-withdrawing group or an unsaturated bond at the α-position or β-position of the carboxyl group. Here, the electron-withdrawing group is preferably a carboxyl group, a cyano group, a nitro group, an aryl group, a carbonyl group, or a halogen.

  Specific examples of such a carboxyl group derivative group or a photosensitive molecule containing a carboxyl group derivative group include α-cyanocarboxylic acid derivatives, α-nitrocarboxylic acid derivatives, α-phenylcarboxylic acid derivatives, and β, γ-olefins. Carboxylic acid derivatives, indene carboxylic acid derivatives and the like can be mentioned. When a photobase generator is used as a basic compound, a base is generated by irradiation with energy rays, and a carboxyl group is decarboxylated and disappears by the action of the generated base.

Photobase generator Examples of the photobase generator include carbamates such as cobalt amine complexes, ketone oxime esters, o-nitrobenzyl carbamates, and formamides.

  Specifically, for example, carbamates such as NBC-101 (CAS No. [119137-03-0], manufactured by Midori Kagaku) can be used. Furthermore, triarylsulfonium salts such as TPS-OH (CAS. No. [58621-56-0]) manufactured by Midori Kagaku can also be used.

  Instead of the photobase generator, a photoacid generator and a basic compound can be used in combination. In this case, an acid is generated from the photoacid generator at the site irradiated with the energy beam, and the basic compound is neutralized.

  On the other hand, at the non-irradiated site, the basic compound acts on the carboxyl group-containing compound to cause a decarboxylation reaction to proceed and the carboxyl group to disappear. This makes it possible to selectively arrange a carboxyl group only at the irradiation site. The photoacid generator described above can be used as the photoacid generator.

Basic Compound Any basic compound can be added as long as it can be neutralized by an acid released from the photoacid generator and acts as a catalyst for the decarboxylation reaction of the carboxyl group-containing compound. Can be used.

  The basic compound may be either an organic compound or an inorganic compound, but is preferably ammonia or a nitrogen-containing organic compound.

  Specific examples include ammonia, primary amines, secondary amines, and tertiary amines.

  The content of these photobase generators and basic compounds is 0.1 to 30% by weight, preferably 0.5 to 15% by weight in the photosensitive composition.

  When the amount is less than 0.1% by weight, the decarboxylation reaction does not sufficiently proceed, and when the amount exceeds 30% by weight, the carboxyl derivative group remaining in the unexposed area may be deteriorated.

  When a photoacid generator and a basic compound are used in combination, the amount of an acid that can be generated from the photoacid generator is naturally larger than the amount of the base of the basic compound. Is preferably at least 1 equivalent, more preferably at least 1.2 equivalent. Here, the equivalent is an amount represented by the following equation.

  Equivalent = (number of moles of photoacid generator × number of acids generated from one molecule of photoacid generator × number of valences of generated acid) ÷ (number of moles of basic compound × valence of basic compound) Examples of the group that generates or eliminates a cationic group or a basic group by irradiation include a photosensitive group used in the first method for producing a composite member of the present invention, which generates or eliminates an anion-exchange group by irradiation with energy rays. The same groups as those described above can be used.

  In the present invention, in the formation of the above-mentioned photosensitive layer, a photosensitive material containing a later-described photosensitive compound for forming a composite member or a photosensitive composition for forming a composite member can be used.

Method of forming photosensitive layer The photosensitive layer can be formed by coating a photosensitive molecule having a photosensitive group or a photosensitive composition containing a photosensitive molecule on the inner surface of the pores of the porous body. . Alternatively, a photosensitive layer may be formed by bonding a molecule having both a group that binds to a functional group present on the inner surface of the pore and a photosensitive group, such as a silane coupling agent, to the inner surface of the hole.

  Alternatively, the photosensitive layer can be formed by modifying the inner surface of the pores by a chemical reaction. For example, a photosensitive graft polymer chain having a photosensitive group may be grown from a growth point formed on the inner surface of the hole by an interface graft polymerization method, and the inner surface of the hole may be covered with the photosensitive graft polymer chain. Furthermore, a functional group such as a sulfonic acid group is introduced into the pore inner surface of a polymer porous sheet having an aromatic ring such as a polyimide porous sheet by a Friedel-Crafts reaction or the like, and the introduced functional group is chemically modified. To form a photosensitive group.

  Since the material selection of the porous body is wide and the photosensitive layer can be easily formed, the photosensitive layer consisting of photosensitive molecules and photosensitive composition is coated on the inner surface of the pores to form the photosensitive layer Is most preferred.

  The photosensitive material to be coated has good applicability and excellent resistance to plating solutions and the like, so that the photosensitive group is the same as described in the method for producing a composite member according to the first or second aspect of the present invention. Those introduced into the main chain or side chain of a similar polymer are preferred.

  For coating, for example, a porous material may be impregnated with a solution of a photosensitive material and then dried. When a solution of a photosensitive material is used, it is desired to dilute the porous material so as not to block the pores. In addition, the means for coating the solution is not particularly limited, and a dipping method, a spin coating method, a spray method, or the like is used. Instead of coating with a solution, a photosensitive layer may be formed by a vapor deposition method or a CVD method.

  The photosensitive layer is preferably formed thin on the inner surface of the pores of the porous body without closing the pores. Although the porous body itself may be photosensitive, it is difficult to sufficiently expose the inside of the porous body because the absorption of the energy beam to be irradiated is increased. It is preferable that a thin photosensitive layer is formed on the surface of a porous body that is made of a material that does not absorb or has low absorption of energy rays to be irradiated.

The layer thickness of the photosensitive layer is not particularly limited, but is preferably set in the range of 1 to 100 nm, more preferably 20 to 50 nm. If it is too thin, the amount of ion-exchange groups is not sufficient, and the plating solution cannot be sufficiently penetrated. On the other hand, if the thickness is too large, the holes may be closed. In addition, the irradiated energy rays are all absorbed near the surface, and the photosensitive layer inside the porous body cannot be sufficiently exposed to light.

  Needless to say, the layer thickness of the photosensitive layer is sufficiently smaller than the hole diameter so as not to block the holes. The thickness of the photosensitive layer is 20% or less, preferably 10% or less of the pore diameter.

Double Exposure Method After capping the protective group on the pattern of the ion-exchange group formed by the pattern exposure, the entire surface may be exposed to generate an ion-exchange group in a portion other than the pattern-exposed portion to make it hydrophilic. According to this method, it is possible to form a conductive portion having a pattern inverted from the pattern subjected to pattern exposure. A method of forming a hydrophilic and a hydrophobic pattern by such two exposures using a carboxyl group as an ion-exchange group is disclosed in JP-A-6-202343. The present invention can also be applied to the second aspect of the method for manufacturing a composite member.

  However, since the carboxyl group has insufficient reactivity, it is difficult to cap a protective group having high resistance to a strongly alkaline plating solution or the like. If an attempt is made to cap a protective group having high resistance, the process tends to be complicated due to the necessity of heating or a special reagent. Further, in an acidic electrolytic copper plating solution or the like, sufficient hydrophilicity cannot be exhibited. On the other hand, since an anion exchange group such as an amino group has high reactivity, it is possible to cap a protective group having high resistance under mild conditions such as room temperature. In addition, it can be ionized even in an acidic electrolytic copper plating solution and exhibit sufficient hydrophilicity.

  As a compound to be capped as a protective group, a compound having both a hydrophobic portion that is easy to repel a plating solution and a binding group that can bind to an anion exchange group is preferable.

  Examples of the hydrophobic site include a substituted or unsubstituted alkyl group, aryl group, aralkyl group, and the like, and a fluorine-substituted group, a siloxane derivative group, and the like can also be used.

  Examples of the binding group include an acidic hydroxyl group such as a phenolic hydroxyl group, a thiophenolic hydroxyl group, a hydroxyl group and a mercapto group bonded to a fluorine-substituted alkyl group, a mercapto group, a carboxyl group, a sulfo group (sulfonic acid group), and a phosphono group. And an acidic group such as a group (phosphate group). These acidic groups are adsorbed as a counter ion of the anion-exchange group, or form an ester bond or the like to be bonded.

  Further, those which react with and bond to an amino group which is an anion exchange group such as an aldehyde group, an epoxy group, an active ester group, an acid anhydride derivative group, a maleimide derivative group, and an alkoxysilyl group can also be used. An aldehyde group, an epoxy group, an active ester group, an acid anhydride derivative group, a maleimide derivative group, or the like is preferably used since a bond having high resistance to a plating solution or the like can be formed. Further, a metal alkoxide derivative group such as an alkoxysilyl group may be used. Examples of the active ester group include a 4-nitrophenyloxycarbonyl group derivative and a benzimidyloxycarbonyl group derivative. Examples of the alkoxysilyl group include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, and a methoxydimethylsilyl group.

(D) Infiltration of plating solution The method of selectively infiltrating the plating solution into the insulating region of the irradiated or unirradiated portion in the porous body is not particularly limited, and various methods can be used. Usually, the porous body is preferably immersed in the plating solution.

(E) Electroplating The method of electrolytic plating and the plating solution used are not particularly limited, and widely known plating methods and plating solutions can be used. In particular, when using a porous body on which a photosensitive layer that generates or eliminates an anion exchange group is formed, an acidic plating solution is preferably used. Usually, a plating solution containing metal ions or metal-containing ions is used. For example, a solution in which fine particles of a polymer or a ceramic are dispersed in the plating solution may be used. The material to be electroplated is not limited to a metal, but may be a ceramic or a polymer.

  It is preferable to add a leveling agent in order to promote plating deposition in the pores of the porous body and to suppress plating deposition after the plating is exposed outside the porous body. Since the supply of the plating solution is not sufficient in the porous body, a portion where the plating is exposed outside the porous body is likely to be preferentially plated. By adding the leveling agent, it becomes possible to perform uniform plating in the porous body. The leveling agent is not particularly limited, and widely known ones can be used. Examples thereof include chloride ions obtained from calcium chloride and the like. In addition, by performing pulse plating in which the polarity applied to the electrodes is severely changed, it is possible to suppress the plating from being preferentially deposited on a portion exposed outside the porous body.

(3) “Reel-to-reel” continuous process The method for manufacturing a composite member according to the first, second, and third aspects described above uses a strip-shaped substrate to perform “reel-to-reel”. In a continuous process. FIG. 3 shows an example of a method for manufacturing a composite member according to the first or second embodiment of the present invention, which is performed in a “reel-to-reel” continuous process. A strip-shaped substrate on which a photosensitive layer is formed is supplied from the reel 14. The wiring pattern is exposed by the exposure device 15 to form a latent image according to the wiring pattern on the photosensitive layer. The substrate on which the latent image is formed is introduced into a plating nucleus adsorption tank 16 containing a plating nucleus solution such as an aqueous chloroplatinic acid solution, and the plating nuclei are adsorbed on the ion-exchange groups on the substrate. Excess plating nucleus solution is removed with an air knife 17. Further, the excess plating solution remaining in the washing tank 18 is washed. Remove excess wash water with an air knife. Next, the base material is introduced into the reduction tank 19, and the plating nucleus is reduced to activate the plating nucleus. When the plating nucleus is a metal colloid, it is not necessary to pass through the reduction tank. The excess reducing solution is washed in a washing tank 20 and then electrolessly plated in an electroless plating tank 21 to form a conductive portion. After the electroless plating, the excess plating solution is removed in a washing tank 22, and the substrate on which the conductive portion is formed is dried in a dryer 23 and then stored in a reel 24.

  FIG. 4 shows an example of a method for manufacturing a composite member according to the third embodiment of the present invention, which is performed in a “reel-to-reel” continuous process. From the reel 25, a photosensitive porous sheet 26, both sides of which are protected by protective films, is supplied as a band-shaped base material. The protective film 28 is peeled off by the roll 27 and collected on the reel 29. The wiring pattern is exposed on the porous sheet from which the protective film has been peeled off by the exposure device 30 to form a latent image (pattern of the plating liquid permeable region). The porous sheet 31 on which the latent image is formed is introduced into the electrolytic plating solution tank 34 filled with the electrolytic plating solution 33 while being wound tightly around the roll electrode 32. At this time, the electrolytic plating solution permeates into the plating solution permeable region of the porous sheet. Further, when the rolled electrode 32 is energized, plating is deposited in the plating solution permeable region to form a conductive portion. The porous sheet 36 on which the conductive portion is formed is cleaned with a water washing tank 37 after removing an excess plating solution with an air knife 35. The porous sheet on which the conductive portion is formed is washed, dried in a dryer 39, and stored in a reel 40.

[IV] Porous substrate for forming composite member (fourth embodiment)
Next, the porous substrate for forming a composite member of the present invention will be described.

  As the porous member for forming a composite member of the present invention used in the method for producing a composite member according to the first, second, or third aspect, a porous body having pores; A photosensitive layer in which anion-exchange groups are generated or eliminated by irradiation with energy rays formed on the surface in the pores.

(1) Porous body having pores Specific examples of the porous body having pores include a porous sheet in which three-dimensional continuous pores are formed in a sheet of a polymer material or the like, polymer fibers and ceramic fibers. Cloth, nonwoven fabric, or the like, in which is entangled in a three-dimensional network.

  Specifically, for example, a sheet produced by stretching a sheet of a crystalline polymer such as polypropylene or polytetrafluoroethylene, or a polyimide formed by utilizing phase separation phenomena such as spinodal decomposition of a polymer or microphase separation, etc. May be used.

  As the cloth and the nonwoven fabric, those manufactured from ceramic fibers or polymer fibers are used.

  As the ceramic fiber, for example, silica glass fiber, alumina fiber, silicon carbide fiber, potassium titanate fiber or the like is used.

  Examples of the polymer fiber include a liquid crystalline polymer such as an aromatic polyamide fiber and an aromatic polyester fiber, a high Tg polymer fiber, a fluorine-based polymer fiber such as a PTFE fiber, a polyparaphenylene sulfide fiber, an aromatic polyimide fiber, and a polybenzo fiber. Oxazole derivative fibers and the like are used.

  The above ceramic fiber and polymer fiber may be mixed, or a composite fiber of ceramic and polymer may be used.

  A nonwoven fabric is more preferable than a cloth because the fibers are more three-dimensionally entangled, the anisotropy of the porous structure is small, and the pore diameter is uniform. Examples of the nonwoven fabric include a nonwoven fabric of a polymer produced by a melt blow method and a nonwoven fabric of fine fibers having a diameter of about 0.1 to 0.3 μm obtained by finely pulverizing fibers of a liquid crystalline polymer such as aromatic polyamide. However, it is preferable because the fiber diameter is fine and the pore diameter is uniform. In order to improve the dimensional stability of these nonwoven fabrics, it is preferable that the fibers are welded to each other or coated with a polymer to prevent the fibers from shifting.

  The average pore diameter of the pores is preferably set in the range of 0.05 to 5 μm, and more preferably in the range of 0.1 to 0.5 μm. If the pore diameter is too small, the plating solution or the like does not sufficiently penetrate into the porous interior, and if the pore diameter is too large, it is difficult to form a fine plated metal pattern, and when exposing with ultraviolet light or visible light, etc. Exposure rays are scattered by the porous structure, and it is difficult to perform pattern exposure with good contrast. The pore diameter should be uniform. The porosity is preferably set in the range of 20 to 95%, and more preferably in the range of 45 to 90%. If the porosity is too small, the plating solution or the like may not sufficiently penetrate, or the conductivity of the formed plated metal pattern may be low. If the porosity is too large, the strength of the porous body will not be sufficient and the dimensional stability will be poor.

When used in the method for producing a composite member according to the first and second aspects of the present invention, the surface of the base material is subjected to a hydrophilic treatment in order to improve wettability with a plating solution or the like. Is good. In particular, when a porous body is used as the base material and the inside of the porous body is plated, the hydrophilic treatment is important.

  The method for performing the hydrophilic treatment is not particularly limited, and a widely known method can be used. For example, a method of applying a hydrophilic substance such as a hydrophilic polymer such as polyvinyl alcohol, a method of modifying the surface by optical, thermal, or chemical treatment, and the like are used.

  Specifically, the surface of the base material is oxidized by irradiating ultraviolet rays under an oxygen stream or an ozone stream, or by exposing to an ozone atmosphere or an ozone solution. Further, for example, there is a method of oxidizing the substrate surface by oxygen plasma treatment in the air or in a vacuum. Moreover, you may process with an acid or an alkali. Further, the hydrophilicity may be increased by an oxidation method as disclosed in JP-A-2000-290413.

  When an oxidation treatment is performed on a polymer, glass, or the like, an acidic group capable of adsorbing a metal cation such as a carboxyl group or a silanol group is generated. However, as described above, according to the method for producing a composite member of the first and second aspects of the present invention using an anion-exchange group, even if these acidic groups are present, there is no risk that plating will abnormally precipitate. .

(2) Photosensitive layer The photosensitive layer in which the anion exchange group is generated or lost by irradiation with energy rays formed on the surface of the pore is formed on the surface of the pore of the porous body. This is a layer having a photosensitive group that generates or loses an anion exchangeable group by irradiation with energy rays.

(A) Anion-exchangeable group The anion-exchangeable group is a group capable of adsorbing anions, and is a cationic group or a basic group.

Cationic group Specifically, examples of the cationic group include aliphatic amines such as ammonium groups, quaternary ammonium salt derivative groups of aromatic amines, and pyridinium groups and imidazolium. And a quaternary ammonium salt derivative group of a nitrogen-containing heterocyclic ring such as a group.

Basic Group Examples of the basic group include an aliphatic or aromatic amino group, and a nitrogen-containing heterocyclic derivative group such as a pyridine residue or an imidazole residue.

(B) Formation of Photosensitive Layer Photosensitive Layer The photosensitive layer can be composed of only a photosensitive compound having a photosensitive group, but may be a mixture with another compound. By irradiating the photosensitive layer containing such a photosensitive group with energy rays in a desired pattern, an ion-exchange group is generated or eliminated at the irradiated site. In particular, when the photosensitive layer is used in the method of manufacturing a composite member according to the first aspect of the present invention, the photosensitive layer is preferably swellable because of the large amount of adsorption of plating nuclei.

Formation of Photosensitive Layer The photosensitive layer can be formed by coating a photosensitive compound having a photosensitive group and a crosslinkable group or a photosensitive composition containing a photosensitive molecule on the surface of a substrate. Alternatively, a photosensitive layer may be formed by binding a molecule having both a photosensitive group and a group that binds to a functional group present on the substrate surface, such as a silane coupling agent, to the substrate surface.

  Further, the photosensitive layer can be formed by modifying the surface of the base material by a chemical reaction.

  For example, a photosensitive graft polymer chain having a photosensitive group may be grown from a growth point formed on the substrate surface by an interface graft polymerization method, and the substrate surface may be covered with the photosensitive graft polymer chain. Further, a photosensitive group may be formed by introducing a functional group into the surface of a substrate of a polymer porous sheet having an aromatic ring such as a polyimide porous sheet and chemically modifying the introduced functional group. To introduce a functional group, a sulfonic acid group or the like may be introduced by a Friedel-Crafts reaction or the like, or a hydroxyl group or a carboxyl group may be introduced by an oxidation technique as disclosed in JP-A-2000-290413. . Forming the photosensitive layer by coating the surface of the substrate with a photosensitive material composed of photosensitive molecules or a photosensitive composition because the material selection of the base material is wide and the photosensitive layer can be easily formed. Is most preferred.

  The layer thickness of the photosensitive layer is not particularly limited, but is preferably set in the range of 1 to 100 nm, more preferably 20 to 50 nm. If the thickness is too small, the amount of ion-exchange groups is not sufficient, and the plating solution cannot be sufficiently penetrated or the amount of plating nuclei adsorbed is not sufficient. On the other hand, if the thickness is too large, the holes may be closed. In addition, the irradiated energy rays are all absorbed near the surface, and the photosensitive layer inside the porous body cannot be sufficiently exposed to light.

  Needless to say, the layer thickness of the photosensitive layer is sufficiently smaller than the hole diameter so as not to block the holes. The thickness of the photosensitive layer is 20% or less, preferably 10% or less of the pore diameter.

(C) Photosensitive group A photosensitive group is a group that generates an anion exchange group by chemically reacting by absorbing irradiated energy rays, or a kind of anion that undergoes a chemical reaction by irradiation. A precursor of an exchangeable group, and the precursor further generates an anion exchangeable group by causing a chemical reaction with a substance present in the surroundings, and further, a base generated from a base generator by energy ray irradiation Either acts to produce an anion-exchangeable group or acts to eliminate the anion-exchangeable group. Among them, a photosensitive group which generates or disappears an anion exchange group by a chemical reaction alone is most preferable. Because it reacts alone, it is less susceptible to the surrounding atmosphere such as humidity, and also tends to occur when forming a photosensitive layer by applying a composition containing a compound having a photosensitive group. This is because it is possible to prevent a variation in reactivity due to the bias. In addition, when the precursor generated by irradiation chemically reacts with surrounding substances to generate anion-exchange groups, the surrounding substances are naturally contained in the atmosphere as moisture, such as water, or may be contained in the photosensitive layer. It is excellent to use a substance that has been previously mixed and contained in the mixture because the process is simple.

  Examples of the photosensitive group that independently generates an anion exchange group by absorbing energy rays include a carbamoyl oxime derivative group, a carbamic acid derivative group, and a formamide derivative group that generate a basic group such as an amine. A carbamic acid derivative of a piperidine derivative is thermally catalyzed by a base to produce a piperidine derivative which is an amine. For this reason, it is possible to generate a large amount of a basic group with a small exposure by combining with a photosensitive group that generates another basic group.

  A chemical reaction by energy beam irradiation produces a precursor of some anion-exchangeable group, and the precursor further generates an anion-exchangeable group by further producing a chemical reaction. Examples of the photosensitive group that generates an anion exchange group by a multi-step reaction include an acyl oxime derivative group and an azide derivative group.

  Examples of the photosensitive group that generates an anion exchange group by acting with a base or the like generated from a base generator by irradiation with energy rays include a carbamic acid derivative group of a piperidine derivative.

Photobase generator In the case of using a photosensitive group which generates an anion exchange group by acting with this base or the like, a photobase generator which generates a base by irradiation with energy rays is added. Upon irradiation with energy rays, a base is generated from the photobase generator, and the protective group is decomposed by the generated base to form an anion exchangeable group.

  As the photobase generator, for example, carbamates such as cobalt amine complexes, ketone oxime esters, o-nitrobenzyl carbamates, and formamides are used, and specifically, for example, NBC-101 (manufactured by Midori Kagaku) Carbamates such as CAS No. [119137-03-0]) and triarylsulfonium salts such as TPS-OH manufactured by Midori Kagaku (CAS No. 58621-56-0) are used.

  Instead of using a photobase generator, a photoacid generator and a basic compound may be combined. That is, at the energy beam irradiation site, an acid is generated from the photoacid generator to neutralize the basic compound.

  On the other hand, at the unirradiated site, a basic compound acts to generate an anion exchangeable group. This makes it possible to selectively dispose an anion-exchange group only in a non-irradiated part.

Photoacid Generator As the photoacid generator, onium salts, diazonium salts, phosphonium salts, iodonium salts and the like having CF ₃ SO ₃ ⁻ , p-CH ₃ PhSO ₃ ⁻ , p-NO ₂ PhSO ₃ ⁻ etc. as counter anions , Triazines, organic halogen compounds, 2-nitrobenzylsulfonic acid esters, iminosulfonates, N-sulfonyloxyimides, aromatic sulfones, quinonediazidesulfonic acid esters, and the like.

  Specifically, as the photoacid generator, for example, triphenylsulfonium triflate, diphenyliodonium triflate, 2,3,4,4-tetrahydroxybenzophenone-4-naphthoquinonediazidosulfonate, 4-N- Phenylamino-2-methoxyphenyldiazonium sulfate, diphenylsulfonylmethane, diphenylsulfonyldiazomethane, diphenyldisulfone, α-methylbenzoin tosylate, pyrogallol trimesylate, benzoin tosylate, naphthalimidyl trifluoromethanesulfonate, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl -S-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylaminoethyl) amino] -4,6-bis (trichloromethyl) -s-triazine dimethyl sulfate, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, -(4-dimethoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, and 2,4,6-tris ( Trichloromethyl) -s-triazine and the like.

  These photoacid generators may be used in combination with an acid multiplying agent that newly generates an acid autocatalytically with an acid. In addition, the photoacid-generating acid multiplying agent may be used alone.

Acid Proliferating Agent Examples of the acid proliferating agent include t-butyl 2-methyl-2- (p-toluenesulfonyloxymethyl) acetoacetate and derivatives thereof, cis-1-phenyl-2- (p-toluenesulfonyloxy). ) -1-cyclohexanol and its derivatives, 3-nitro-4- (t-butoxycarbonyloxy) benzyl tosylate and its derivatives, 3-phenyl- such as 3-phenyl-3,3-ethylenedioxypropyl tosylate 3,3-ethylenedioxypropylsulfonate derivatives, 2-hydroxybicycloalkane-1-sulfonate derivatives such as cis-3- (p-toluenesulfonyloxy) -2-pinanol, 1,4-bis (p-toluenesulfonyloxy ) Sulfonate induction of 1,4-cyclohexanediol such as cyclohexane And trioxane derivatives such as 2,4,6-tris [2- (p-toluenesulfonyloxy) ethyl] -1,3,5-trioxane. Examples of the photoacid-generating acid proliferating agent include 3-phenyl-3,3-ethylenedioxypropylsulfonate derivatives such as 3-phenyl-3,3-o-nitrophenylethylenedioxypropyl tosylate.

Basic Compound The basic compound to be used may be any one as long as it is neutralized by the acid released from the photoacid generator and acts as a catalyst for the reaction of forming an anion-exchange group. It can be either an organic compound or an inorganic compound. Preferably, ammonia, primary amines, secondary amines, tertiary amines and the like are used.

  A photosensitive group that loses an anion-exchange group by irradiation with an energy beam means that the group has an anion-exchange group before irradiation, and this anion-exchange group is released by the energy beam irradiation or becomes hydrophobic. It is a group that changes to a group.

Specifically, for example, Cl ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , BF ₄ ⁻ , ClO ₄ ⁻ , CF ₃ SO ₃ ⁻ , HSO ₄ ⁻ , FSO ₃ ⁻ , F ₂ PO ₂ ⁻ , _{p-CH 3 -C 6 H 4} -SO 3 -, p-NO 2 -C 6 H 4 -SO 3 - diazonium salt and a counter anion anion such as, phosphonium salts, iodonium salts, sulfonium salts and arsonium salts And other groups having a structure such as an onium salt. These can adsorb metal-containing ions and metal-containing compounds by an anion exchange reaction. Since it is charged to a positive charge, metal colloids can be adsorbed. Further, it is decomposed by energy beam irradiation and becomes nonionic, so that it becomes difficult to adsorb plating nuclei.

  The photosensitive layer is exposed to an alkaline or acidic aqueous solution during adsorption or plating of plating nuclei, so that the photosensitive groups that generate or disappear anion-exchange groups are hardly dissolved in them. And those supported or bonded to a polymer compound or the like. In the present invention, the polymer refers to a polymer having a repeating unit, and the polymer compound refers to a polymer having no specific repeating unit.

  Examples of the polymer include phenolic novolak resins, xylenol novolak resins, vinylphenol resins, phenolic resins such as cresol novolak resins, polyamide resins, polyimide resins, polyester resins, polyolefin resins, polyacrylate derivatives and polymethacrylate derivatives. An acrylic resin-based resin, a polysiloxane derivative, and the like can be given. Among them, it is preferable to use a phenol resin or an acrylic resin from the viewpoint of applicability and the like.

  As the polymer compound, a polymer compound having an aromatic ring and a carbon chain, preferably a branched one is preferable.

  The molecular weight of the polymer or polymer compound is not particularly limited, but the molecular weight (weight average molecular weight in the case of a polymer) is preferably 1,000 to 5,000,000, and more preferably 2000 to 50,000.

  When the molecular weight of the polymer or the high molecular compound is too small, the film-forming property is poor, and the solvent resistance to a plating solution or the like may be reduced. That is, it is easily dissolved in a plating solution or the like. Also, it is difficult to impart swelling properties to the polymer or polymer compound without impairing the resistance to solvents. On the other hand, when the molecular weight is excessively large, the solubility in the solvent for coating is reduced, and the coatability is also deteriorated.

  If the amount of the photosensitive group in the polymer or the polymer compound is too small, the plating nucleus cannot be sufficiently adsorbed. If the amount is too large, the plating nucleus is easily dissolved in the plating solution or the like, and the produced composite member absorbs moisture. It becomes easy to cause troubles such as insulation failure.

  The introduction ratio of the photosensitive group that generates or disappears the anion exchange group into the polymer or polymer compound is preferably 5 to 300%, more preferably 30 to 70%. Is good. Here, the introduction ratio is represented by the following formula.

Introduction ratio of photosensitive group to polymer (%) = (number of groups generating or eliminating anion-exchange groups) / (number of monomer units of polymer) × 100
Introduction rate (%) of photosensitive group into polymer compound = (number of groups generating or disappearing anion exchange group) / (molecular weight of polymer compound / 100) × 100
In order to increase the solvent resistance and make it difficult to dissolve in a plating solution or the like, it is preferable to crosslink a polymer or a polymer compound. To crosslink a polymer or polymer compound, a radical generator such as an organic peroxide is added, and a carbon-carbon bond is formed between the molecules of the polymer or polymer compound by a hydrogen abstraction reaction in the polymer or polymer compound. It may be generated. Further, a crosslinkable group may be introduced into the main chain or side chain of the polymer.

Crosslinkable Group As the crosslinkable group, the crosslinkable groups may be cross-linked by self-polymerization, or may be cross-linked by forming a bond with another substance in the photosensitive layer.

  Specific examples of the crosslinkable group capable of self-polymerization include, for example, an epoxy group such as a glycidyl group, a vinyl ether group, a chloromethylphenyl group, a methylol group, a benzocyclobutene group, a vinyl group, an acryloyl group, a methacryloyl group, a maleimidyl group, Examples thereof include an alkoxysilyl group, an acetoxysilyl group, an enoxysilyl group, an oximesilyl group, and derivatives thereof.

  These crosslinkable groups are crosslinked as required by light irradiation, heating, or by the action of a catalyst.

  As a catalyst, an acid group or a base catalyst is used for an epoxy group, a methylol group, a vinyl ether group, an alkoxysilyl group, an acetoxysilyl group, an enoxysilyl group, and an oximesilyl group, and a vinyl group, an acryloyl group, a methacryloyl group, and maleimidyl are used. A radical generator is used for a radical polymerizable group such as a group having a multiple bond such as a group. The crosslinkable group which is crosslinked by a radical reaction is preferable because the bond formed by the crosslinking is excellent in resistance to a strong alkaline solution such as a plating solution or a strongly acidic solution.

  Further, since the reaction proceeds promptly even at room temperature, heat treatment is usually unnecessary. For this reason, it is possible to prevent a decrease in dimensional stability and a thermal deterioration due to the heat treatment of the base material.

  Examples of the crosslinkable group in the case of forming a bond with another substance in the photosensitive layer to form a crosslink include a hydroxyl group, an isocyanate group, a carboxylic anhydride group, a maleimidyl group, an aldehyde group, and an alkoxysilyl group.

Crosslinking Aid At this time, a crosslinking aid having a plurality of groups capable of binding to the crosslinkable group in one molecule is used in order to bond with these crosslinkable groups to form a crosslink bond.

  As the crosslinking aid, for example, alkoxysilanes, aluminum alkoxides, carboxylic anhydrides, bismaleimide derivatives, isocyanate compounds, polyvalent methylol compounds, epoxy compounds, etc. are used for the hydroxyl groups. Polyhydric alcohols and the like are used for the isocyanate group, carboxylic anhydride group and alkoxysilyl group.

  What crosslinks by reacting with an anion exchange group may be used. For example, an epoxy group, a chloromethylphenyl group, a methylol group, an alkoxysilyl group, a maleimidyl group, an isocyanate group, a carboxylic anhydride group, an aldehyde group and the like react with an amino group and crosslink. In particular, the epoxy group is excellent because the property of adsorbing plating nuclei can be maintained well even after the amino group has reacted.

  Alternatively, a cross-linking aid having a plurality of these groups in one molecule may be simply added to cross-link the polymers into which the anion exchange groups have been introduced. In these cases, a catalyst such as an acid catalyst may be appropriately added.

  As the crosslinkable group, the following groups that can be dimerized by irradiation with energy rays can also be used. Such a group is excellent in that it absorbs a part of the energy ray but can selectively crosslink only the irradiated part. For example, cinnamoyl group, cinnamylidene group, chalcone residue, isocoumarin residue, 2,5-dimethoxystilbene residue, styrylpyridinium residue, thymine residue, α-phenylmaleimidyl group, anthracene residue, and 2-pyrone Residue.

  The rate of introduction of the crosslinkable group into the polymer or polymer compound is preferably in the range of 1 to 100%, and more preferably in the range of 10 to 50%. Here, the introduction ratio is represented by the following equation.

Introduction rate of crosslinkable group into polymer (%) = (number of crosslinkable groups) / (number of monomer units of polymer) × 100
Introduction rate of crosslinkable group into polymer compound (%) = (number of groups generating or disappearing anion exchangeable group) / (molecular weight of polymer compound / 100) × 100
If the rate of introduction of the crosslinkable group into the polymer or polymer compound is too low, it becomes difficult to sufficiently crosslink, and it is easy to dissolve in a plating solution or the like. On the other hand, if the crosslinkable group is introduced excessively, when crosslinked, it becomes difficult to swell in plating nucleus solution and the like, and the photosensitive layer cures and contracts, and the base material is deformed or the photosensitive layer May be peeled off.

  The crosslinking reaction is preferably performed after forming the photosensitive layer. If cross-linking occurs before the formation of the photosensitive layer, the solubility of the polymer in the solvent decreases, and it becomes difficult to apply the polymer to the insulating substrate. After the formation of the photosensitive layer, the crosslinking reaction is preferably advanced by stimulation such as heating, irradiation with energy rays, and moisture in the air.

  Energy beam irradiation is preferably performed by energy beam irradiation when generating or eliminating anion exchange groups.

Energy rays Irradiation energy rays are not particularly limited, such as ultraviolet rays, visible rays, infrared rays, etc., X-rays, electron rays, α-rays, γ-rays, and heavy ion beams. Usually, ultraviolet rays, visible rays, electron beams and the like are most often used.

  Further, a catalyst which is activated by energy beam irradiation can be blended.

  As the catalyst, a photoacid generator, a photobase generator, and a radical generator are used.

  As described above, the crosslinking reaction is most preferably a radical reaction, and it is preferable to use a radical generator in combination with a radical polymerizable crosslinking compound or a crosslinking group.

Radical generator As the radical generator, for example, the following organic peroxides can be used.

  For example, ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, and acetylacetone peroxide; 1,1-bis (t-hexylperoxy) -3,3,5- Trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, di-t-butylperoxy-2-methyl Cyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 2,2-bis (t-butylperoxy) butane, n-butyl-4 , 4-bis (t-butylperoxy) valerate, Peroxyketals such as 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl Hydroperoxides such as hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide; 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butyl Dialkyl peroxides such as peroxy) hexyne, isobutyryl Oxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide, m-toluoyl and benzoyl peroxide, diacyl peroxide such as benzoyl peroxide , Di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethylperoxydicarbonate, di-2-ethylhexylperoxy Peroxycarbonates such as dicarbonate, di-3-methoxybutylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, α, α′-bi (Neodecanoyl peroxy) diisopropylbenzene, cumyl peroxy neodecanoate, 1,1,3,3-tetramethylbutyl peroxy neododecanate, 1-cyclohexyl-1-methylethyl peroxy neodecanoate , T-hexylperoxy neodecanoate, t-butyl peroxy neodecanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexyl Peroxy 2-ethylhexanoate, t-butyl peroxy 2-ethylhexyl Noate, t-butylperoxyisobutyrate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymereic acid, t-butylperoxy 3,5,5-trimethylhexanoate, t-butylperoxy Laurate, 2,5-dimethyl-2,5-bis (m-toluylperoxy) hexane, t-butylperoxy isopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxy-m-toluylbenzoate, t-butylperoxybenzoate, bis (t-butylperoxy) ) Isophthalate -Oxyesters, t-butylperoxyallyl monocarbonate, t-butyltrimethylsilyl peroxide, 3,3 ′, 4,4′-tetrakis (t-butylperoxycarbonyl) benzophenone, and 2,3-dimethyl-2, 3-diphenylbutane and the like. In particular, polyfunctional radicals such as 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane and 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone The generator is preferable because it acts also as a crosslinking aid. Azonitriles such as azobisisobutyronitrile other than peroxides can also be used.

Sensitizer Various sensitizers may be added to the photosensitive layer. By adding a sensitizer, the sensitivity can be improved, and the photosensitive wavelength can be variously changed according to the light source used.

  In the case where the inside of the porous substrate is to be exposed to light, it is preferable to expose the inside of the porous substrate to energy rays that easily transmit through the substrate such as light having a wavelength other than the absorption wavelength of the substrate.

  For example, a polyimide porous substrate or the like often absorbs light having a wavelength of about 500 nm or less. Therefore, for example, it is difficult to expose the inside of the porous material by g-line or i-line. Even in such a case, by using a visible light sensitizer having an absorption band in a wavelength region of 500 nm or more, it is possible to satisfactorily expose the inside of the porous material.

  Specific examples of the sensitizer include, for example, aromatic hydrocarbons and derivatives thereof, benzophenone and derivatives thereof, o-benzoyl benzoate and its derivatives, acetophenone and its derivatives, benzoin and benzoin ether and its derivatives, xanthone and its derivatives Derivatives, thioxanthone and its derivatives disulfide compounds, quinone compounds, halogenated hydrocarbon-containing compounds and amines, 3-ethyl-5-[(3-ethyl-2 (3H) -benzothiazolylidene) ethylidene] -2- Merocyanine compounds such as thioxo-4-oxoazolidinone, 5-[(1,3-dihydro-1,3,3-trimethyl-2H-indole-2-ylidene) ethylidene] -3-ethyl-2-thioxo-4-oxazolidinone Dye, 3-butyl-1,1-dimethyl-2 [2 [2-diphenylamino-3-[(3-butyl-1,3-dihydro-1,1-dimethyl-2H-benz [e] indole-2-ylidene) ethylidene] -1-cyclopenten-1-yl ] Ethienyl] -1H-benz [e] indolium percolate, 2- [2- [2-chloro-3-[(3-ethyl-1,3-dihydro-1,1-dimethyl-2H-benz [e] Indole-2-ylidene) ethylidene] -1-cyclohexen-1-yl] ethenyl] -1,1-dimethyl-3-ethyl-1H-benz [e] indolium tetrafluoroborate, 2- [2- [2- Chloro-3-[(3-ethyl-1,3-dihydro-1,1-dimethyl-2H-benz [e] indole-2-ylidene) ethylidene] -1-cyclopenten-1-yl] [Enyl] -1,1-dimethyl-3-ethyl-1H-benz [e] cyanine dyes such as indolium iodide, squarium cyanine dyes, 2- [p- (dimethylamino) styryl] benzothiazole, 2- [ Styryl dyes such as p- (dimethylamino) styryl] naphtho [1,2-d] thiazole and 2-[(m-hydroxy-p-methoxy) styryl] benzothiazole; eosin B (CI No. 45400) ), Eosin J (CI No. 45380), cyanosine (CI No. 45410), bengal rose, erythrosine (CI No. 45430), 2,3,7-trihydroxy-9- Xanthene dyes such as phenylxanthene-6-one and rhodamine 6G, thionine (CI No. 52000), Azure A (C . I. No. 52005), thiazine dyes such as Azure C (CI No. 52002), pyronin B such as pyronin B (CI No. 45005), and pyronin GY (CI No. 45005); 3-acetyl Coumarin, 3-acetyl-7-diethylaminocoumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (dibutylamino) coumarin, 3- (2-benzimidazolyl) -7- (Diethylamino) coumarin, 10- (2-benzothiazolyl) -2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H, 11H- [1] benzopyrano [6, 7,8-ij] quinolizin-11-one, 3- (2-benzothiazolyl) -7- (dioctylamino) coumarin, 3-carbet Xy-7- (diethylamino) coumarin, 10- [3- [4- (dimethylamino) phenyl] -1-oxo-2-propenyl] -2,3,6,7-tetrahydro-1,1,7,7 Coumarin dyes such as -tetramethyl-1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolizin-11-one; 3,3′-carbonylbis (7-diethylaminocoumarin); Ketocoumarin dyes such as 3'-carbonyl-7-diethylaminocoumarin-7'-bis (butoxyethyl) aminocoumarin, 3,3'-carbonylbis (7-dibutylaminocoumarin), 4- (dicyanomethylene) -2- Methyl-6- (p-dimethylaminostyryl) -4H-pyran, 4- (dicyanomethylene) -2-methyl-6- (p-dibutylaminostyryl) There is a DCM-based dyes such as 4H- pyran.

  The compounding ratio of such a sensitizer is usually from 0.001 to 10% by weight, preferably from 0.01 to 5% by weight, based on the amount of the compound capable of producing or eliminating an anion exchange group upon exposure. .

  The sensitizer may be introduced not only into the photosensitive layer but also into, for example, a side chain of a polymer having a photosensitive group. When the photosensitive layer is sufficiently thin, a layer containing a sensitizer may be laminated on the photosensitive layer.

  In the present invention, in the formation of the above-mentioned photosensitive layer, a photosensitive material containing a later-described photosensitive compound for forming a composite member or a photosensitive composition for forming a composite member can be used.

(4) Protective film It is desirable that the surface of the porous substrate be wrapped with a polymer or metal protective film. For example, in the case of a sheet-like porous body, it is preferable that the porous body is sandwiched between two protective films. The protective film can prevent oxygen and moisture from entering the inside of the porous body, prevent the photosensitive layer from deteriorating, and significantly improve the storage stability of the porous body. Dry film resists and the like are also usually laminated with a protective film, but since the porous body has a larger surface area in contact with the outside air than such dry film resists and the like, the photosensitive layer is formed of oxygen, moisture, or acid in the air. And bases.

  The protective film is very effective for improving the storage stability of the porous body. It is preferable to fill the pores of the porous body with dry nitrogen or argon gas or the like. Abnormal exposure of the photosensitive layer may be prevented by using a light-shielding protective film. The protective film is usually removed before or after irradiation with the energy beam, and a subsequent plating step is performed.

  As the protective film, a polymer film of polyethylene terephthalate or the like having a thickness of about 5 to 30 μm, a metal foil of aluminum or stainless steel, or a composite film in which silica gel or an aluminum vapor-deposited film is formed on the surface of a polymer film of polyethylene terephthalate or the like is used. A conductive protective film such as a metal can also serve as an electrode during electrolytic plating.

  In the case where the film is continuously formed by a reel-to-reel method using a sheet-like porous substrate, such a protective film can also serve as a carrier film, and improves the dimensional stability of the porous body. .

  When used as a carrier film, only one of the two protective films on the back and front may be removed, and the remaining one may be left for the subsequent adsorption step or plating step. Such a protective film is preferably attached to the porous body by adhesion because it can be easily peeled off.

[V] Photosensitive compound for forming composite member (fifth embodiment), photosensitive composition (sixth embodiment)
Next, the photosensitive compound for forming a composite member and the photosensitive composition of the present invention will be described.

  The photosensitive compound for forming a composite member of the present invention used in the method for producing a composite member according to the first, second, and third aspects of the present invention can be anion-exchanged by irradiating a main chain or a side chain with light. A polymer or polymer compound having a photosensitive group that generates or eliminates a photosensitive group and a crosslinkable group, and the composition for forming a composite member of the present invention includes a compound having a photosensitive group, a polymer or a polymer compound, It is a composition comprising a compound having a crosslinkable group, a mixture with a polymer or a polymer compound. In the present invention, the polymer refers to a polymer having a repeating unit, and the polymer compound refers to a polymer having no specific repeating unit. Further, the compound refers to a compound having a smaller molecular weight than the above-mentioned polymer compound. When producing a composite member using these photosensitive compounds and photosensitive compositions, a solvent, an acid generator, a base generator, a sensitizer, and a surfactant are added to the photosensitive compound or the photosensitive composition. It can be used as a photosensitive material in which characteristics such as film forming properties are improved by adding components such as an agent.

(1) Photosensitive compound for forming a composite member (a) Photosensitive group A photosensitive group is a compound which generates an anion exchange group by chemically reacting alone by absorbing the irradiated energy rays, or Irradiation causes a chemical reaction to produce a precursor of some anion-exchangeable group, and the precursor further generates an anion-exchangeable group by causing a chemical reaction with a substance present in the surroundings. Either one that generates an anion exchange group by acting with a base or the like generated from a base generator, or one that loses an anion exchange group by irradiation with energy rays. Among them, a photosensitive group which generates or disappears an anion exchange group by a chemical reaction alone is most preferable. Because it reacts alone, it is less susceptible to the surrounding atmosphere such as humidity, and also tends to occur when forming a photosensitive layer by applying a composition containing a compound having a photosensitive group. This is because it is possible to prevent a variation in reactivity due to the bias. In addition, when the precursor generated by irradiation chemically reacts with surrounding substances to generate anion-exchange groups, the surrounding substances are naturally contained in the atmosphere as moisture, such as water, or may be contained in the photosensitive layer. It is excellent to use a substance that has been previously mixed and contained in the mixture because the process is simple.

  Examples of the photosensitive group that independently generates an anion exchange group by absorbing energy rays include a carbamoyl oxime derivative group, a carbamic acid derivative group, and a formamide derivative group that generate a basic group such as an amine. A carbamic acid derivative of a piperidine derivative is thermally catalyzed by a base to produce a piperidine derivative which is an amine. For this reason, it is possible to generate a large amount of a basic group with a small exposure by combining with a photosensitive group that generates another basic group.

なお、式中、Ｒ１は炭素数１〜２０の置換または非置換のアルキル基、アリール基、アラルキル基、Ｒ２は炭素数１〜２０の置換または非置換のアリール基を示す。Ｒ１の具体例としては、メチル基、フェニル基、ナフチル基、アンスリル基など。Ｒ２の具体例としては、フェニル基、ナフチル基、アンスリル基などが挙げられる。 Specific examples of the photosensitive group which independently generates an anion exchange group by irradiation with energy rays As the carbamoyl oxime derivative group, for example, the following groups are used.

In the formula, R1 represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, and R2 represents a substituted or unsubstituted aryl group having 1 to 20 carbon atoms. Specific examples of R1 include a methyl group, a phenyl group, a naphthyl group, and an anthryl group. Specific examples of R2 include a phenyl group, a naphthyl group and an anthryl group.

As the carbamic acid derivative group, for example, the following groups are used.

なお、式中、Ｒ１は炭素数１〜２０の置換または非置換のアリール基を示す。 Carbamic acid derivative groups as shown below can also be used.

In the formula, R1 represents a substituted or unsubstituted aryl group having 1 to 20 carbon atoms.

なお、式中、Ｒは炭素数１から２０の置換または非置換の２価の芳香環構造。具体的には例えばフェニレンなどを示す。 As the formamide derivative group, for example, the following groups are used.

In the formula, R is a substituted or unsubstituted divalent aromatic ring structure having 1 to 20 carbon atoms. Specifically, for example, phenylene is shown.

  A chemical reaction by energy beam irradiation produces a precursor of some anion-exchangeable group, and the precursor further generates an anion-exchangeable group by further producing a chemical reaction. Examples of the photosensitive group that generates an anion exchange group by a multi-step reaction include an acyl oxime derivative group and an azide derivative group.

なお、式中、Ｒ１、Ｒ２はそれぞれ独立に炭素数１〜２０の置換または非置換のアルキル基、アリール基、アラルキル基を示す。 As a photosensitive group acyloxime derivative group that generates a precursor of some anion exchange group by causing a chemical reaction by energy beam irradiation to generate an anion exchange group by further generating a chemical reaction by the precursor, For example, the following are used.

In the formula, R1 and R2 each independently represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group.

なお、式中、Ｒは炭素数１から２０の置換または非置換の２価の芳香環構造を示す。具体的には例えばフェニレンなどが挙げられる。 As the azide derivative group, for example, the following groups are used.

In the formula, R represents a substituted or unsubstituted divalent aromatic ring structure having 1 to 20 carbon atoms. Specific examples include phenylene.

  A photosensitive group that loses an anion-exchange group by irradiation with an energy beam means that the group has an anion-exchange group before irradiation, and this anion-exchange group is released by the energy beam irradiation or becomes hydrophobic. It is a group that changes to a group.

Specifically, for example, Cl ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , BF ₄ ⁻ , ClO ₄ ⁻ , CF ₃ SO ₃ ⁻ , HSO ₄ ⁻ , FSO ₃ ⁻ , F ₂ PO ₂ ⁻ , _{p-CH 3 -C 6 H 4} -SO 3 -, p-NO 2 -C 6 H 4 -SO 3 - diazonium salt and a counter anion anion such as, phosphonium salts, iodonium salts, sulfonium salts and arsonium salts And other groups having a structure such as an onium salt. These can adsorb metal-containing ions and metal-containing compounds by an anion exchange reaction. Since it is charged to a positive charge, metal colloids can be adsorbed. Further, it is decomposed by energy beam irradiation and becomes nonionic, so that it becomes difficult to adsorb plating nuclei.

なお、式中、Ｒは炭素数１から２０の置換または非置換の２価の芳香環構造を示す。具体的には例えばフェニレンを示す。また、置換基としては、具体的には例えばニトロ基、メトキシ基、モルホリノ基、塩素などが挙げられる。Ａ⁻は、Ｃｌ⁻、ＰＦ_６ ⁻、ＡｓＦ_６ ⁻、ＳｂＦ_６ ⁻、ＢＦ_４ ⁻、ＳｎＣｌ_６ ^２−、ＦｅＣｌ_４ ⁻、ＢｉＣｌ_５ ^２−、ＣｌＯ_４ ⁻、ＣＦ_３ＳＯ_３ ⁻、ＨＳＯ_４ ⁻、ＦＳＯ_３ ⁻、Ｆ_２ＰＯ_２ ⁻、ｐ−ＣＨ_３−Ｃ_６Ｈ_４−ＳＯ_３ ⁻、ｐ−ＮＯ_２−Ｃ_６Ｈ_４−ＳＯ_３ ⁻等の陰イオンを示す。 The following groups are used as the photosensitive group diazonium salt derivative group in which the anion exchange group is eliminated by irradiation with energy rays or changes to a hydrophobic group.

In the formula, R represents a substituted or unsubstituted divalent aromatic ring structure having 1 to 20 carbon atoms. Specifically, for example, phenylene is shown. In addition, specific examples of the substituent include a nitro group, a methoxy group, a morpholino group, and chlorine. A ^{- _{is, Cl -, PF 6 -,}} AsF 6 -, SbF 6 -, BF 4 -, SnCl 6 2-, FeCl 4 -, BiCl 5 2-, ClO 4 -, CF 3 SO 3 -, HSO 4 - _{^{, FSO 3 -, F 2 PO}} 2 -, p-CH 3 -C 6 H 4 -SO 3 -, p-NO 2 -C 6 H 4 -SO 3 - represents an anion such as.

  Examples of the photosensitive group that generates an anion exchange group by acting with a base or the like generated from a base generator by irradiation with energy rays include a carbamic acid derivative group of a piperidine derivative.

(B) Crosslinkable group As the crosslinkable group, the crosslinkable groups may be cross-linked by self-polymerization, or may be cross-linked by forming a bond with another substance in the photosensitive layer.

  Specific examples of the crosslinkable group capable of self-polymerization include, for example, an epoxy group such as a glycidyl group, a vinyl group, an acryloyl group, a methacryloyl group, a vinyl ether group, a chloromethylphenyl group, a methylol group, a benzocyclobutene group, a maleimidyl group, Examples thereof include an alkoxysilyl group, an acetoxysilyl group, an enoxysilyl group, an oximesilyl group, and derivatives thereof.

  These crosslinkable groups are crosslinked by light irradiation, heating, or the action of a catalyst.

(C) Polymer and Polymer Compound In the photosensitive compound for forming a composite member of the present invention, the photosensitive layer is exposed to an alkaline or acidic aqueous solution when a plating nucleus is adsorbed or plated. A photosensitive group or a crosslinkable group that generates or disappears an anion exchangeable group is carried or bound to a polymer or a polymer compound so as to be hardly dissolved in the polymer or polymer compound.

  Examples of the polymer include phenolic novolak resins, xylenol novolak resins, vinylphenol resins, phenolic resins such as cresol novolak resins, polyamide resins, polyimide resins, polyester resins, polyolefin resins, polyacrylate derivatives and polymethacrylate derivatives. Acrylic resin-based resin, polysiloxane derivative and the like. Among them, it is preferable to use a phenol resin or an acrylic resin from the viewpoint of applicability and the like.

  The above-mentioned polymer compound is a polymer compound having an aromatic ring and a carbon chain, and is preferably a branched one.

  The molecular weight of the polymer or polymer compound is not particularly limited, but the weight average molecular weight is preferably 1,000 to 5,000,000, and more preferably 2000 to 50,000.

  When the molecular weight of the polymer or the high molecular compound is too small, the film formability is poor and the solvent resistance to a plating solution or the like may be reduced. That is, it is easily dissolved in a plating solution or the like. Also, it is difficult to impart swelling properties to the polymer or polymer compound without impairing the resistance to solvents. On the other hand, when the molecular weight is excessively large, the solubility in the solvent for coating is reduced, and the coatability is also deteriorated.

(D) Introduced amount of photosensitive group and cross-linkable group If the introduced amount of the photosensitive group in the polymer is too small, the plating nucleus cannot be sufficiently adsorbed, and if it is too large, it becomes easy to dissolve in a plating solution or the like. In addition, the manufactured composite member easily absorbs moisture, and easily causes problems such as insulation failure.

  The introduction ratio of the photosensitive group that generates or disappears the anion exchange group into the polymer or polymer compound is preferably 5 to 300%, more preferably 30 to 70%. good. Here, the introduction ratio is represented by the following formula.

Introduction ratio of photosensitive group to polymer (%) = (number of groups generating or eliminating anion-exchange groups) / (number of monomer units of polymer) × 100
Introduction rate (%) of photosensitive group into polymer compound = (number of groups generating or disappearing anion exchange group) / (molecular weight of polymer compound / 100) × 100
The rate of introduction of the crosslinkable group into the polymer or polymer compound is preferably in the range of 1 to 100%, and more preferably in the range of 10 to 50%. The introduction rate here is represented by the following equation.

Introduction rate of crosslinkable group into polymer (%) = (number of crosslinkable groups) / (number of monomer units of polymer) × 100
Introduction rate of crosslinkable group into polymer compound (%) = (number of groups generating or disappearing anion exchange group) ÷ (molecular weight of polymer compound ÷ 100) × 100
If the amount of the crosslinkable group introduced into the polymer or polymer compound is too small, it will be difficult to crosslink sufficiently, and it will be easily dissolved or swelled in a plating solution or the like. On the other hand, if the crosslinkable group is introduced excessively, it becomes difficult to swell in plating nucleus solution and the like, and when crosslinked, the photosensitive layer cures and shrinks, and the base material is deformed or the photosensitive layer is removed from the base material. May be peeled off.

Photosensitive Compound for Forming a Composite Member The photosensitive compound for forming a composite member of the present invention described above is more preferably an acrylate or methacrylate having the photosensitive group and an acryl having the crosslinkable group. A polymer which is a binary copolymer of an acid ester or a methacrylic ester, or a terpolymer obtained by copolymerizing an acrylic or methacrylic ester having a group having a sensitizing effect with the polymer, and further, a solubility And a quaternary copolymer obtained by copolymerizing an acrylic acid ester or a methacrylic acid ester having a hydrophobic group or the like for controlling the viscosity. Instead of the acrylate or methacrylate, a styrene derivative, a norbornene derivative, an N-substituted maleimide derivative, a vinyl alcohol derivative, or the like may be used.

なお、式中、Ｒ１は水素あるいはメチル基。Ｒ２は炭素数１〜２０の置換または非置換のアルキル基、アリール基、アラルキル基、Ｒ３は炭素数１〜２０の置換または非置換のアリール基を示す。Ｒ２の具体例としては、メチル基、フェニル基、ナフチル基、アンスリル基など。Ｒ３の具体例としては、フェニル基、ナフチル基、アンスリル基などが挙げられる。 As the monomer unit having a photosensitive group, for example, a monomer unit having a carbamoyloxy derivative group represented by the following general formula as a photosensitive group is used.

In the formula, R1 is hydrogen or a methyl group. R2 represents a substituted or unsubstituted alkyl group, aryl group or aralkyl group having 1 to 20 carbon atoms, and R3 represents a substituted or unsubstituted aryl group having 1 to 20 carbon atoms. Specific examples of R2 include a methyl group, a phenyl group, a naphthyl group, and an anthryl group. Specific examples of R3 include a phenyl group, a naphthyl group and an anthryl group.

なお、式中、Ｒ１は水素あるいはメチル基を示す。 As the monomer unit having a photosensitive group, for example, a monomer unit having a carbamic acid derivative group represented by the following general formula as a photosensitive group is used.

In the formula, R1 represents hydrogen or a methyl group.

なお、式中、Ｒ１は水素あるいはメチル基を示す。 Further, as the monomer unit having a photosensitive group, for example, a monomer unit having a formamide derivative group represented by the following general formula as a photosensitive group is also used.

In the formula, R1 represents hydrogen or a methyl group.

なお、式中、Ｒ１は水素、メチル基を示す。また、Ｒ２、Ｒ３はそれぞれ独立に炭素数１〜２０の置換または非置換のアルキル基、アリール基、アラルキル基を示す。Ｒ２，Ｒ３の具体例としては、メチル基、フェニル基、ナフチル基、アンスリル基などが挙げられる。 As the monomer unit having a photosensitive group, for example, an acrylate or methacrylate monomer unit having an acyloxime derivative group represented by the following general formula as a photosensitive group is also used.

In the formula, R1 represents hydrogen or a methyl group. R2 and R3 each independently represent a substituted or unsubstituted alkyl group, aryl group or aralkyl group having 1 to 20 carbon atoms. Specific examples of R2 and R3 include a methyl group, a phenyl group, a naphthyl group, and an anthryl group.

なお、式中、Ｒ１は水素あるいはメチル基を示す。また、Ｒ２は炭素数１から１０の炭化水素鎖を示す。Ｒ２の具体例としては例えばメチレン、あるいはエチレンが挙げられる。 Further, as a monomer unit having a photosensitive group, for example, a monomer unit having an azide derivative group represented by the following general formula is also used. Example.

In the formula, R1 represents hydrogen or a methyl group. R2 represents a hydrocarbon chain having 1 to 10 carbon atoms. Specific examples of R2 include methylene and ethylene.

なお、式中、Ｒ１は、水素、メチル基を示す。Ｒ１、Ｒ２は、それぞれ独立に炭素数１〜２０の置換または非置換のアルキル基、アリール基、アラルキル基を示す。Ｒ２，Ｒ３の具体例としては、メチル基、フェニル基、ナフチル基、アンスリル基などが挙げられる。Ａ⁻は、Ｃｌ⁻、ＰＦ_６ ⁻、ＡｓＦ_６ ⁻、ＳｂＦ_６ ⁻、ＢＦ_４ ⁻、ＣｌＯ_４ ⁻、ＣＦ_３ＳＯ_３ ⁻、ＨＳＯ_４ ⁻、ＦＳＯ_３ ⁻、Ｆ_２ＰＯ_２ ⁻、ｐ−ＣＨ_３−Ｃ_６Ｈ_４−ＳＯ_３ ⁻、ｐ−ＮＯ_２−Ｃ_６Ｈ_４−ＳＯ_３ ⁻等の陰イオンを示す。 As the monomer unit having a photosensitive group, for example, an acrylate or methacrylate monomer unit having a sulfonium group represented by the following general formula as a photosensitive group is also used.

In the formula, R1 represents hydrogen or a methyl group. R1 and R2 each independently represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group. Specific examples of R2 and R3 include a methyl group, a phenyl group, a naphthyl group, and an anthryl group. A ⁻ is Cl ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , BF ₄ ⁻ , ClO ₄ ⁻ , CF ₃ SO ₃ ⁻ , HSO ₄ ⁻ , FSO ₃ ⁻ , F ₂ PO ₂ ⁻ , p-CH ^{_{3 -C 6 H 4 -SO 3 -}} , p-NO 2 -C 6 H 4 -SO 3 - represents an anion such as.

なお、式中、それぞれＲ１は水素あるいはメチル基を表す。 As the monomer unit having a crosslinkable group, for example, a unit represented by the following general formula is used.

In the formula, R1 represents a hydrogen or a methyl group.

なお、式中、Ｒ１，Ｒ２はそれぞれ独立に水素、メチル基を表す。

In the formula, R1 and R2 each independently represent hydrogen or a methyl group.

なお、式中、Ｒ１，Ｒ２は、それぞれ独立に水素、メチル基を表す。

In the formula, R1 and R2 each independently represent hydrogen or a methyl group.

As the monomer having a group exhibiting a sensitizing effect, for example, a monomer represented by the following general formula is used.

  In the formula, R1 represents a hydrogen or methyl group, and R2 represents a substituted or unsubstituted aryl group having 1 to 20 carbon atoms. Specific examples of R2 include a phenyl group, a naphthyl group and an anthryl group.

  As the monomer having a hydrophobic group, for example, an acrylate, methacrylate, or styrene derivative having a substituted or unsubstituted alkyl group, aryl group, or aralkyl group having 1 to 20 carbon atoms as an ester moiety is used. .

  Regarding the copolymerization ratio of various monomers, the copolymer ratio of the photosensitive monomer is preferably 10% or more, and more preferably 30 to 90%. When no crosslinkable monomer is contained, the copolymer ratio of the photosensitive monomer is preferably 30 to 60%. The copolymer ratio of the crosslinkable monomer is preferably about 5 to 30%. In this case, the copolymer ratio of the photosensitive monomer is preferably 60 to 90%.

Specific examples of the photosensitive compound for forming a composite member Specific examples of the photosensitive compound for forming a composite member include the following.

（重量平均分子量１万から５万程度、（ａ＋ｂ）／（ａ＋ｂ＋ｃ）＝０．２〜０．９程度、ａ／（ａ＋ｂ）＝０．１〜０．６程度、Ｒ１、Ｒ２はそれぞれ独立にメチル基、フェニル基など炭素数１〜１２程度の置換または非置換のアルキル基、アリール基、アラルキル基を示す。）
このポリマーは感光性基から発生したアミノ基が、グリシジル基の架橋反応の触媒として作用する。またアミノ基がグリシジル基と反応して生じる二級あるいは３級のアミノ基も陰イオン交換基として機能することができる。 Example 1
A polymer having a photosensitive group that generates an anion-exchangeable group (amino group) by light irradiation as shown by the following chemical formula (30) and a glycidyl group that is a crosslinkable group in a side chain

(Weight average molecular weight of about 10,000 to 50,000, (a + b) / (a + b + c) = about 0.2 to 0.9, a / (a + b) = about 0.1 to 0.6, R1 and R2 are each independently A substituted or unsubstituted alkyl group having about 1 to 12 carbon atoms such as a methyl group and a phenyl group, an aryl group, and an aralkyl group.)
In this polymer, an amino group generated from a photosensitive group acts as a catalyst for a glycidyl group crosslinking reaction. A secondary or tertiary amino group generated by reacting an amino group with a glycidyl group can also function as an anion exchange group.

（重量平均分子量１万から５万程度、（ａ＋ｂ）／（ａ＋ｂ＋ｃ＋ｄ）＝０．２〜０．９程度、ａ／（ａ＋ｂ）＝０．１〜０．６程度、ｃ／（ｃ＋ｄ）＝０．１〜０．２程度、Ｒ１，Ｒ２はそれぞれ独立にメチル基、フェニル基など炭素数１〜１２程度の置換または非置換のアルキル基、アリール基、アラルキル基を示す。）
このポリマーはラジカル発生剤、特にＢＴＴＢなどの多官能ラジカル発生剤を添加して用いるのが良い。 Example 2
A photosensitive group that generates an anion-exchangeable group (amino group) by light irradiation as shown in the following chemical formula (31) is used as a side chain, a vinyl group that is a crosslinkable group is used as a side chain, and carbon-carbon double Polymer having a bond in the main chain

(Weight average molecular weight of about 10,000 to 50,000, (a + b) / (a + b + c + d) = about 0.2 to 0.9, a / (a + b) = about 0.1 to 0.6, c / (c + d) = 0 About 0.1 to 0.2, and R1 and R2 each independently represent a substituted or unsubstituted alkyl, aryl, or aralkyl group having about 1 to 12 carbon atoms such as a methyl group or a phenyl group.
This polymer is preferably used by adding a radical generator, particularly a polyfunctional radical generator such as BTTB.

（重量平均分子量１万から５万程度、ｍ／（ｍ＋ｎ）＝０．２〜０．９程度）
このポリマーは感光性基が光照射によって陰イオン交換性基を消失すると同時にトリフルオロメタンスルホン酸を発生する。この酸がグリシジル基の架橋反応の触媒にもなる。 Example 3
Polymer having a photosensitive group capable of eliminating an anion exchange group (sulfonium group) by light irradiation as shown by the following chemical formula (32) and a glycidyl group in a side chain

(Weight average molecular weight of about 10,000 to 50,000, m / (m + n) = about 0.2 to 0.9)
This polymer generates trifluoromethanesulfonic acid at the same time that the photosensitive group loses the anion exchange group by light irradiation. This acid also serves as a catalyst for the crosslinking reaction of the glycidyl group.

（重量平均分子量１万から５万程度、ｍ／（ｍ＋ｎ）＝０．２〜０．９程度、Ｒ６はメチル基、エチル基、ブチル基、イソプロピル基、フェニル基など炭素数１〜６程度の置換または非置換のアルキル基、アリール基、アラルキル基など。）このポリマーは感光性基が光照射によって陰イオン交換性基を消失すると同時にトリフルオロメタンスルホン酸を発生する。この酸がアルコキシシリル基の架橋反応の触媒にもなる。これらの中でも特に、ラジカル架橋性である具体例２のポリマーが良い。 Example 4
A polymer having a photosensitive group capable of eliminating an anion exchange group (sulfonium group) by light irradiation as shown by the following chemical formula (33) and an alkoxysilyl group in a side chain

(Weight average molecular weight: about 10,000 to 50,000, m / (m + n) = about 0.2 to 0.9, R6 is a group having about 1 to 6 carbon atoms such as methyl group, ethyl group, butyl group, isopropyl group, phenyl group, etc. (Substituted or unsubstituted alkyl group, aryl group, aralkyl group, etc.) This polymer generates trifluoromethanesulfonic acid at the same time that the photosensitive group loses an anion exchange group by irradiation with light. This acid also serves as a catalyst for the crosslinking reaction of the alkoxysilyl group. Among them, the polymer of the specific example 2 which is radically crosslinkable is particularly preferable.

(2) Photosensitive Composition for Forming Composite Member The photosensitive composition for forming a composite member of the present invention comprises a compound, polymer or polymer compound having a photosensitive group that generates or disappears the anion-exchange group, A composition comprising the compound having a crosslinkable group, a polymer or a polymer compound. In the composite member-forming photosensitive composition, the photosensitive group, the crosslinkable group, the compound, the polymer, and the high molecular compound may be the same as those described in the composite member-forming photosensitive compound. it can. The photosensitive group or the crosslinkable group is preferably introduced into a polymer or a polymer compound because of its excellent coatability and resistance to a plating solution. As the polymer or polymer compound having a photosensitive group, specifically, a homopolymer or copolymer such as an acrylate ester, a methacrylic ester, a styrene derivative, a norbornene derivative, or an N-substituted maleimide derivative having the photosensitive group And polyester or polyether polymer compounds having a plurality of photosensitive groups. Examples of the polymer or polymer compound having a crosslinkable group include those having the above-mentioned crosslinkable group, and specifically, an epoxy resin, a polybutadiene resin, a silicone resin, a polyester having a plurality of crosslinkable groups or a polyester. Ether polymer compounds and the like can be mentioned. The composition ratio of the polymer or polymer compound having a photosensitive group is 1 to 99% by weight, preferably 20 to 95% by weight in the photosensitive composition.

(3) Photosensitive Material for Forming Composite Member The photosensitive compound for forming a composite member and the photosensitive composition for forming a composite member of the present invention may further comprise, if necessary, the following photobase generator, photoacid generator, and acid Components such as a proliferating agent, a catalyst, a crosslinking assistant, a radical generator, and a sensitizer may be blended to form a photosensitive material for forming a composite member. Generally, this material is dissolved in a solvent to form a solution, and this solution is applied to a substrate and dried to form a photosensitive layer. The solvent is not particularly limited as long as it can dissolve the components constituting the photosensitive material. Examples of the organic solvent include ethers such as tetrahydrofuran (THF), glyme and diglyme, ethyl acetate, ethyl lactate, and the like. Esters such as ethyl acetoacetate and propylene glycol monoethyl ether acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol; toluene, cumene and petroleum ether. Can be used. Water may be used. The concentration of this photosensitive material can be used in the range of 0.1 to 30%. If the concentration is higher than this, application becomes difficult, while if it is lower than this, the coating film thickness becomes thin and the efficiency of the coating operation decreases.

When using a photosensitive group that generates an anion-exchange group by the action of a base, such as a carbamic acid derivative group of a piperidine derivative, as a photosensitive group of the photosensitive compound for forming a composite member, irradiation with energy rays is performed. A photobase generator that generates a base is added. Upon irradiation with energy rays, a base is generated from the photobase generator, and an anion exchange group is generated by the action of the generated base.

  As the photobase generator, for example, carbamates such as cobalt amine complexes, ketone oxime esters, o-nitrobenzyl carbamates, and formamides are used, and specifically, for example, NBC-101 (manufactured by Midori Kagaku) Carbamates such as CAS No. [119137-03-0]) and triarylsulfonium salts such as TPS-OH manufactured by Midori Kagaku (CAS No. 58621-56-0) are used.

  Instead of using a photobase generator, a photoacid generator and a basic compound may be combined. That is, at the energy beam irradiation site, an acid is generated from the photoacid generator to neutralize the basic compound.

  On the other hand, at the unirradiated site, a basic compound acts to generate an anion exchangeable group. This makes it possible to selectively dispose an anion-exchange group only in a non-irradiated part.

Photoacid Generator As the photoacid generator, onium salts, diazonium salts, phosphonium salts, iodonium salts and the like having CF ₃ SO ₃ ⁻ , p-CH ₃ PhSO ₃ ⁻ , p-NO ₂ PhSO ₃ ⁻ etc. as counter anions , Triazines, organic halogen compounds, 2-nitrobenzylsulfonic acid esters, iminosulfonates, N-sulfonyloxyimides, aromatic sulfones, quinonediazidesulfonic acid esters, and the like.

  Specifically, as the photoacid generator, for example, triphenylsulfonium triflate, diphenyliodonium triflate, 2,3,4,4-tetrahydroxybenzophenone-4-naphthoquinonediazidosulfonate, 4-N- Phenylamino-2-methoxyphenyldiazonium sulfate, diphenylsulfonylmethane, diphenylsulfonyldiazomethane, diphenyldisulfone, α-methylbenzoin tosylate, pyrogallol trimesylate, benzoin tosylate, naphthalimidyl trifluoromethanesulfonate, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl -S-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylaminoethyl) amino] -4,6-bis (trichloromethyl) -s-triazine dimethyl sulfate, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, -(4-dimethoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, and 2,4,6-tris ( Trichloromethyl) -s-triazine and the like.

These photoacid generators may be used in combination with an acid multiplying agent that newly generates an acid autocatalytically with an acid. In addition, the photoacid-generating acid multiplying agent may be used alone.

Acid Proliferating Agent Examples of the acid proliferating agent include t-butyl 2-methyl-2- (p-toluenesulfonyloxymethyl) acetoacetate and derivatives thereof, and cis-1-phenyl-2- (p-toluenesulfonyloxy). ) -1-cyclohexanol and its derivatives, 3-nitro-4- (t-butoxycarbonyloxy) benzyl tosylate and its derivatives, 3-phenyl- such as 3-phenyl-3,3-ethylenedioxypropyl tosylate 3,3-ethylenedioxypropylsulfonate derivatives, 2-hydroxybicycloalkane-1-sulfonate derivatives such as cis-3- (p-toluenesulfonyloxy) -2-pinanol, 1,4-bis (p-toluenesulfonyloxy ) Sulfonate induction of 1,4-cyclohexanediol such as cyclohexane Body, 2,4,6-tris [2-(p-toluenesulfonyloxy) ethyl] etc. trioxane derivatives such as 1,3,5-trioxane and the like. Examples of the photoacid-generating acid proliferating agent include 3-phenyl-3,3-ethylenedioxypropylsulfonate derivatives such as 3-phenyl-3,3-o-nitrophenylethylenedioxypropyl tosylate.

Basic compounds Any basic compound used in combination with the photoacid generator can be used as long as it is neutralized by the acid released from the photoacid generator and acts as a catalyst for the formation reaction of the anion exchange group. And an organic compound or an inorganic compound may be used. Preferably, ammonia, primary amines, secondary amines, tertiary amines and the like are used.

Cross-linking catalyst The cross-linking catalyst is selected according to the cross-linking group of the contained photosensitive compound for forming a composite member. For example, an acid or base catalyst is used for a crosslinkable group such as an epoxy group, a methylol group, a vinyl ether group, an alkoxysilyl group, an acetoxysilyl group, an enoxysilyl group, and an oximesilyl group, and a vinyl group, an acryloyl group, a methacryloyl group, and the like. A radical generator is used for the crosslinkable group.

  For example, in the case of using a crosslinkable group that forms a bond with another substance and crosslinks, such as a hydroxyl group, an isocyanate group, a carboxylic anhydride group, a maleimidyl group, an aldehyde group, and an alkoxysilyl group, these crosslinkable groups are linked to each other. A crosslinking aid for bonding is added.

Crosslinking Aid As the crosslinking aid, one having a plurality of groups capable of binding to a crosslinkable group in one molecule is used in order to form a crosslinkable bond with these crosslinkable groups.

  As the crosslinking aid, for example, alkoxysilanes, aluminum alkoxides, carboxylic anhydrides, bismaleimide derivatives, isocyanate compounds, polyvalent methylol compounds, epoxy compounds, etc. are used for the hydroxyl groups. Polyhydric alcohols and the like are used for the isocyanate group, carboxylic anhydride group and alkoxysilyl group.

When the crosslinking group contained in the photosensitive compound for forming a composite member containing a radical generator is a radical polymerizable group such as a group having a multiple bond such as a vinyl group, an acryloyl group, a methacryloyl group, and a maleimidyl group, the radical A generator is added. As the radical generator, for example, the following organic peroxides can be used.

  For example, ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, and acetylacetone peroxide; 1,1-bis (t-hexylperoxy) -3,3,5- Trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, di-t-butylperoxy-2-methyl Cyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 2,2-bis (t-butylperoxy) butane, n-butyl-4 , 4-bis (t-butylperoxy) valerate, Peroxyketals such as 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl Hydroperoxides such as hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide; 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butyl Dialkyl peroxides such as peroxy) hexyne, isobutyryl Oxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide, m-toluoyl and benzoyl peroxide, diacyl peroxide such as benzoyl peroxide , Di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethylperoxydicarbonate, di-2-ethylhexylperoxy Peroxycarbonates such as dicarbonate, di-3-methoxybutylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, α, α′-bi (Neodecanoyl peroxy) diisopropylbenzene, cumyl peroxy neodecanoate, 1,1,3,3-tetramethylbutyl peroxy neododecanate, 1-cyclohexyl-1-methylethyl peroxy neodecanoate , T-hexylperoxy neodecanoate, t-butyl peroxy neodecanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexyl Peroxy 2-ethylhexanoate, t-butyl peroxy 2-ethylhexyl Noate, t-butylperoxyisobutyrate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymereic acid, t-butylperoxy 3,5,5-trimethylhexanoate, t-butylperoxy Laurate, 2,5-dimethyl-2,5-bis (m-toluylperoxy) hexane, t-butylperoxy isopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxy-m-toluylbenzoate, t-butylperoxybenzoate, bis (t-butylperoxy) ) Isophthalate -Oxyesters, t-butylperoxyallyl monocarbonate, t-butyltrimethylsilyl peroxide, 3,3 ′, 4,4′-tetrakis (t-butylperoxycarbonyl) benzophenone, and 2,3-dimethyl-2, 3-diphenylbutane and the like. In particular, polyfunctional radicals such as 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane and 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone The generator is preferable because it acts also as a crosslinking aid. Azonitriles such as azobisisobutyronitrile other than peroxides can also be used.

Sensitizer Various sensitizers may be added. By adding a sensitizer, it becomes possible to improve the sensitivity of the photosensitive group contained in the contained photosensitive compound for forming a composite member, or to change the photosensitive wavelength in various ways according to the light source used.

  In particular, when light is to be exposed to the inside of the porous base material, it is preferable to perform exposure with an energy ray that easily transmits through the base material, such as light having a wavelength other than the absorption wavelength of the base material.

  For example, a polyimide porous substrate or the like often absorbs light having a wavelength of about 500 nm or less. Therefore, for example, it is difficult to expose the inside of the porous material by g-line or i-line. In such a case, by using a visible light sensitizer having an absorption band in a wavelength region of 500 nm or more, it is possible to satisfactorily expose the inside of the porous material.

  Specific examples of the sensitizer include, for example, aromatic hydrocarbons and derivatives thereof, benzophenone and derivatives thereof, o-benzoyl benzoate and its derivatives, acetophenone and its derivatives, benzoin and benzoin ether and its derivatives, xanthone and its derivatives Derivatives, thioxanthone and its derivatives disulfide compounds, quinone compounds, halogenated hydrocarbon-containing compounds and amines, 3-ethyl-5-[(3-ethyl-2 (3H) -benzothiazolylidene) ethylidene] -2- Merocyanine compounds such as thioxo-4-oxoazolidinone, 5-[(1,3-dihydro-1,3,3-trimethyl-2H-indole-2-ylidene) ethylidene] -3-ethyl-2-thioxo-4-oxazolidinone Dye, 3-butyl-1,1-dimethyl-2 [2 [2-diphenylamino-3-[(3-butyl-1,3-dihydro-1,1-dimethyl-2H-benz [e] indole-2-ylidene) ethylidene] -1-cyclopenten-1-yl ] Ethienyl] -1H-benz [e] indolium percolate, 2- [2- [2-chloro-3-[(3-ethyl-1,3-dihydro-1,1-dimethyl-2H-benz [e] Indole-2-ylidene) ethylidene] -1-cyclohexen-1-yl] ethenyl] -1,1-dimethyl-3-ethyl-1H-benz [e] indolium tetrafluoroborate, 2- [2- [2- Chloro-3-[(3-ethyl-1,3-dihydro-1,1-dimethyl-2H-benz [e] indole-2-ylidene) ethylidene] -1-cyclopenten-1-yl] [Enyl] -1,1-dimethyl-3-ethyl-1H-benz [e] cyanine dyes such as indolium iodide, squarium cyanine dyes, 2- [p- (dimethylamino) styryl] benzothiazole, 2- [ Styryl dyes such as p- (dimethylamino) styryl] naphtho [1,2-d] thiazole and 2-[(m-hydroxy-p-methoxy) styryl] benzothiazole; eosin B (CI No. 45400) ), Eosin J (CI No. 45380), cyanosine (CI No. 45410), bengal rose, erythrosine (CI No. 45430), 2,3,7-trihydroxy-9- Xanthene dyes such as phenylxanthene-6-one and rhodamine 6G, thionine (CI No. 52000), Azure A (C . I. No. 52005), thiazine dyes such as Azure C (CI No. 52002), pyronin B such as pyronin B (CI No. 45005), and pyronin GY (CI No. 45005); 3-acetyl Coumarin, 3-acetyl-7-diethylaminocoumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (dibutylamino) coumarin, 3- (2-benzimidazolyl) -7- (Diethylamino) coumarin, 10- (2-benzothiazolyl) -2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H, 11H- [1] benzopyrano [6, 7,8-ij] quinolizin-11-one, 3- (2-benzothiazolyl) -7- (dioctylamino) coumarin, 3-carbet Xy-7- (diethylamino) coumarin, 10- [3- [4- (dimethylamino) phenyl] -1-oxo-2-propenyl] -2,3,6,7-tetrahydro-1,1,7,7 Coumarin dyes such as -tetramethyl-1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolizin-11-one; 3,3′-carbonylbis (7-diethylaminocoumarin); Ketocoumarin dyes such as 3'-carbonyl-7-diethylaminocoumarin-7'-bis (butoxyethyl) aminocoumarin, 3,3'-carbonylbis (7-dibutylaminocoumarin), 4- (dicyanomethylene) -2- Methyl-6- (p-dimethylaminostyryl) -4H-pyran, 4- (dicyanomethylene) -2-methyl-6- (p-dibutylaminostyryl) There is a DCM-based dyes such as 4H- pyran.

  The mixing ratio of components such as a photobase generator, a photoacid generator, an acid multiplying agent, a catalyst, a crosslinking aid, a radical generator, and the like is 0.1 to 30 wt. %, Preferably 1 to 15% by weight. The compounding ratio of the sensitizer is usually 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on the photosensitive compound for forming a composite member.

  Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to only these examples.

Evaluation method Evaluations in the following Examples and Comparative Examples were performed by the following methods.

  [Evaluation of Plating Failure] Evaluation of the presence of plating failure and abnormal deposition of plating was performed by observing the formed plating pattern with an optical microscope and a scanning electron microscope.

  [Evaluation of Conductivity] The conductivity was evaluated by measuring the resistance value of the formed plating pattern by a four-terminal method.

(Example 1)
In Example 1, as an example of the method for producing the composite member according to the first or second aspect of the present invention, a method for forming a copper pattern on a porous sheet using a photosensitive polymer that generates an amino group upon exposure is described. explain.

Synthesis of Polymer 1 Polymer 1 which was a random copolymer represented by the following chemical formula (34) was used as a photosensitive polymer that generates an amino group that is an anion exchange group upon exposure.

ポリマー１はアゾビスイソブチロニトリル（以下ＡＩＢＮと称す）をラジカル重合開始剤として用いたラジカル重合法により下記の如き重合方法により合成した重量平均分子量３万のものである。

The polymer 1 has a weight average molecular weight of 30,000 synthesized by the following polymerization method by a radical polymerization method using azobisisobutyronitrile (hereinafter, referred to as AIBN) as a radical polymerization initiator.

  First, in a 100 ml eggplant flask dried and replaced with argon gas, 1: 1 g of a monomer represented by the following chemical formula (35), 2: 3 g of a monomer represented by the following chemical formula (36), and 0.1 g of AIBN were placed in dry tetrahydrofuran. A solution dissolved in 14 g (hereinafter referred to as THF) was put together with a stirrer.

溶液はフラスコに入れた後、１分間アルゴンガスでバブリングして脱気した。アルゴン気流下、ゆっくり攪拌しながら６０℃で４０時間加熱した。加熱後、室温に戻してからメタノール溶媒に再沈した。再沈後、ガラスフィルターで沈殿を濾別した。濾過物を真空乾燥して、白色粉末としてポリマー１を得た。

The solution was put into a flask and degassed by bubbling with argon gas for 1 minute. The mixture was heated at 60 ° C. for 40 hours while stirring slowly under an argon stream. After heating, the temperature was returned to room temperature and then reprecipitated in a methanol solvent. After reprecipitation, the precipitate was separated by filtration with a glass filter. The filtrate was dried under vacuum to obtain Polymer 1 as a white powder.

Formation of Photosensitive Layer A hydrophilic polytetrafluoroethylene (PTFE) resin porous sheet (average pore diameter: 0.2 μm, film thickness: 20 μm) was immersed in a 5% by weight THF solution of the synthesized polymer 1. After the solution was sufficiently immersed in the porous sheet by immersion, the porous sheet was pulled out, air-dried, and the inner surface of the pores of the porous sheet was coated with polymer 1. Even after the coating, the pores of the porous sheet were not closed and maintained a porous state.

Exposure Using a parallel exposure device (PLA501 manufactured by Canon Inc.), exposure was performed under the condition of a light amount of ² J / cm ² through a wiring pattern mask having a line width of 20 μm and a space of 30 μm. An image was formed.

Adsorption of plating nuclei The porous sheet on which the pattern latent image was formed was immersed in a 10 wt% aqueous solution of chloroplatinic acid for 30 minutes to adsorb chloroplatinate ions to amino groups. After the adsorption, it was washed with distilled water to remove excess chloroplatinic acid aqueous solution. After washing, it was immersed in a 0.01 M aqueous solution of sodium borohydride for 5 minutes, and then washed with distilled water.

Plating Further, it is immersed in an electroless copper plating solution PS-503 at 40 ° C. for 3 hours to perform copper plating, and a composite that can be used as a wiring sheet having a mask-shaped Cu wiring pattern having a line width of 20 μm and a space of 30 μm is formed. A member was obtained. In addition, plating was performed in the same manner using a mask of a via pattern having a diameter of 50 μm to obtain a composite member that can be used as a wiring sheet (via sheet) having vias formed therein.

Evaluation In the manufactured wiring sheet and via sheet, plating failure and the like due to peeling of the photosensitive composition layer were not observed, and a composite member having good wiring and via patterns was able to be produced.

Applications After laminating four wiring sheets and three via sheets alternately, impregnate a resin solution obtained by adding 5 parts by weight of dicumyl peroxide to 100 parts by weight of 1,2-polybutadiene (molecular weight: 8000), and then 170 ° C. And cured for 1 hour to produce a multilayer wiring board.

(Comparative Example 1)
As a comparative example of Example 1, an attempt was made to manufacture a wiring sheet using a polymer that generates a cation exchange group as follows, instead of Polymer 1. First, 1 part by weight of a naphthalimide / trifluoromethanesulfonate as a photoacid generator was added to a random copolymer of polymethyl methacrylate-polytetrahydromethacrylate (60 mol%: 40 mol%, Mw = 40000). An acetone solution was prepared so that the total of the resin and the solid content of the photoacid generator was 1 part by weight to prepare a photosensitive composition. Using the same porous sheet as in Example 1, the above-described photosensitive composition was coated on the porous sheet by a dipping method.
After the application, the porous sheet was exposed using the same exposure apparatus and mask as in Example 1 to form a latent image on the exposed portion. Thereafter, the deprotection reaction was promoted by heating on a hot plate to generate a carboxyl group as a cation exchange group in the exposed area.
After the sheet on which the latent image was formed was immersed in a 0.5 M aqueous solution of copper sulfate for 5 minutes, washing with distilled water was repeated three times. Subsequently, the substrate was immersed in a 0.01 M aqueous solution of sodium borohydride for 30 minutes, and then washed with distilled water. After cleaning, the wiring sheet was immersed in the same electroless copper plating solution PS-503 as in Example 1 at 40 ° C. for 3 hours and plated with copper to prepare a wiring sheet. In the manufactured wiring sheet, a part of the plating pattern which was considered to be caused by peeling of the photosensitive layer from the porous sheet was observed.

(Example 2)
Example 2 also describes, as an example of the method for producing a composite member according to the first or second aspect of the present invention, an example in which a porous sheet made of a nonwoven fabric of fine aramid fibers is used as a base material.

Production of Nonwoven Fabric Fine aramid fibers having a diameter of 0.2 to 0.3 μm (trade name: Tiara, manufactured by Daicel Chemical Co., Ltd.) were strained to produce a 50 μm thick nonwoven fabric.

Hydrophilizing treatment This nonwoven fabric is degreased, washed with methanol, immersed in a mixed solution of 5 mmol of N-hydroxyphthalimide, 0.05 mmol of cobalt acetylacetonate (II) and 30 ml of acetic acid, and placed under an oxygen atmosphere (1 atm). ), And subjected to a hydrophilization treatment by oxidizing by standing at 75 ° C. for 4 hours. After the hydrophilic treatment, the substrate was washed.

The nonwoven fabric subjected to the hydrophilic treatment was immersed in a 5% by weight THF solution of the coating polymer 1. After the solution was sufficiently immersed in the nonwoven fabric by immersion, the solution was pulled up, air-dried, and the fiber surface of the nonwoven fabric was coated with polymer 1. Even after the coating, the pores of the nonwoven fabric were not closed and maintained a porous state.

Exposure Exposure was performed using a parallel exposure device (PLA501 manufactured by Canon Inc.) under the condition of a light amount of 200 mJ / cm ² through a wiring pattern mask having a line width of 100 μm and a space of 200 μm. A pattern latent image formed with amino groups was formed.

Adsorption of plating nuclei The nonwoven fabric on which the pattern latent image was formed was immersed in a 0.1N hydrochloric acid aqueous solution for 10 minutes. The amino group is changed to an ammonium salt by hydrochloric acid. After immersion, the substrate was washed with water and then immersed in an aqueous solution of complex 1 represented by the following chemical formula (37). Complex 1 has a sodium salt of a carboxyl group as a binding group. This binding group adsorbs to the ammonium base which is an anion exchange group.

錯体１の水溶液に３０分間浸漬して、アミノ基に錯体１を吸着させた。吸着後、蒸留水で洗浄して余分の錯体１を除去した。洗浄後、水素化ホウ素ナトリウム０．０１Ｍ水溶液に５分間浸漬後、蒸留水で洗浄した。

The complex 1 was immersed in an aqueous solution of the complex 1 for 30 minutes to adsorb the complex 1 to the amino group. After the adsorption, extra complex 1 was removed by washing with distilled water. After washing, it was immersed in a 0.01 M aqueous solution of sodium borohydride for 5 minutes, and then washed with distilled water.

Plating Further, the copper sheet is immersed in an electroless copper plating solution PS-503 at 40 ° C. for 3 hours to perform copper plating, and the composite sheet can be used as a wiring sheet having a Cu wiring pattern formed on a mask with a line width of 100 μm and a space of 200 μm. A member was obtained.

Evaluation In the wiring pattern, a wiring having a width of 100 μm was formed with a thickness of about 20 μm on the exposed surface side of the nonwoven fabric. No abnormal deposition of plating was observed in the unexposed areas. This was impregnated with an epoxy resin, and heated and cured at 120 ° C. for 1 hour under a nitrogen stream while applying pressure, thereby producing a wiring board. The manufactured wiring board had a sufficient bending strength, and the sheet resistance of the wiring was about 1.5 mΩ / □ or less and had a sufficient conductivity.

(Example 3)
Example 3 also describes, as an example of the method for producing the composite member according to the first or second aspect of the present invention, an example in which a porous sheet made of a nonwoven fabric of PPS fibers produced by a melt blow method is used as a base material.

Production of Nonwoven Fabric A nonwoven fabric having a thickness of 50 μm made of PPS fibers having a diameter of about 1 to 2 μm produced by a melt blow method was produced.

Hydrophilic treatment This non-woven fabric was subjected to a plasma treatment in the air with a plasma irradiator (manufactured by Keyence Corporation) to perform a hydrophilic treatment.

Formation of Wiring Pattern After the hydrophilicity-imparting treatment, a wiring board having a wiring having a width of 100 μm and a thickness of about 20 μm was manufactured in the same manner as in Example 2.

Evaluation This wiring board had a sufficient bending strength, and the sheet resistance of the wiring was about 1.5 mΩ / □ and had a sufficient conductivity.

(Example 4)
(Batch formation of surface wiring and via)
In Example 4, as an example of the method of manufacturing the composite member according to the first or second aspect of the present invention, a surface sheet and a via were formed on a porous sheet using a photosensitive polymer that generates an amino group upon exposure. A method of forming a batch by multiple exposures will be described.

Formation of Photosensitive Layer A PTFE porous sheet (average pore diameter: 0.2 μm, film thickness: 30 μm) subjected to hydrophilization treatment was immersed in a 5% by weight THF solution of Polymer 1 similar to that used in Example 1. After immersion, the solution was sufficiently permeated into the porous sheet and then pulled up, air-dried, and the inner surface of pores of the porous sheet was coated with polymer 1. Even after the coating, the pores of the porous sheet were not closed and maintained a porous state.

Exposure Using a parallel exposure device (PLA501 manufactured by Canon Inc.), exposure was performed at a light amount of ² J / cm ² through a mask on which a wiring pattern having a line width of 50 μm and a space of 50 μm and a via pattern having a diameter of 50 μm were formed. did. As a mask, a halftone mask having a transmittance of a via pattern portion of 100% and a transmittance of a wiring pattern portion of 10% was used. By this exposure, the wiring pattern portion is exposed only near the surface of the porous sheet, and the via pattern portion is exposed through the porous sheet.

Adsorption of plating nuclei The exposed porous sheet was immersed in a 10 wt% aqueous solution of chloroauric acid for 30 minutes to adsorb chloroaurate ions to amino groups. After the adsorption, it was washed with distilled water to remove excess chloroauric acid aqueous solution. After washing, it was immersed in a 0.01 M aqueous solution of sodium borohydride for 5 minutes, and then washed with distilled water.

Plating Further, copper plating is performed by immersing in an electroless copper plating solution PS-503 at 40 degrees for 3 hours to form a Cu surface wiring having a line width of 50 μm, a space of 50 μm, a thickness of 10 μm, and a Cu via having a diameter of 50 μm. Thus, a composite member that can be used as a wiring sheet was obtained.

Evaluation The sheet resistance of the Cu surface wiring was about 2 mΩ / □, indicating a sufficient conductivity. When this composite member is attached to both sides of a core wiring board such as a double-sided wiring board, a build-up wiring board can be manufactured.

(Example 5)
(Example using base-proliferating photosensitive polymer)
In Example 5, as an example of the method for producing a composite member according to the first aspect of the present invention, a polymer that generates an amino group by exposure and a base-proliferating polymer that self-proliferates an amino group by the amino group are used. A method for forming a copper pattern on a porous sheet using the combined photosensitive polymer will be described.

Formation of Photosensitive Layer A PTFE porous sheet (average pore diameter) obtained by subjecting a 5% by weight solution of a mixture of polymer 1 and base proliferating polymer 2 represented by the following chemical formula (38) to a weight ratio of 1: 2 by 5% by weight was prepared. (0.2 μm, film thickness 20 μm). After the solution was sufficiently immersed in the porous PTFE sheet by immersion, the solution was pulled out, air-dried, and the surface of the porous sheet inside the pores was coated with the polymer 1. Even after the coating, the pores of the porous sheet were not closed and maintained a porous state.

露光
平行露光器（キャノン（株）製ＰＬＡ５０１）で、ライン幅１００μｍ、スペース２００μｍの配線パターンのマスクを介して光量２００ｍＪ／ｃｍ^２の条件で露光した。露光後、１３０度で５分間加熱処理して、露光部に陰イオン交換性基であるアミノ基が生成したパターン潜像を形成した。

Exposure Exposure was performed using a parallel exposure device (PLA501, manufactured by Canon Inc.) under the conditions of a light amount of 200 mJ / cm ² through a wiring pattern mask having a line width of 100 μm and a space of 200 μm. After the exposure, a heat treatment was performed at 130 ° C. for 5 minutes to form a pattern latent image in which an amino group as an anion-exchange group was formed in the exposed portion.

Adsorption of plating nuclei The porous sheet on which the pattern latent image was formed was immersed in an aqueous hydrochloric acid solution and an aqueous solution of complex 1 similar to those used in Example 2. Complex 1 has a sodium salt of a carboxyl group as a binding group. This binding group is adsorbed on the amino group.

  The complex 1 was immersed in an aqueous solution of the complex 1 for 30 minutes to adsorb the complex 1 to the amino group. After the adsorption, extra complex 1 was removed by washing with distilled water. After washing, it was immersed in a 0.01 M aqueous solution of sodium borohydride for 5 minutes, and then washed with distilled water.

Plating Further, the copper sheet is immersed in an electroless copper plating solution PS-503 at 40 ° C. for 3 hours to perform copper plating, and the composite sheet can be used as a wiring sheet having a Cu wiring pattern formed on a mask with a line width of 100 μm and a space of 200 μm. A member was obtained.

Evaluation The wiring pattern was formed such that wiring having a width of 100 μm was penetrated on the front and back of the porous sheet. No abnormal deposition of plating was observed in the unexposed areas. This was impregnated with an epoxy resin, and heated and cured at 120 ° C. for 1 hour under a nitrogen stream while applying pressure, thereby producing a wiring board. The manufactured wiring board had a sufficient bending strength, and the sheet resistance of the wiring was about 1.5 mΩ / □ and had a sufficient conductivity.

(Example 6)
(Example using a photosensitive polymer that loses an anion exchange group)
In Example 6, as an example of the method for manufacturing the composite member according to the first aspect of the present invention, a copper pattern is formed on a porous sheet by using a photosensitive polymer having a photosensitive group that loses an anion exchange group. How to do it.

Synthesis of Polymer 3 As a polymer for forming a photosensitive layer, a copolymer 3 of monomer 3, monomer 4, and methyl methacrylate represented by the following chemical formulas (39) and (40) was synthesized. The monomer 3 has a group that loses an anion exchange group (sulfonium group) by light irradiation, and the monomer 4 has a polyhedral oligosilsesquioxane derivative group that is a three-dimensionally crosslinkable group.

共重合体ポリマー３の合成は、３種類のモノマーの混合物を脱気したテトラヒドロフラン（ＴＨＦ）に溶解した混合溶液に、重合開始剤として２，２’−アゾビスイソブチロニトリル（ＡＩＢＮ）を加えて、アルゴン雰囲気下、重合することによって行った。ポリマー３の重量平均分子量＝１７万。各モノマーのポリマー３中における重量分率は次の通り。モノマー３＝１７％、モノマー４＝２２％、メチルメタクリレート＝６１％。

Synthesis of the copolymer 3 is performed by adding 2,2′-azobisisobutyronitrile (AIBN) as a polymerization initiator to a mixed solution obtained by dissolving a mixture of three kinds of monomers in degassed tetrahydrofuran (THF). The polymerization was performed by polymerization under an argon atmosphere. Weight average molecular weight of polymer 3 = 170,000. The weight fraction of each monomer in Polymer 3 is as follows. Monomer 3 = 17%, Monomer 4 = 22%, Methyl methacrylate = 61%.

Formation of Photosensitive Layer A hydrophilic PTFE porous sheet (average pore diameter: 0.2 μm, film thickness: 20 μm) was immersed in a 5% by weight THF solution of the synthesized polymer 3. After immersion, the solution was sufficiently permeated into the porous sheet and then pulled up, air-dried, and the pore inner surface of the porous sheet was coated with a polymer. Even after the coating, the pores of the porous sheet were not closed and maintained a porous state.

Exposure Exposure was performed using a parallel exposure device CANON PLA501 under the condition of a light amount of 800 mJ / cm ² through a mask of a dot array pattern (dot pitch = 500 μm) having a dot-shaped light-shielding portion with a dot diameter of 200 μm. Since the anion exchange group (sulfonium group) in the exposed area was decomposed and lost anion exchange ability, a pattern latent image in which the anion exchange group was arranged only in the unexposed area could be formed.

Adsorption of plating nuclei The porous sheet on which the pattern latent image was formed was immersed in the same aqueous solution of complex 1 as used in Example 2. Complex 1 has a sodium salt of a carboxyl group as a binding group. This binding group adsorbs to the sulfonium group which is an anion exchange group.

  The complex 1 was immersed in an aqueous solution of the complex 1 for 30 minutes to adsorb the complex 1 to a sulfonium group which is an anion exchange group. After the adsorption, extra complex 1 was removed by washing with distilled water. After washing, it was immersed in a 0.01 M aqueous solution of sodium borohydride for 5 minutes, and then washed with distilled water.

Plating After washing with distilled water, immersion in an electroless copper plating solution PS-503 at 40 degrees for 3 hours to perform copper plating, and forming a dot array having a dot diameter of 200 μm and a dot pitch of 500 μm on the front and back surfaces of the porous sheet. A composite member that can be used as an anisotropic conductive sheet through which copper was deposited was obtained. In the prepared composite member, no poor plating or the like caused by peeling of the photosensitive composition layer was observed, and a favorable copper pattern was formed.

(Example 7)
(Example using a photosensitive polymer that loses an anion exchange group)
Example 7 In Example 7, a copper pattern was formed on a resin substrate using a photosensitive polymer having a photosensitive group that disappears an anion exchange group as an example of a method for manufacturing a composite member according to the first aspect of the present invention. How to do it.

Synthesis of Polymer 4 Polymer 4 represented by the following chemical formula (41) was used as a polymer for forming a photosensitive layer. The sulfonium group in the side chain of the polymer functions as an anion exchange group, and loses an anion exchange ability upon exposure.

ポリマー４は以下のようにして合成した。還流管を装着した３００ｍｌナスフラスコ中、キシリレンジクロライド１０ｇのメタノール溶液（０．７５Ｍ）に１５ｇのテトラヒドロチオフェンを加え、５０度で２０時間攪拌した。攪拌後、溶媒を留去した。メタノールに少量の水を混合した混合溶媒少量に残留物を溶解し、０度のアセトン中に再沈した。沈殿を０度のアセトンで洗浄した後、真空乾燥し、白色沈殿を得た。

Polymer 4 was synthesized as follows. In a 300 ml eggplant flask equipped with a reflux tube, 15 g of tetrahydrothiophene was added to a methanol solution (0.75 M) of 10 g of xylylene dichloride, and the mixture was stirred at 50 degrees for 20 hours. After stirring, the solvent was distilled off. The residue was dissolved in a small amount of a mixed solvent obtained by mixing a small amount of water with methanol, and reprecipitated in acetone at 0 ° C. The precipitate was washed with acetone at 0 ° C., and then dried under vacuum to obtain a white precipitate.

  Under an argon stream, 3.51 g of the obtained white precipitate was dissolved in 50 ml of degassed water, and 50 ml of a 0.1 M aqueous sodium hydroxide solution was added dropwise over 5 minutes while cooling with ice. After the addition, the mixture was stirred for 1 hour under ice cooling. After stirring, a 1 M aqueous hydrochloric acid solution was added to neutralize the solution to about pH 6. After the neutralization, the reaction solution was filled in a semi-permeable membrane (trade name: Spectra / Pore 3, Mw3500), and dialyzed against water degassed by blowing argon gas for 3 days. After dialysis, an aqueous solution of Polymer 4 was obtained as a pale yellow liquid.

Formation of Photosensitive Layer An aqueous solution of the obtained polymer 4 was applied on a glass fiber reinforced bismaleimide-triazine resin substrate whose surface was roughened. The coating was performed by a spin coating method at a rotation speed of 3000 rpm. After the application, the film was air-dried at room temperature to form a thin film of polymer 4 on the substrate surface.

Exposure Exposure was performed on a bismaleimide-triazine resin substrate on which a thin film of polymer 4 was formed through a mask of a wiring pattern (line pitch = 500 μm) having a line-shaped light-shielding portion with a line width of 200 μm under a light amount of 7 J / cm ² . . Since the anion exchange group (sulfonium group) in the exposed area was decomposed and lost anion exchange ability, a pattern latent image in which the anion exchange group was arranged only in the unexposed area could be formed.

Adsorption of plating nuclei A bismaleimide-triazine resin substrate on which a pattern latent image was formed was immersed in a 10% by weight aqueous solution of sodium chloroaurate for 30 minutes to adsorb chloroaurate ions on sulfonium groups. After the adsorption, it was washed with distilled water to remove excess sodium chloroaurate aqueous solution. After washing, it was immersed in a 0.01 M aqueous solution of sodium borohydride for 5 minutes, and then washed with distilled water. The unexposed portion exhibited purple due to surface plasmon absorption of the generated fine gold particles.

Plating After washing with distilled water, copper plating was performed by immersion in an electroless copper plating solution PS-503 at 40 degrees for 3 hours. After copper plating, it is heat-treated at 200 ° C. for 30 minutes under a nitrogen stream, and can be used as a wiring board having copper deposited on a bismaleimide-triazine resin substrate in a line shape with a line width of 200 μm and a line pitch of 500 μm. A composite member was obtained. In this heating step, the remaining sulfonium groups of the polymer 4 are eliminated and changed to non-ionic and heat-resistant polyparaphenylene vinylene or its oxide without fear of corrosion.

Evaluation In the prepared composite member, no poor plating or the like due to peeling of the photosensitive composition layer was observed, and a favorable copper pattern was formed. The sheet resistance of the wiring was about 1.5 mΩ / □, indicating a sufficient conductivity. Further, the peeling strength of the wiring from the substrate was as good as 1 N / cm or more.

(Example 8)
(Example using a silane coupling type photosensitive compound)
In Example 8, as an example of the method for producing a composite member according to the second aspect of the present invention, a photosensitive compound having both a group binding to a functional group on the substrate surface and a photosensitive group in one molecule was used. A method for forming a copper pattern on a glass substrate will be described.

Formation of Photosensitive Layer A solution of a photosensitive composition in which a photosensitive compound represented by the following chemical formula (42) and triisopropoxyaluminum were mixed at a weight ratio of 80: 1 was prepared.

調整した感光性組成物溶液を、常法により清浄にしたガラス基板上に、スピンコーティング法により塗布した。塗布後、ホットプレート上でガラス基板を１００℃で１分間加熱して、塗布膜を乾燥させて感光性層を形成した。得られた感光性層の厚さは５ｎｍ程度であった。感光性化合物から発生するシラノール基はガラス表面のシラノール基と脱水縮合反応によりシロキサン結合を形成する。

The prepared photosensitive composition solution was applied on a glass substrate cleaned by a conventional method by a spin coating method. After the application, the glass substrate was heated on a hot plate at 100 ° C. for 1 minute, and the applied film was dried to form a photosensitive layer. The thickness of the obtained photosensitive layer was about 5 nm. The silanol group generated from the photosensitive compound forms a siloxane bond with the silanol group on the glass surface by a dehydration condensation reaction.

Exposure The glass substrate on which the photosensitive layer is formed is exposed under a condition of a light amount of 50 mJ / cm ² through a mask of a wiring pattern having a line width of 200 μm (line pitch = 500 μm), and an amino group is formed in an exposed portion. A latent image was formed.

Adsorption of plating nuclei The glass substrate on which the pattern latent image was formed was immersed in a 10 wt% aqueous solution of chloroplatinic acid for 30 minutes to adsorb platinum complex ions to amino groups. After the adsorption, it was washed with distilled water to remove excess chloroplatinic acid aqueous solution. After washing, it was immersed in a 0.01 M aqueous solution of sodium borohydride for 5 minutes, and then washed with distilled water.

Plating After washing with distilled water, copper plating was performed by immersion in an electroless copper plating solution PS-503 at 40 ° C. for 5 hours. A composite member that can be used as a wiring board having copper deposited on a glass substrate in a line shape with a line width of 200 μm and a line pitch of 500 μm was obtained.

Evaluation In the prepared composite member, no poor plating or the like due to peeling of the photosensitive composition layer was observed, and a favorable copper pattern was formed. The sheet resistance of the wiring was about 8 mΩ / □, indicating conductivity that can be used as the wiring.

Formation of Inversion Pattern A fluorine compound (3-perfluorohexyl-1,2-epoxypropane) was brought into contact with the glass substrate on which the above-described pattern latent image was formed, and heated at 80 degrees for 10 minutes. Thereby, the fluorine compound forms a bond with the amino group generated in the exposed area and is adsorbed. The portion where the fluorine compound is adsorbed changes to water repellency. After the adsorption, the entire surface was exposed under the condition of a light quantity of 200 mJ / cm ² . As a result, amino groups were generated in portions other than the portion where the fluorine compound was adsorbed. After the entire surface exposure, the glass substrate was immersed in a 10% by weight aqueous solution of sodium chloroaurate for 30 minutes to adsorb chloroaurate ions to amino groups. After the adsorption, it was washed with distilled water to remove excess sodium chloroaurate aqueous solution. After washing, it was immersed in a 0.01 M aqueous solution of sodium borohydride for 5 minutes, and then washed with distilled water. After washing with distilled water, it was immersed in an electroless copper plating solution PS-503 at 40 degrees for 5 hours to perform copper plating. A composite member which was used as a wiring substrate in which copper was deposited on a glass substrate in a line shape having a line width of 300 μm and a line pitch of 500 μm, which was inverted from the mask pattern at the time of the first exposure, was obtained.

(Example 9)
(Electrolytic plating)
In Example 9, as an example of the manufacturing method according to the third embodiment of the present invention, a wiring or via was formed on a porous sheet by electrolytic plating using a photosensitive polymer which generates an amino group which is an anion exchangeable group upon exposure. A method for forming the same will be described.

Formation of Photosensitive Layer A PTFE porous sheet (average pore diameter: 0.2 μm, film thickness: 20 μm) subjected to hydrophilization treatment was immersed in the same 5% by weight THF solution of Polymer 1 as used in Example 1. After immersion, the solution was sufficiently permeated into the porous sheet and then pulled up, air-dried, and the inner surface of pores of the porous sheet was coated with polymer 1. Even after the coating, the pores of the porous sheet were not closed and maintained a porous state.

Exposure Using a parallel exposure device (PLA501 manufactured by Canon Inc.), a light amount of 1.2 J / cm ^{2 was} passed through a mask on which a wiring pattern having a line width of 50 μm and a space of 50 μm and a via pattern having a diameter of 50 μm were formed. To form a pattern latent image in which an amino group was formed in the exposed portion.

Electroplating The exposed porous sheet was attached to a 0.5 mm-thick copper electrode via a conductive adhesive tape. This was immersed in an electrolytic plating solution and electrolytically plated at an applied voltage of 6 V using a copper plate as a counter electrode. As the electrolytic plating solution, a mixed solution of copper sulfate and calcium chloride was used. Since the electrolytic plating solution is acidic, the amino group generated in the exposed portion changes to an ammonium ion having strong hydrophilicity. For this reason, the plating solution selectively penetrated into the exposed portion. Copper is deposited only on the exposed portion where the plating solution has penetrated by electrolytic plating, and used as a wiring sheet or an anisotropic conductive sheet in which a Cu wiring having a line width of 50 μm and a space of 50 μm and a Cu via having a diameter of 50 μm are formed. Thus, a composite member was obtained.

Evaluation When the cross section of the portion of the Cu wiring and the Cu via was observed with a scanning electron microscope, the pores of the porous sheet were almost completely filled with copper.

(Example 10)
In Example 10, as an example of the manufacturing method according to the third aspect of the present invention, a wiring or via was formed on a porous sheet by electrolytic plating using a photosensitive polymer which disappears a sulfonyl group which is an anion exchange group by exposure. A method for forming the same will be described.

Synthesis of Polymer 5 A copolymer 5 of the same monomer 3 as used in Example 6 and polymethyl methacrylate (PMMA) was synthesized. Synthesis of the copolymer 5 is performed by adding 2,2′-azobisisobutyronitrile (AIBN) as a polymerization initiator to a mixed solution obtained by dissolving a mixture of two kinds of monomers in degassed tetrahydrofuran (THF). The polymerization was performed by polymerization under an argon atmosphere. Weight average molecular weight of polymer 3 = 30,000. The weight fraction of each monomer in Polymer 5 is as follows. Monomer 3 = 32%, methyl methacrylate = 68%.

Formation of Photosensitive Layer A hydrophilic PTFE porous sheet (average pore diameter: 0.2 μm, film thickness: 20 μm) was immersed in a 5% by weight THF solution of the synthesized polymer 5. After immersion, the solution was sufficiently permeated into the porous sheet and then pulled up, air-dried, and the pore inner surface of the porous sheet was coated with a polymer. Even after the coating, the pores of the porous sheet were not closed and maintained a porous state.

Exposure Exposure was performed using a parallel exposure unit CANON PLA501 under a condition of a light amount of 1.2 J / cm ² through a mask of a dot array pattern (dot pitch = 500 μm) having a dot-shaped light-shielding portion with a dot diameter of 200 μm. The anion exchange group (sulfonium group) in the exposed area is decomposed and changes to hydrophobic. On the other hand, the anion exchange group present in the dot-shaped unexposed portion is hydrophilic, and the plating solution can penetrate.

Electroplating The exposed porous sheet was tightly wound and fixed on a stainless steel cylinder having a diameter of 2 cm. This was immersed in an electrolytic plating solution and electrolytically plated at an applied voltage of 6 V using a copper plate as a counter electrode. As the electrolytic plating solution, a mixed solution of copper sulfate and calcium chloride was used. The electrolytic plating solution selectively permeated into the unexposed portions where the sulfonium group was present. When the stainless steel electrode is energized, copper is deposited only on the unexposed portions where the plating solution has penetrated by electrolytic plating, and a wiring sheet having a dot array pattern (dot pitch = 500 μm) with a dot diameter of 200 μm and a Cu via is formed. A composite member that can be used as an anisotropic conductive sheet was obtained.

Evaluation When the cross section of the portion of the Cu wiring and the Cu via was observed with a scanning electron microscope, the pores of the porous sheet were almost completely filled with copper.

(Example 11)
In Example 11, as an example of the method of manufacturing the composite member according to the third aspect of the present invention, a method of continuously forming a copper pattern on a porous sheet using a roll-shaped electrode will be described.

Preparation of Porous Sheet In the same manner as in Example 9, a porous sheet on which a pattern latent image was formed was prepared.

  The porous sheet had a band shape of 5 cm in width and 1 m in length.

Electroplating Using Rolled Electrode The porous sheet on which the latent image was formed was continuously electroplated using the rolled electrode. FIG. 6 shows a schematic view of the electrolytic plating apparatus used in FIG. The porous sheet on which the latent image is formed is pulled out from the reel 41 and introduced into the electrolytic plating tank 43. The electrolytic plating bath 43 is filled with an electrolytic plating solution 44. The porous sheet is immersed in the electrolytic plating solution while being wound around the rotating roll-shaped electrode 45 and in close contact therewith. Electric current is applied to the roll-shaped electrode 45 and the counter electrode 46 made of copper, and plating is deposited on a plating solution permeable region (in the case of this embodiment, an exposed portion) of the porous sheet in close contact with the roll-shaped electrode 45 to form a conductive portion. Is formed. The porous sheet 47 on which the conductive portion is formed is inspected by a test roll 48 to determine whether the conductive portion is penetrated on the front and back of the porous sheet. The inspection roll is a roll having a pair of surfaces coated with conductive rubber. The two rolls are arranged so as to sandwich the porous sheet, and contact the front and back surfaces of the porous sheet, respectively. By measuring the conductivity between the two rolls, it is confirmed that the conductive portion is formed penetrating the front and back of the porous sheet. After the inspection, it is introduced into the washing tank 49, and the remaining electrolytic plating solution is washed away. After the cleaning, the porous sheet having the conductive portion formed thereon is wound around a reel 50.

  As the roll electrode 45, a stainless steel cylinder having a diameter of 2 cm and a length of 10 cm was used. The distance between the surface of the roll electrode 45 and the surface of the counter electrode 46 was 1 cm. The same electrolytic plating solution as in Example 9 was used. The speed at which the porous sheet was fed was adjusted based on the results of inspection by the inspection roll 48. As a result, a composite member that can be used as a wiring sheet or an anisotropic conductive sheet having a Cu wiring having a line width of 50 μm and a space of 50 μm and a Cu via having a diameter of 50 μm was obtained.

Evaluation When the cross section of the portion of the Cu wiring and the Cu via was observed with a scanning electron microscope, the pores of the porous sheet were almost completely filled with copper.

(Example 12)
In Example 12, as an example of the photosensitive compound for forming a composite member of the present invention, a photosensitive polymer having a photosensitive group generating an anion exchange group and a crosslinkable group was used. A method of manufacturing the composite member according to the second aspect will be described.

Photosensitive polymer and photosensitive composition Photosensitive polymers 6 and 7 represented by the following chemical formulas (43) and (44) were used. Both polymer 6 and polymer 7 were synthesized by a radical polymerization method.

ポリマー６
重量平均分子量Ｍｗ＝３１０００、ａ：ｂ：ｃ＝２：５：１
ポリマー７
重量平均分子量Ｍｗ＝２２０００、ａ：ｂ：ｃ：ｄ＝６：１４：５：１
ポリマー７は５重量％のＢＴＴＢを添加して用いた。

Polymer 6
Weight average molecular weight Mw = 31000, a: b: c = 2: 5: 1
Polymer 7
Weight average molecular weight Mw = 22000, a: b: c: d = 6: 14: 5: 1
Polymer 7 was used with the addition of 5 wt% BTTB.

Formation of copper pattern A Cu wiring pattern was formed in the same manner as in Example 1 except that a polymer 6 or a composition of polymer 7 and BTTB was used as a polymer for forming a photosensitive layer. A composite member on which a wiring pattern was formed could be formed.

  Also, using a composition of polymer 6 or polymer 7 and BTTB, after immersing in an aqueous solution of chloroplatinic acid, washing with water, and then performing ultrasonic cleaning with acetone for 2 minutes, the same procedure as in Example 1 was repeated for Cu wiring. When the patterns were formed, a composite member having a Cu wiring pattern formed thereon could be formed without any problem.

  However, as a comparative example, a Cu wiring pattern was formed in the same manner as in Example 1 except that polymer 1 was immersed in an aqueous solution of chloroplatinic acid, washed with water, and then subjected to ultrasonic cleaning with acetone for 5 minutes. Microscopic observation of a defect in the Cu wiring pattern, which is considered to be caused by peeling of the photosensitive layer, could be confirmed in some parts of the wiring.

  From this, it was found that the polymer 6 or the polymer 7 having a crosslinkable group had improved durability against a solvent (in this case, acetone) as compared with the polymer 1.

  Polymer 6 or polymer 7 can also be used in the method for producing a composite member according to the third aspect of the present invention.

(Example 13)
In Example 13, a first embodiment of the present invention using a photosensitive polymer having a photosensitive group capable of eliminating an anion exchange group and a crosslinkable group as an example of the photosensitive compound for forming a composite member of the present invention. The method of manufacturing the composite member will be described.

Photosensitive polymer and photosensitive composition Photosensitive polymers 8 and 9 represented by the following chemical formulas (45) and (46) were used. Both Polymer 8 and Polymer 9 were synthesized by a radical polymerization method.

ポリマー８
重量平均分子量Ｍｗ＝３４０００、ｍ：ｎ＝７：３
ポリマー９
重量平均分子量Ｍｗ＝２１０００、ｍ：ｎ：ｌ＝６：５：１
ポリマー９は５重量％のＢＴＴＢを添加して用いた。

Polymer 8
Weight average molecular weight Mw = 34000, m: n = 7: 3
Polymer 9
Weight average molecular weight Mw = 21000, m: n: l = 6: 5: 1
Polymer 9 was used with the addition of 5 wt% BTTB.

Formation of copper pattern A Cu wiring pattern was formed in the same manner as in Example 6 except that a polymer 8 or a composition of polymer 9 and BTTB was used as a polymer for forming the photosensitive layer. A composite member on which a wiring pattern was formed could be formed.

  The same procedure as in Example 6 was repeated except that a polymer 8 or a composition of polymer 9 and BTTB was used, immersed in an aqueous solution of complex 1, washed with water, and then subjected to ultrasonic cleaning with acetone for 2 minutes. When the patterns were formed, a composite member having a Cu wiring pattern formed thereon could be formed without any problem.

  However, as a comparative example, a Cu wiring pattern was formed in the same manner as in Example 6, except that the polymer 5 was immersed in an aqueous solution of the complex 1, washed with water, and then subjected to ultrasonic cleaning with acetone for 5 minutes. Microscopic observation of a defect in the Cu wiring pattern, which is considered to be caused by peeling of the photosensitive layer, could be confirmed in some parts of the wiring. By the way, when produced in the same manner as in Example 6 except that the polymer 5 was used, such a defect of the Cu wiring pattern was not recognized.

  From this, it was found that the polymer 6 or the polymer 7 having a crosslinkable group has improved durability against a solvent (in this case, acetone) as compared with the polymer 5.

  Polymer 8 or polymer 9 can also be used in the method for producing a composite member according to the third aspect of the present invention.

(Example 14)
In Example 14, as an example of the photosensitive material for forming a composite member of the present invention, a photosensitive polymer having an azide derivative group, which is a photosensitive group generating an anion exchange group, A method for producing a composite member according to the first or second aspect of the present invention using a photosensitive material containing a phenol novolak resin that reacts with and crosslinks with the nitrene produced by the reaction will be described.

Photosensitive Polymer and Crosslinking Aid A photosensitive azide group-containing polymer represented by the following chemical formula (47) was used. The azide group-containing polymer was synthesized from partially acetylated polyvinyl alcohol. The phenol novolak resin used had a molecular weight of 6,500.

Polymer A polymer having a weight average molecular weight Mw of 24,000 and an m: n ratio of 6: 4 was used.
Formation of Copper Pattern When forming the photosensitive layer, a Cu wiring pattern was formed in the same manner as in Example 1, except that a mixed solution of 9: 1 by weight of the azide group-containing polymer and the phenol novolak resin was applied. However, similarly, a composite member having a Cu wiring pattern formed thereon could be formed. The azide group-containing polymer or a mixture of this polymer and a phenol novolak resin can be used in the method for producing a composite member according to the third aspect of the present invention.

FIGS. 1A to 1E are diagrams illustrating a manufacturing process of a method for manufacturing a composite member according to a third embodiment of the present invention. The sectional view of the base material in each process is shown. It is sectional drawing of the manufacturing apparatus which manufactures using the roll-shaped electrode in the 3rd aspect of the manufacturing method of the composite member of this invention. 5 is an example of a manufacturing apparatus when performing the first or second aspect of the method for manufacturing a composite member of the present invention in a “reel-to-reel” continuous process. 6 is an example of a manufacturing apparatus when the third aspect of the method for manufacturing a composite member of the present invention is performed in a “reel-to-reel” continuous process. 6 is an example of a manufacturing apparatus when the third aspect of the method for manufacturing a composite member of the present invention is continuously performed using a roll electrode.

Explanation of reference numerals

DESCRIPTION OF SYMBOLS 1 Porous sheet 2 Electrode 3 Plating solution permeable area 4 Conductive part 5 deposited by electrolytic plating 5 Conductive part formed penetrating porous sheet 6 Conductive part formed protruding on the upper surface of porous sheet 7 Roll shape Electrode 8 Sheet-like porous body having plating solution-permeable region 9 formed Plating solution-permeable region 10 Electroplating solution 11 Electroplating solution tank 12 Conducting part 13 deposited and formed through sheet-shaped porous body Conductive part 14 Reel for supplying a photosensitive porous sheet having a photosensitive layer formed thereon 15 Exposure device 16 Plating nucleus adsorption tank 17 containing a solution such as aqueous chloroplatinic acid solution 17 Air knife 18 for removing residual liquid 18 Rinse with water Tank 19 Reduction tank 20 for reducing and metallizing plating nuclei 20 Rinse tank 21 Electroless plating tank 22 Rinse tank 23 Dryer 24 Reel 25 for accommodating porous sheet formed with conductive part Reel 26 for supplying a photosensitive porous sheet protected on its surface with a protective film Photosensitive porous sheet 27 protected on both sides with a protective film Roll 28 for peeling off the protective film Peeled-off protective film 29 Reel 30 for collecting peeled protective film Exposure device 31 Exposure device 31 Porous sheet on which latent image has been formed by exposure Roll electrode 33 Electroplating solution 34 Electroplating solution tank 35 Air knife for removing plating solution 36 Porous sheet on which conductive portion is formed 37 Rinse tank 38 Air knife 39 for removing rinsing water Dryer 40 Reel 41 containing porous sheet on which conductive portion is formed Porous on which latent image is formed Reel 42 for supplying a sheet Porous sheet 43 on which a latent image is formed Electrolytic plating tank 44 Electroplating solution 45 Roll electrode 46 Reel for accommodating the porous sheet formed of 47 conductive portion is formed porous sheet 48 inspection roll 49 a water washing tank 50 conductive parts

Claims (3)

In a method of manufacturing a composite member for selectively forming a conductive portion at a predetermined portion of an insulating porous body, the conductive portion is formed by the following electrode installation step, surface partial modification step, plating solution infiltration step, electrolysis A method for producing a composite member, which is performed through a plating step.
Electrode setting step: a step of setting an electrode on the porous body;
Surface Partial Reforming Step: A part of the porous body is modified to change its surface energy, and a pattern is obtained in which the affinity of the modified part for water is different from the affinity of the non-reformed part for water. Forming,
Plating solution infiltration step: a step of selectively infiltrating a plating solution into an insulated region of a modified portion or a non-modified portion in the porous body selected in contact with the electrode surface;
Electroplating step: a step of energizing the electrodes to deposit electroplating in the region to form a conductive portion. The surface part modification step irradiates the porous body with energy rays to change the surface energy of the inner surface of the pores of the irradiation part, and the irradiated part or the non-irradiated part is selectively hydrophilic. The method for producing a composite member according to claim 1, wherein the method is an energy beam irradiation step for forming the composite member. The inner surface of the pores of the porous body is characterized in that a photosensitive layer made of a photosensitive substance whose surface energy is changed by irradiation with energy rays, which is different from a substance constituting the porous body, is formed. A method for manufacturing a composite member according to claim 2.

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