JP4314236B2 - Method for manufacturing composite member, photosensitive composition, insulator for manufacturing composite member, composite member, multilayer wiring board, and electronic package - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite member, having high flexibility in the design of a conductive circuit, with no influence on selecting the material of an insulator or molding and processing the insulator at a low cost, having no abnormal deposition of a metal on the insulator and being capable of easily forming a conductive part that has a fine pattern. <P>SOLUTION: A composite member is provided, wherein a conductive part is formed via an organic compound on at least one of the surface or inside of a porous insulator. The content of the organic compound, that exists between the insulator and the conductive part per unit area on the surface of the insulator, is larger than the content of the organic compound that exists other than the part between the insulator and the conductive part per unit area on the surface of the insulator. <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

  The present invention relates to a method of manufacturing a composite member that is used for a wiring board or the like in the fields of electricity, electronics, communication, and the like and in which a conductive portion such as wiring is formed on an insulator. Moreover, this invention relates to the photosensitive composition and insulator which can be used suitably for such a manufacturing method. Furthermore, the present invention relates to a composite member manufactured by such a method, a multilayer wiring board including the composite member, and an electronic package.

  In recent years, high integration and miniaturization of various electric and electronic parts including semiconductors have been progressing. It is certain that this trend will intensify in the future. In connection with this, fine wiring of metal wiring, fine pitch, three-dimensional wiring, and the like have been attempted in order to perform high-density mounting on a printed wiring board.

  In particular, three-dimensional wiring is indispensable for high-density mounting, and various methods have been proposed for manufacturing a wiring board having three-dimensional wiring.

  However, according to the conventional method for manufacturing a wiring board, it is difficult to easily form a fine three-dimensional wiring having a three-dimensional free shape.

  When forming a three-dimensional wiring on a wiring board, a multilayer wiring board structure is configured by stacking two-dimensional wiring boards, as represented by, for example, a build-up wiring board. In such a multilayer wiring board structure, adjacent wiring layers are coupled by conductive columns called vias.

  Conventionally, such vias have been formed by the following method. First, through holes (via holes) are provided in the insulator by a photolithography process using photosensitive polyimide, resist, or the like. Then, vias are formed by selectively plating or filling the holes with conductive paste. In order to form vias by such a method, steps of resist application, exposure, and etching are required. For this reason, it takes time and it is difficult to improve the yield.

As another example of the via formation method, there is a method in which a via hole having a predetermined size is provided in an insulator using a drill or a CO ₂ laser, and the hole is plated or filled with a conductive paste.

  However, with such a method of drilling an insulator, it is difficult to freely form a fine via of several tens of microns or less at a desired position.

  In the method described in JP-A-7-207450, a compound having a hydrophilic group is allowed to enter the pores of a three-dimensional porous film such as PTFE, and in this state, a low-pressure mercury lamp (wavelengths of 185 nm and 254 nm) is used. Perform pattern exposure. Thereby, a hydrophilic group is formed on the three-dimensional porous film. Furthermore, metal plating is performed on the three-dimensional porous film.

  However, in the above-described method, since the exposure is performed with light having a short wavelength, the material constituting the three-dimensional porous film is deteriorated. In addition, the exposure light is absorbed by the three-dimensional porous film so that the exposure light does not penetrate into the porous body and fine vias cannot be formed.

  Further, in the above-described method, PTFE constituting the three-dimensional porous film reacts with the exposure light to selectively generate a hydrophilic group, but this PTFE has poor molding processability and high cost. And so on.

  Japanese Patent Application Laid-Open No. 11-24977 describes another method for forming a via. In this method, first, the entire surface of the insulator made of a porous material is impregnated with a photosensitive composition containing a photosensitive reducing agent and a metal salt. Next, post pattern exposure is performed to reduce the cation of the metal salt in the exposed portion to a metal nucleus. Thereafter, the photosensitive composition in the unexposed area is washed and removed, and further, electroless plating or solder is applied to the remaining metal core, thereby forming a via having a desired pattern.

  However, in this method, the entire surface of the porous insulator is impregnated with the photosensitive composition containing the metal salt, so that the metal salt adsorbed on the portion corresponding to the unexposed portion is completely removed after exposure. Is difficult. Therefore, in the subsequent reduction process, a phenomenon occurs in which metal nuclei are deposited in an undesired portion. Such abnormal deposition of metal nuclei causes a problem in insulating characteristics between adjacent vias and wiring layers as the pattern becomes finer.

  In addition, the via formed in the insulator substrate by the conventional method for manufacturing a wiring substrate has a structure in which the insulator and the conductive portion are in direct contact with each other. In that case, since both are inferior in adhesiveness, the problem that an electroconductive part will peel from an insulator board | substrate will arise in use.

  Furthermore, when a multilayer wiring board is configured by laminating a plurality of wiring boards formed by a conventional wiring board manufacturing method, the electrical connection between the wiring layers of each wiring board and the electrical conductivity of the wiring are further improved. Was demanded.

The present invention has a high degree of freedom in designing a conductive circuit, does not cause deterioration of the insulator due to exposure, and can easily form a conductive portion having a fine pattern without abnormal metal deposition on the insulator. An object is to provide a composite member.

In order to solve the above problems, the present invention is a conductive portion on the insulator surface or at least one of the predetermined region within the porous, a composite member consisting formed through an organic compound, the organic compound Is formed by exposing a photosensitive composition containing a compound that has a structure different from that of the porous insulator and generates an ion-exchange group, and the conductive portion covers the inner pore surface of the insulator. It is formed by coating with a photosensitive composition, selectively generating ion-exchange groups in the exposed area, selectively binding metal ions or metal fine particles thereto, and metallizing by contacting with a reducing agent, of the organic compounds present between the insulator and the conductive portion is exposed portion, the content per unit surface area in the insulator surface, in addition to between the insulator and the conductive portion is an unexposed portion The organic compound present , To provide a composite member, characterized in that more than the content per unit surface area in the insulator surface.

According to the present invention, it is possible to easily form a conductive portion having a fine pattern with a high degree of freedom in designing a conductive circuit, without causing deterioration of the insulator by exposure, and without an abnormal deposition of metal on the insulator. it composite member capable is Ru are provided.

  Hereinafter, the present invention will be described in detail.

  The method for producing the composite member of the present invention will be described with reference to FIG. 1, taking as an example the case of forming a conductive portion extending in the planar direction and thickness direction of a sheet-like insulator.

  FIG. 1 is a schematic sectional view showing a method for producing a composite member of the present invention.

  In the present invention, at least the steps (1) to (3) and, if necessary, the following (4) and (5) are performed to form a conductive portion having a fine pattern on the insulator. Here, the case where the photosensitive composition containing the compound which produces | generates an ion exchange group by light irradiation is used is shown. Each step will be described below.

  Step (1): First, as shown in FIG. 1A, a photosensitive composition layer 2 containing a compound that generates an ion-exchange group by light irradiation is formed on the insulator 1. In the case where the pattern of the conductive portion is formed in the planar direction and the thickness direction of the insulator 1, the insulator 1 can be easily and accurately formed by using a porous body.

  Step (2): Next, as shown in FIG. 1B, the photosensitive composition layer 2 formed on the insulator 1 is subjected to pattern exposure through a mask 3 to expose the photosensitive composition layer 2. An ion exchange group is generated in part 4. When the insulator 1 is a porous body, the inside of the insulator 1 is also exposed.

  Step (3): Thereafter, a metal ion or a metal is bonded to the ion-exchangeable group generated in the exposed portion 4 by pattern exposure in the step (2) as shown in FIG.

  Step (4): If necessary, the conductivity is improved by reducing the metal ions bound to the ion exchange groups of the exposed portion 4 to metallize the metal ions as shown in FIG. 1 (d). Let

  Step (5): Further, if necessary, electroless plating 5 is applied to the conductive portion formed in the exposed portion 4 as shown in FIG.

  In addition, when the photosensitive composition containing the compound which lose | disappears an ion exchange group by exposure is used, the ion exchange group of an exposure part lose | disappears in a 2nd process, and an ion exchange group remains in an unexposed part. As a result, a negative pattern is formed.

  In steps (1) to (3) (if necessary (4) and (5)) relating to the method for producing a composite member of the present invention, complicated procedures such as resist coating, etching, and resist peeling are required. No process is required. Therefore, the process is simplified as compared with a conventional method for manufacturing a wiring substrate in which a through hole is formed using photolithography or a mechanical technique. In addition, if a porous body is used as the insulator, there is no step of selectively filling plating or a conductive paste to form a conductive portion, and the work becomes easy.

  In addition, the accuracy of the pattern shape of the conductive portion can be improved, and a fine pattern controlled to several tens of μm or less can be easily formed. For this reason, the degree of freedom in designing the conductive portion formed in the insulator is also improved.

  In the method for manufacturing a wiring board described in Japanese Patent Application Laid-Open No. 11-24977, it is necessary to previously form a photosensitive composition containing a metal salt on the entire insulator. On the other hand, in the present invention, since such a process is not necessary, a phenomenon that metal nuclei are deposited in an undesired portion does not occur. As a result, it is possible to form a conductive portion having a fine pattern shape with high accuracy only in a desired portion.

  In the first and second embodiments of the present invention, as a compound that generates or disappears an ion-exchange group by light irradiation, a compound that generates an ion-exchange group by light irradiation with a wavelength of 280 nm or more is used as exposure light. Light having a wavelength of 280 nm or more is used. Thereby, damage caused to the insulator by exposure is reduced, and deterioration of the insulator is reduced. Further, the absorption of exposure light in the insulator is reduced. For this reason, it becomes advantageous when forming the electroconductive part penetrated in the film thickness direction especially using the insulator which consists of a porous body. In particular, for use in a wiring board, when the insulator is a polymer, it is necessary to use a heat resistant polymer. Many heat-resistant polymers often have an aromatic / heterocyclic structure such as a benzene ring in the main chain or side chain, and the aromatic / heterocyclic structure absorbs light in the ultraviolet region. For example, the benzene ring has an absorption peak near 254 nm. For this reason, light with a short wavelength of 280 nm or less is almost absorbed, and it is difficult to expose through the film thickness direction. By using light having a long wavelength with little absorption of an aromatic / heterocyclic structure as exposure light, a conductive part having a fine pattern with higher accuracy can be formed.

  In the third aspect of the present invention, at least one selected from an onium salt derivative, a sulfonium ester derivative, a carboxylic acid derivative, and a naphthoquinonediazide derivative is used as the compound that generates an ion-exchange group by light irradiation. Photosensitive compounds containing derivatives are used. The compound group enumerated here is rich in versatility, and easily generates an ion exchange group by light irradiation. For this reason, the conductive part having a fine pattern can be formed with high accuracy. Furthermore, they can be applied to any insulator such as ceramic or organic insulating material. Therefore, it is possible to use an insulator having a low cost and high moldability.

  In the method using PTFE described in JP-A-7-207450, a liquid such as water or alcohol is usually used as a compound having a hydrophilic group, and exposure is performed in a state in which these liquids are wet in a porous film. Need to do. For this reason, there existed problems, such as a process and an exposure apparatus becoming complicated. However, according to the present invention, such a problem does not occur, and the conductive portion can be easily formed.

  In the production method of the present invention, a photosensitive composition containing at least a naphthoquinone diazide derivative and a carbodiimide derivative is preferably used.

  The naphthoquinone diazide derivative acts as a photosensitive component, and it is preferable to use a derivative added to a compound having a high molecular weight, such as a phenol resin addition type, in consideration of film forming properties. At this time, the naphthoquinonediazide derivative easily generates an ion-exchangeable carboxyl group with a high resolution by irradiating light having a wavelength longer than the wavelength of i-line (365 nm). The only product produced as a by-product during the reaction is nitrogen, which is easily discharged out of the system as a gas. Therefore, it does not affect the subsequent metal ion substitution reaction and the electroless plating process performed as necessary.

  In addition, the polycarbodiimide derivative has a carbodiimide structure showing high reactivity with active hydrogen compounds contained in alcohol, thiol, amine and the like. By blending such a polycarbodiimide derivative, it can be easily reacted with a naphthoquinonediazide derivative. Thus, by reacting both derivatives, the photosensitive composition layer has a three-dimensional gelled structure. For this reason, it becomes insoluble in both water-based and organic solvent-based solvents, and heat resistance can be improved. As a result, the adhesive strength between the conductive portion and the insulator can be improved, and the chemical resistance and heat resistance of the entire composite member can be improved.

  In the present invention, a porous body is preferably used as the insulator. In particular, when the photosensitive composition containing a naphthoquinone diazide derivative is coated on the surface of the internal pores of the porous body, conducting the process (2) as described above allows highly accurate pattern shape conductivity. The part can be formed.

  When a conductive part is formed by the method of the present invention using a sheet-like insulator in the planar direction and the thickness direction, the resulting composite member is preferably configured as follows. This will be described with reference to FIG.

  In FIG. 2, the schematic of an example of the composite member manufactured by the method of this invention is shown. As shown in FIG. 2, a photosensitive composition layer 22 containing a compound that generates an ion-exchange group by exposure exists on the surface of the porous insulator 21. By performing exposure, an organic compound 24 containing an ion exchange group is formed in the exposed portion. The ion exchange group of the organic compound 24 carries metal ions and metal fine particles by an ion exchange reaction or an adsorption reaction. By subsequently performing electroless plating, a conductive portion 23 having a thickness is formed. Thus, a composite member is produced by the method of the present invention. Here, the organic compound 24 is firmly bonded to both the insulator 21 and the conductive portion 23 to improve the adhesion between them. Thus, in the composite member in which the organic compound 24 exists between the insulator 21 and the conductive portion 23, the amount of the organic compound 24 on the surface of the insulator 21 preferably satisfies the following conditions. That is, it is desirable that the amount of the organic compound 24 present without contacting the conductive portion 23 is smaller than the amount of the organic compound 24 present at the interface between the insulator 21 and the conductive portion 23. The hydrophilic ion exchange group contributes to the improvement of the adhesion between the conductive portion 23 and the insulator 21. However, when a hydrophilic group of an organic compound is present in addition to the portion where the conductive portion 23 is formed, metal migration is likely to occur between the adjacent conductive portions 23. In addition, the hygroscopicity is increased and the insulating properties are lowered.

  A multilayer wiring board can be produced using the composite member produced by the method of the present invention. First, a conductive part is formed by the method of the present invention over the planar direction and the thickness direction of a sheet-like insulator to manufacture a composite member. A multilayer wiring board produced by laminating a plurality of composite members obtained in this way will be described with reference to FIG.

  FIG. 3 is a schematic view showing an example of a multilayer wiring board using a composite member manufactured by the method of the present invention. As shown in FIG. 3, the multilayer wiring board 31 is configured by laminating a plurality of porous films made of an insulator 34 having conductive portions such as vias 32 and wirings 33. The via 32 and the wiring 33 are formed by filling a metal in the surface or inside of the fine hole of the porous film. A conductive portion 35 made of only a conductive material such as metal is formed on the end face of such a conductive portion.

  That is, in the multilayer wiring board 31 shown in FIG. 3, a layer 35 made of a conductor containing no insulator component exists on the outermost surface of the conductive portions 32 and 33 in each porous film. For this reason, the resistance of the conductive portion can be reduced. Particularly in a high frequency region, the impedance characteristics can be improved by the skin effect of these structures.

  The composite member produced by the method of the present invention can be used as a wiring board in a single layer without being laminated. An electronic package can be obtained by electrically connecting an electronic component on such a wiring board or a multilayer wiring board as described above.

  Since the conductive part having a fine pattern is formed with high precision on the wiring board in the electronic package thus configured, high-density mounting is possible. Specific examples of the wiring board or multilayer wiring board described above are suitable for multilayer wiring boards, interposers, 3D wiring, etc., which are indispensable for high-density mounting such as portable devices and micromachines, flip chip, and spherical semiconductor mounting. Multi-layer wiring, three-dimensional wiring, etc. that can be used in

  Hereinafter, the present invention will be described in more detail.

  In the present invention, the insulator on which conductive portions such as wirings and vias are formed may be made of any insulator material, and specific examples thereof include resins and ceramics.

  Examples of the resin include glass epoxy resin, bismaleimide-triazine resin and PPE resin, which are conventionally used as insulators for printed wiring boards, and other polyethers such as polyolefins, acrylic polymers, and polyallyl ethers. And resins generally called engineering plastics, such as polyesters such as polyarylate, polyamide, and polyethersulfone.

  Examples of the ceramic include glass, alumina, and aluminum nitride.

  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 planar direction but also in the thickness direction on the sheet-like insulator, a porous body made of an insulating material is used. By using it, an accurate conductive part can be easily formed.

  A porous body made of a resin can be easily produced by a method such as a wet method or a dry method.

  For example, when producing a porous resin sheet by a wet method, first, an inorganic fine powder and an organic solvent, which are pore forming agents, are added to a resin and kneaded to prepare a mixture. Subsequently, after forming this into a film, an inorganic fine powder and an organic solvent are extracted with a solvent. Then, it extends | stretches as needed.

  For example, when producing a porous resin sheet by a dry method, a mixture prepared in the same manner as in the wet method is extruded into a sheet. Next, after heat treatment as necessary, this is uniaxially or biaxially stretched.

  Even when the porous resin sheet is produced by any of these wet methods and dry methods, if necessary, the stretched resin sheet may be subjected to heat treatment for dimensional stability. In addition, a desired porous resin sheet can be easily produced by forming the resin sheet and then making it porous after forming the resin sheet without adding the above-described additives.

  Moreover, as a porous body made of ceramics, for example, alumina can be produced by anodizing aluminum in an electrolytic solution.

  In the manufacturing method of the composite member according to the present invention, when the conductive portion is three-dimensionally formed, that is, for example, when the conductive portion is formed not only in the planar direction but also in the thickness direction on the sheet-like insulator, The inside of the body is also exposed. At this time, in order to prevent exposure light from being scattered, the pore size of the porous body is preferably sufficiently small with respect to the exposure wavelength. However, if the pore diameter is too small, the photosensitive composition may be difficult to impregnate or exposure light may not be transmitted. Especially when wiring is formed, the filled metal needs to be well continuous in the pores, but if the pore diameter is too small, the metal may be in a fine particle state separated from each other in the pores. There is. In order to avoid such inconvenience, the pore diameter of the porous body is preferably 30 to 2000 nm, more preferably 50 to 1000 nm, and most preferably set in the range of 100 to 500 nm.

  Even when the pore diameter deviates from the above-mentioned range and is considerably larger than the exposure wavelength, a liquid having a refractive index close to or the same as that of the porous body or an amorphous solid having a low boiling point is filled in the pores to prevent scattering. For example, scattering during exposure can be prevented. However, if the pore diameter becomes too large, it will be difficult to sufficiently fill the pores with metal by plating or the like, and it will be difficult to reduce the width of the conductive portion to several tens of μm or less. Further, when a multilayer wiring board is manufactured, a short circuit between layers tends to occur. Taking these into consideration, it is desirable that the pore size of the porous body be set to 5 μm or less even when a liquid for preventing scattering is used during exposure.

  In addition, the porous body is a porous material having three-dimensionally continuous pores in order to produce a composite member having a pattern in the film thickness direction, in particular, a line-shaped part continuously connected in the two-dimensional direction. The body is desirable.

  Furthermore, it is preferable that the continuous pores existing in the porous body are regularly and uniformly formed in order to prevent scattering of exposure light. This is also effective for miniaturization of the conductive line.

  In addition, the continuous pores in the porous body need to be opened to the outside of the porous body, and it is desirable that the number of closed cells having no open end is as small as possible. Further, in order to improve the electrical conductivity of the wiring, it is desirable that the porosity is high in a range where the mechanical strength of the porous body is maintained. Specifically, the porosity is preferably 40% or more, and more preferably 60% or more.

  The porous body having three-dimensionally continuous pores as described above can be produced by various methods. For example, beads laminated, green sheets, porous bodies prepared using a laminated structure of beads as a template, porous bodies formed using a laminate of bubbles or liquid bubbles as a template, silica obtained by supercritical drying of silica sol A porous body made by removing an appropriate phase from a phase-separated structure such as an airgel, a porous body formed from a microphase-separated structure of a polymer, a co-continuous structure generated by spinodal decomposition of a mixture of polymer or silica, A porous material produced by an emulsion templating method or the like; H. Cumpston et al. (Nature, vol. 398, 51, 1999) and M.C. A porous body produced using a three-dimensional stereolithography as reported by Campbell et al. (Nature, vol. 404, 53, 2000) can be used.

  Examples of the porous body prepared by filling the voids of the laminated structure of beads with resin or metal oxide gel and then curing the beads and then removing the beads are, for example, Y. A. Vlasov et al. (Adv. Mater. 11, No. 2, 165, 1999) and S. A. Johnson et al. (Science Vol. 283,963, 1999) have reported.

  In addition, since a porous body having a regular and high porosity can be produced at low cost, a porous body such as a polymer formed using a laminate of bubbles or liquid bubbles as a template is preferable. For example, S. H. Park et al. (Adv. Mater. 10, No. 13, 1045, 1998) and S. A. Jenekhe et al. (Science Vol. 283, 372, 1999).

  A silica airgel having continuous pores with a porosity of 90% or more and a pore diameter of about 100 nm or less obtained by supercritical drying of silica sol is preferable because of its high porosity and excellent transparency.

  A porous body formed from a phase-separated structure represented by a polymer or the like is most preferable because the pore diameter can be easily controlled and can be produced at low cost.

  The porous body produced from the microphase separation structure can easily control the state of the inner surface of the pores. That is, when one phase of the microphase separation structure is removed, it is not completely removed but partially remains on the inner surface of the pore. Thereby, the surface state of the inner surface of the hole can be changed. For example, in the case where an ABC type triblock copolymer having a sufficiently large molecular weight of A and C as compared with B is used to remove the C phase and form a porous body composed of the A phase. The B phase is disposed on the inner surface of the pores. Therefore, the properties of the inner surface of the pores can be changed without greatly changing the properties of the entire porous body. Therefore, the adhesiveness between the impregnating resin and the porous body can be improved. In this case, since the B phase is completely bonded to the A phase by chemical bonding, it is superior to a normal surface adsorption type surface treatment agent.

  The phase separation structure exhibited by the polymer is not particularly limited, and examples thereof include a phase separation structure formed by spinodal decomposition exhibited by the polymer blend, and a micro phase separation structure exhibited by the block copolymer and graft copolymer. The microphase-separated structure exhibited by the block copolymer or graft copolymer is the best because the pore size can be easily controlled and a regular porous structure can be formed.

  Among the microphase-separated structures, the co-continuous structure is a phase-separated structure composed of two phases that are three-dimensionally continuous, and is porous with three-dimensionally continuous pores by selectively removing one phase. It is preferable because a solid body can be formed. Of these co-continuous structures, an OBDD structure or a Gyroid structure is preferable. Moreover, it is preferable that the weight fraction in the copolymer of the polymer chain which comprises a porous body is set to the range of 30 to 70%.

  The pore diameter of the obtained porous body can be controlled by the molecular weight of the polymer chain constituting the phase to be removed from the phase separation structure. In addition, the pore diameter of the porous body can be controlled by mixing such a homopolymer having good compatibility with the polymer chain. By using a method of mixing homopolymers, a porous body having a pore diameter of 100 nm or more that is difficult to form with only a copolymer can be produced relatively easily. However, when the amount of the homopolymer mixed is too large, the regularity of the phase separation structure is lowered. Therefore, the mixing amount of the homopolymer is preferably 10% or less by weight with respect to the copolymer.

  A three-dimensional porous body made of a co-continuous structure has continuous pores having correlation distances of 2√3 times and 4 times the radius of rotation of the cross section of the microdomain constituting the three-dimensional porous structure. . This can be confirmed by a small angle X-ray scattering method or a light scattering method. Note that having a correlation distance means that the existence probability of a surrounding domain with respect to a distance r from the center of a predetermined domain (at the point of the distance r, the point forms a domain instead of a hole) This means that there is a distance at which the existence probability is maximum when the probability of being a filling region is measured.

  The method for selectively removing one phase from the microphase separation structure is not particularly limited, and various methods can be employed. For example, there is a method of chemically cutting two bonding sites using a telechelic polymer and then etching one polymer chain. Further, a method of selectively decomposing and removing one phase by ozone oxidation, or a method of removing it by oxygen plasma or photolysis may be used. Furthermore, it is also possible to selectively decompose and remove one phase by irradiating energy rays such as β rays.

  The polymer material for producing the porous body from the phase separation structure is not particularly limited, and any material can be used. Examples thereof include polyolefins, acrylic polymers, polyethers such as polyallyl ethers, polyesters such as polyarylates, polyamides, polyimides, polyethers, and polyether sulfones.

  When a porous body is used as the substrate for wiring formation, a heat resistant polymer such as polyimide, polyamide, polyallyl ether, polyarylate, and polyethersulfone is particularly preferable. In addition, a polymer having a double bond in a side chain or main chain obtained by polymerizing a conjugated diene monomer such as 1,2-bond type or 1,4-bond type polybutadiene may be used.

  A porous body made of polyimide can be produced, for example, by the following method. First, polyamic acid, which is a polyimide precursor, and a thermally decomposable polymer such as polyethylene oxide, polypropylene oxide, and polymethyl methacrylate are mixed. At this time, phase separation may be performed as a block copolymer or a graft copolymer. Next, heat treatment is performed to convert the polyamic acid into polyimide, and at the same time, the thermally decomposable polymer is volatilized and removed.

  From the viewpoint of the regularity of the structure, it is preferable to use a block copolymer or a graft copolymer. However, when pores of 100 nm or more are formed, the molecular weight of the thermally decomposable polymer chain is about 100,000 or more, so that it is relatively difficult to synthesize a block copolymer. Therefore, for example, it is preferable to introduce a linking group at the end of the thermally decomposable polymer chain and then synthesize a graft copolymer. You may adjust the hole diameter of a porous body by adding a homopolymer to a block copolymer or a graft copolymer. However, when the amount of the homopolymer mixed is too large, the regularity of the phase separation structure is lowered. Therefore, the mixing amount of the homopolymer is preferably 10% or less by weight with respect to the copolymer. At this time, the addition of a crosslinkable plasticizer such as bismaleimides promotes the formation of a microphase separation structure and improves the heat resistance and mechanical strength of the porous body.

  In addition, 1,2-bonded polybutadiene, that is, poly (vinylethylene) is three-dimensionally cross-linked by the addition of a radical generator or a cross-linking agent, resulting in a cured polymer having excellent heat resistance, electrical properties, moisture resistance, and mechanical properties. . In addition, since poly (vinylethylene) can be polymerized by living, it is possible to produce a block copolymer having a high molecular weight and a uniform molecular weight distribution. Therefore, when a block copolymer of poly (vinylethylene) and polymethacrylic acid ester that can be decomposed and removed by β-rays is used, a regular porous body having a desired pore size composed of a crosslinked poly (vinylethylene) is formed. can do. Also in this case, the pore diameter of the porous body can be controlled by adding a homopolymer.

  As the radical generator, organic peroxides such as general dicumyl peroxide and azonitriles such as azobisisobutyronitrile can be used. Among them, generation of polyfunctional radicals such as 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane and 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone The agent is preferable because it also acts as a crosslinking agent.

  The amount of radical generator added is preferably 0.1 to 20% by weight, more preferably 1 to 5% by weight, based on the polymer chain to be crosslinked. If the radical generator is too small, the crosslinking density is small, and if it is too large, the crosslinked product may become porous or the microphase separation structure may be disturbed.

  Examples of the crosslinking agent include bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) ether, 2,2′-bis [4- (paraaminophenoxy) phenyl] propane, and 2,2′-bis [4- Bismaleimides such as (paraaminophenoxy) phenyl] hexafluoropropane are preferred. The addition amount is preferably 0.1 to 20% by weight, more preferably 1 to 5% by weight, based on the polymer chain to be crosslinked. If it is too small, the crosslinking density is small, and if it is too large, the microphase separation structure may be disturbed.

  If the crosslinking reaction proceeds before the microphase separation structure is formed, the formation of the microphase separation structure is inhibited. Therefore, it is preferable that the crosslinking reaction is started after the microphase separation structure is sufficiently formed. The formation of the microphase-separated structure proceeds above the glass transition temperature of each polymer chain forming the copolymer. Therefore, it is preferable that the glass transition temperature of the polymer chain is sufficiently lower than the radical generation temperature of the radical generator.

  Examples of the most preferable composition include diblock copolymer or triblock copolymer of poly (vinylethylene) chain, poly (methyl methacrylate) chain, and poly α-methylstyrene chain, and 2,2- Bis (4,4-di-t-butylperoxycyclohexyl) propane or 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone in weight percent with respect to the poly (vinylethylene) chain 1 to 5% added. In particular, it is best to use 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone as the radical generator.

  First, after heating at a temperature equal to or higher than the glass transition temperature of each polymer chain to form a microphase separation structure, the temperature may be gradually raised and heated above the thermal decomposition temperature of the radical generator to be crosslinked and cured. However, if the temperature is too high at this time, the order-disorder transition temperature may be passed before sufficient crosslinking is performed, and there is a possibility that the material will melt and become uniform. In that respect, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone is advantageous because it generates radicals by ultraviolet irradiation without thermal decomposition.

  A diblock copolymer or triblock copolymer of poly (vinylethylene) chain and polymethyl methacrylate chain has a sufficiently high microphase separation structure because the glass transition temperature of polymethyl methacrylate is relatively high at around 105 ° C. Cross-linking reaction is likely to occur before However, since polymethyl methacrylate is easily vaporized by β-ray irradiation, it can be made porous by solvent washing or heat treatment at a relatively low temperature. Since the glass transition temperature of polymethylmethacrylate is close to the crosslinking initiation temperature, a microphase separation structure may be formed by slowly evaporating the solvent from the solution to form a cast film. In this case, if the solvent is evaporated at a temperature sufficiently lower than the thermal decomposition temperature of the radical generator, the formation of the microphase molecular structure is not hindered by crosslinking. However, the production of such a cast film takes a relatively long time and the productivity is not high. The same can be said when poly α-methylstyrene is used instead of polymethyl methacrylate.

  Instead of polymethyl methacrylate and poly α-methyl styrene, polymethacrylates substituted with alkyl groups having 3 to 6 carbon atoms, and substituted poly α-methyl styrenes with phenyl groups substituted with similar alkyl groups Since the glass transition temperature is lowered, the above-described problems can be avoided. That is, the microphase separation structure can be rapidly formed by heat-treating the copolymer film (or molded product) at a temperature equal to or higher than the glass transition temperature. For example, poly n-propyl methacrylate and poly n-butyl methacrylate have low glass transition temperatures of 35 ° C. and 25 ° C., respectively. Similarly, poly α-methylstyrene butylated at the 4-position shows a low glass transition temperature. When the number of simple primes of the alkyl group is more than 6, although a lower glass transition temperature is exhibited, at the same time, a crosslinking reaction is easily caused by β-ray irradiation. Poly n-propyl methacrylate, poly n-butyl methacrylate, and poly s-butyl methacrylate are exemplified as those having both a low glass transition temperature and an effect of promoting decomposition by β-ray irradiation, particularly poly n-butyl methacrylate, poly Most preferred is s-butyl methacrylate.

  When an alkyl group is branched like a 2-ethylhexyl group, it is excellent in that the effect of promoting decomposition by β-ray irradiation is hardly suppressed even when the number of carbon atoms increases. However, it is inferior to the above poly n-butyl methacrylate and poly s-butyl methacrylate in terms of practicality from the viewpoint of easy availability of monomers.

  Furthermore, polyisobutylene, polypropylene, or the like can be used as a polymer chain that achieves both a low glass transition temperature and a decomposition promoting effect by β-ray irradiation.

  Although there is no restriction | limiting in particular as the irradiation amount of (beta) ray, It is good to set to the range of 100Gy-10MGy, Furthermore, it is preferable to set to 1KGy-1MGy, More desirably, 10KGy-200KGy. If the irradiation amount is too small, the degradable polymer chain will not be sufficiently decomposed. Conversely, if the irradiation amount is too large, the degradation product of the degradable polymer chain may be cured by three-dimensional crosslinking, etc. This is because the chain may be broken down. The acceleration voltage varies depending on the thickness of the copolymer molded body, that is, the penetration length of β-rays into the molded body. For example, in the case of a thin film of about several tens of μm or less, about 20 kV to 2 MV is preferable. In addition, in the case of a film of 100 μm or more, a bulk molded body, etc., about 500 kV to 10 MV is preferable. When the molded body contains a metal molded body or the like, it is possible to increase the sweeping acceleration voltage.

  When the β-ray irradiation is performed, the 1,2-bonded polybutadiene chain is cross-linked, so that the amount of the radical generator may be reduced or may not be added at all. In this case, it is not always necessary to reduce the glass transition temperature. Poly (vinylethylene) cross-linked products have been tried to be used for wiring boards because of their excellent properties, but there is a problem that the adhesiveness of the wiring to copper is not good.

  However, in the composite member of the present invention, such a problem is avoided because wiring and vias such as copper are integrated with the porous body.

  Next, the manufacturing method of the composite member which concerns on this invention is demonstrated for each process with reference to FIG.

<Step 1>
Step (1): First, a photosensitive composition layer 2 containing a compound that generates or disappears an ion exchange group by exposure is formed on an insulator 1 as shown in FIG. In addition, in FIG. 1, the example using the photosensitive composition containing the compound which produces | generates an ion exchange group by exposure is shown.

  When the conductive portion is formed in the planar direction and the thickness direction of the insulator 1, the conductive portion can be easily and accurately formed by using the insulator 1 as a porous body.

  The photosensitive composition used in the manufacturing method of the composite member which concerns on this invention contains the compound which produces | generates an ion exchange group by light irradiation, or the compound which lose | disappears an ion exchange group by light irradiation. However, the compound which produces | generates an ion exchange group by exposure may produce an ion exchange group by the multistep reaction triggered by the chemical reaction by exposure. Such a compound first generates a chemical reaction by exposure to generate a precursor of some ion-exchange group, and this precursor further generates a chemical reaction to generate an ion-exchange group.

  As a compound which produces | generates an ion exchange group by exposure, the compound which generate | occur | produces the functional group which has ion exchange ability by exposure (i) is mentioned.

  In addition, as a compound that loses an ion-exchange group by exposure, (ii) a functional group having a functional group having ion exchange ability before exposure and having a hydrophobic property that hardly dissolves or swells in water after exposure. And compounds that generate groups.

Examples of the functional group having ion exchange properties in the above (i) and (ii) include hydrophilic functional groups, such as a —COOX group, —SO ₃ X group, —PO ₃ X ₂ group (X is a hydrogen atom) , typical metal belonging to alkali metals or alkaline earth metals and periodic table 1 group, and are selected from ammonium groups) and -NH ₂ OH, and the like.

In particular, in (i) and (ii), as the functional group having ion exchange ability, a functional group having a cation exchange ability is desirable because it can easily exchange ions with metal ions. Examples of such cation exchange groups include acidic groups such as —COOX group, —SO ₃ X group, and —PO ₃ X ₂ group (where X is a hydrogen atom, an alkali metal or alkaline earth metal, and periodic table I, A typical metal belonging to Group II, an ammonium group) is particularly preferred. If these are contained, after the metal ion exchange, which is a subsequent step, stable adsorption with the reduced metal or metal fine particles can be obtained.

  Of the above-described cation exchange groups, those having a pKa value of 7.2 or less determined from ion dissociation properties in water are more preferable. When the pKa value exceeds 7.2, the number of bonds per unit area is small in the subsequent step of bonding metal ions or metals (step (3)). Therefore, there is a possibility that desired conductive properties may not be obtained in the conductive portions formed thereafter.

  In the first and second embodiments of the present invention, a compound that generates or disappears an ion-exchange group when irradiated with light having a wavelength of 280 nm or longer is used as the compound that generates or disappears an ion-exchange group when irradiated with light.

  Specific examples of compounds that generate ion-exchangeable groups upon irradiation with light having a wavelength of 280 nm or more include naphthoquinone diazide derivatives, o-nitrobenzyl ester derivatives, p-nitrobenzyl ester sulfonate derivatives, and naphthyl or phthalimide trifluorosulfonates. Derivatives and the like.

  In particular, when a naphthoquinone diazide derivative is used, sufficiently fine patterning is possible in a short time with light having a wavelength of 280 nm or more with low energy. Further, the naphthoquinonediazide derivative causes light bleaching during exposure and becomes transparent in a wavelength region of about 300 nm or more. Therefore, it is possible to expose deeply in the film thickness direction, which is very suitable when exposing through the film thickness direction of the porous sheet.

For example, the exposure reaction when naphthoquinonediazide is used as a compound that generates an ion-exchange group is shown in the following chemical formula (1).

  As shown in the chemical formula (1), the naphthoquinone diazide formed on the insulator generates —COOH groups by exposure to water and the presence of water in the next step.

  The photosensitive composition layer is exposed in a metal ion-containing aqueous solution, alkali or acidic aqueous solution in a subsequent step. Since the photosensitive composition ionized by the ion exchange reaction is easily dissolved in the aqueous solution, it is more easily peeled off than the insulator as the base material. Therefore, in order to prevent peeling from the substrate, it is preferable that a group that generates an ion-exchange group is supported or bonded to a polymer compound such as a polymer, and the group that generates an ion-exchange group is shared by the polymer compound. Most preferably it is chemically bonded by a bond.

  In this case, the molecular weight of the polymer or polymer compound is preferably 1000 or more, and more preferably 2000 or more. In the case of a polymer having a molecular weight of 1000 or less, applicability to an insulator as a base material is deteriorated, and uniform application may be difficult. Moreover, it becomes easy to produce deterioration by exposure to the alkali or acidic aqueous solution in a plating process.

  To simply prevent peeling from the substrate, a low molecular monomolecular film having both a group capable of chemically bonding to the substrate and an ion-exchange group may be formed on the surface of the substrate. For example, JP-A-6-202343 discloses a method for forming a monomolecular film of a silane coupling agent having a naphthoquinonediazide group that is exposed to an ion-exchange group on the surface of a glass substrate.

  However, in the case of a monomolecular layer, the inventors have found that the adsorption amount of the plating nucleus is small and sufficient plating cannot be performed. By using the polymeric photosensitive composition as described above, the substrate surface can be coated with a certain thickness. Therefore, since a sufficient amount of plating nuclei are adsorbed, good plating can be performed.

  From such a viewpoint, in the present invention, the compound that generates an ion-exchange group by irradiation with light having a wavelength of 280 nm or more includes 1,2-naphthoquinonediazidosulfonyl-substituted phenol resin derivative, 1,2-naphthoquinonediazidesulfonyl-substituted polystyrene derivative. Etc. are suitable.

  Another example of a compound that generates an ion-exchange group by irradiation with light having a wavelength of 280 nm or longer is a compound in which a protective group is introduced into an ion-exchange group such as a carboxyl group contained in the polymer structure. It is done. When this compound is used, a photoacid generator that generates an acid upon irradiation with light having a wavelength of 280 nm or more is added to the photosensitive composition. An acid is generated from the photoacid generator by subsequent exposure, and the protecting group is decomposed by the generated acid to generate an ion-exchange group. Examples of the polymer include phenolic resins such as phenol novolac resin, xylenol novolac resin, vinylphenol resin, and cresol novolac resin, and carboxyl group-containing polymers such as polyamic acid, polyacrylic acid, and polymethacrylic acid.

  Examples of the protecting group for the phenolic resin include tert-butyl ester derivative substituents such as a tert-butoxycarbonylmethyl group and a tert-butoxycarbonylethyl group.

  On the other hand, in polyamic acid, polyacrylic acid, etc., as a protective group for the carboxyl group in the structure, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl group Groups, benzylalkoxy groups, 2-acetoxyethyl groups, 2-methoxyethyl groups, methoxymethyl groups, 2-ethoxyethyl groups, 3-methoxy-1-propyl groups, etc., trimethylsilyl groups, triethylsilyl groups, triphenyl Examples include alkylsilyl groups such as silyl groups.

  Moreover, o-nitrobenzyl ester group is mentioned as a protective group which produces | generates ion exchange groups, such as carboxylic acid, only by light irradiation, without using a photo-acid generator.

Suitable photoacid generators for the 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. , Salts such as phosphonium salts and iodonium salts, organic halogen compounds, and orthoquinone-diazide sulfonic acid esters can be used.

  By using a composition that generates an ion-exchange group by such chemical amplification, high sensitivity to light can be achieved. The use of these compositions becomes effective as the pattern becomes finer, particularly when light transmittance in the film thickness direction is required, such as the formation of a three-dimensional pattern on a porous substrate. come.

On the other hand, irradiation with light having a wavelength of 280 nm or more loses the ion-exchangeable group, that is, generates a functional group having an ion-exchange ability before exposure and having a hydrophobic property that hardly dissolves or swells in water after exposure. As the compound, the following compounds can be used. That is, an acidic group such as —COOX group, —SO ₃ X group or —PO ₃ X ₂ group which is an ion-exchange group (where X is a hydrogen atom, an alkali metal or an alkaline earth metal, and periodic tables I and II). It is a compound having a typical metal to which the group belongs, an ammonium group) in its composition skeleton, and its ion exchange ability disappears upon irradiation with light.

  As a compound that generates a functional group that has an ion exchange capacity before exposure and has a hydrophobic property that hardly dissolves or swells in water after exposure, a decarboxylation reaction is performed by light irradiation in the presence of a basic substance. Examples thereof include a carboxyl group-containing compound that can be generated and decomposed. In this case, in addition to the aforementioned carboxyl group-containing compound, a photoacid generator and a basic compound are added to the photosensitive composition. In such a composition, the acid generated by exposure neutralizes the basic compound involved in the decarboxylation reaction. For this reason, the ion exchange ability of the exposed portion disappears due to a mechanism in which the carboxyl group remains in the exposed portion and the decarboxylation reaction proceeds in the unexposed portion.

  As the carboxyl group-containing compound that can be decomposed by causing a decarboxylation reaction, any compound can be selected, but a compound in which the decarboxylation reaction easily proceeds with a basic compound is preferable. Examples of such a compound 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-containing compound include α-cyanocarboxylic acid derivatives, α-nitrocarboxylic acid derivatives, α-phenylcarboxylic acid derivatives, β, γ-olefin carboxylic acids and the like.

  Examples of the photoacid generator to be added include the photoacid generators described above, and those that generate an acid at a wavelength of 280 nm or more are particularly preferable.

  As the basic compound to be added, any compound can be used as long as it is neutralized by the acid released from the photoacid generator and acts as a catalyst for the decarboxylation reaction of the carboxyl group-containing compound. The basic compound may be either an organic compound or an inorganic compound, but a nitrogen-containing compound is preferred. Specific examples include ammonia, primary amines, secondary amines, and tertiary amines. The content of these 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 proceed sufficiently. When the amount exceeds 30% by weight, the carboxyl group-containing compound remaining in the unexposed area may be deteriorated.

  In addition, since the photosensitive composition layer is exposed to a metal ion-containing aqueous solution or an alkali or acidic aqueous solution in a later step, a group that causes an ion-exchangeable group disappearance reaction is prevented from dissolving in the polymer or polymer compound. Those supported or bonded to each other are preferred. As already explained, it is most preferable that the group causing the ion exchange group disappearance reaction is chemically bonded to a polymer or a polymer compound having a molecular weight of 1000 or more.

  In the third aspect of the present invention, at least one selected from the group consisting of an onium salt derivative, a sulfonium ester derivative, a carboxylic acid derivative, and a naphthoquinonediazide derivative is used as the compound that generates an ion exchange group upon exposure. Derivatives are used.

Examples of the onium salt derivatives include diazonium salts, phosphonium salts, iodonium salts, sulfonium salts and the like having CF ₃ SO ₃ ⁻ , p-CH ₃ PhSO ₃ ⁻ , p-NO ₂ PhSO ₃ ^— or the like as a counter anion. More specifically, trifluoroacetate derivatives such as diphenyliodonium, 4,4′-dibutylphenyliodonium, triphenylsulfonium, naphthylsulfonium, trifluoromethanesulfonate derivatives, and toluenesulfonic acid derivatives.

  Examples of the sulfonium ester derivatives include benzoin tosylate derivatives, o-nitrobenzyl tosylate derivatives, p-nitrobenzyl ester derivatives of arylsulfonic acid, p-nitrobenzyl-9,10-diethoxyanthracene-2- Examples thereof include sulfonate derivatives.

  Examples of the carboxylic acid derivative include the above-described phenol resin, a hydroxyl group of polyamic acid or polyacrylic acid, or a polymer in which a carboxyl group is protected. Examples of the polymer include a phenol novolac resin derivative, a xylenol novolac resin derivative, vinyl, and the like. Examples thereof include phenolic resin derivatives such as phenol resin derivatives and cresol novolak resin derivatives, and carboxyl group-containing polymer derivatives such as polyamic acid derivatives, polyacrylic acid derivatives, and polymethacrylic acid derivatives.

  Examples of the protecting group for the phenolic resin derivative include tert-butyl ester derivative substituents such as a tert-butoxycarbonylmethyl group and a tert-butoxycarbonylethyl group.

  On the other hand, in polyamic acid, polyacrylic acid, etc., a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group as a protecting group for the carboxyl group in the structure. , Alkoxy groups such as benzylalkoxy group, 2-acetoxyethyl group, 2-methoxyethyl group, methoxymethyl group, 2-ethoxyethyl group, 3-methoxy-1-propyl group, trimethylsilyl group, triethylsilyl group, triphenylsilyl And alkylsilyl groups such as groups. These generate carboxyl groups by acting with a suitable photoacid generator.

  Examples of naphthoquinone diazide derivatives include naphthoquinone diazide-4-sulfonic acid derivatives, naphthoquinone diazide-5-sulfonic acid derivatives, naphthoquinone diazide sulfonyl halide derivatives, and esterified products thereof.

  In addition, since the photosensitive composition layer containing a compound as described above is exposed to a metal ion-containing aqueous solution or an alkali or acidic aqueous solution in a later step, an ion-exchange group generation reaction is performed so as not to be dissolved therein. A group in which the generated group is supported or bonded to a polymer or a polymer compound is preferable. As already explained, it is most preferable that the group causing the ion exchange group disappearance reaction is chemically bonded to a polymer or a polymer compound having a molecular weight of 1000 or more.

  From such a viewpoint, 1,2-naphthoquinonediazidosulfonyl-substituted phenol resin derivative, 1,2-naphthoquinonediazidesulfonyl-substituted polystyrene derivative, etc., or ion exchange by deprotection using a photoacid generator of a polymer functional group protecting group Sex group generation is preferred.

In the fourth aspect of the present invention, a functional group having a hydrophobic property of disappearing an ion-exchangeable group by exposure, that is, having an ion-exchange ability before exposure but hardly dissolved or swollen in water after exposure. A photosensitive composition containing the generated compound is used. Such a compound is a compound having an ion exchange group in its skeleton and extinguishing the ion exchange ability by light irradiation. As an ion-exchange group, an acidic group such as —COOX group, —SO ₃ X group or —PO ₃ X ₂ group (where X is a hydrogen atom, an alkali metal or an alkaline earth metal, and periodic groups I and II) A typical metal to which the group belongs, and an ammonium group).

  Carboxyl group-containing compounds that can be decomposed by a decarboxylation reaction as compounds that generate hydrophobic functional groups that have ion-exchange ability before exposure and are difficult to dissolve or swell in water after exposure Is mentioned. In this case, in addition to the above-mentioned carboxyl group-containing compound, it is added to the photoacid generator, the basic compound and the photosensitive composition. In such a composition, the acid generated by exposure neutralizes the basic compound involved in the decarboxylation reaction. For this reason, the ion exchange ability of the exposed portion disappears due to a mechanism in which the carboxyl group remains in the exposed portion and the decarboxylation reaction proceeds in the unexposed portion.

  As the carboxyl group-containing compound that can be decomposed by causing a decarboxylation reaction, any compound can be selected, but a compound in which the decarboxylation reaction easily proceeds with a basic compound is preferable. Examples of such a compound 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-containing compound include α-cyanocarboxylic acid derivatives, α-nitrocarboxylic acid derivatives, α-phenylcarboxylic acid derivatives, β, γ-olefin carboxylic acids, and the like.

  Examples of the photoacid generator to be added include the above-mentioned photoacid generators, and those that generate an acid at a wavelength of 280 nm or more are particularly preferable.

  As the basic compound to be added, any compound can be used as long as it is neutralized by the acid released from the photoacid generator and acts as a catalyst for the decarboxylation reaction of the carboxyl group-containing compound. The basic compound may be either an organic compound or an inorganic compound, but a nitrogen-containing compound is preferred. Specific examples include ammonia, primary amines, secondary amines, and tertiary amines. The content of these 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 proceed sufficiently. When the amount exceeds 30% by weight, the carboxyl group-containing compound remaining in the unexposed area may be deteriorated.

  In addition, since the photosensitive composition layer is exposed to a metal ion-containing aqueous solution or an alkali or acidic aqueous solution in a later step, a group that causes an ion-exchangeable group disappearance reaction is prevented from being dissolved in the polymer or the polymer. Those supported or bonded to molecular compounds are preferred. As already explained, it is most preferable that the group causing the ion exchange group disappearance reaction is chemically bonded to a polymer or a polymer compound having a molecular weight of 1000 or more.

  As described above, according to the method of the present invention, first, by performing pattern exposure, ion exchange groups are selectively arranged in the exposed or unexposed area of the photosensitive composition layer. A region having such an ion exchange group is hydrophilic, but a region not including the ion exchange group is likely to be hydrophobic in many cases. However, in this invention, it is preferable that the area | region where the ion exchange group of a photosensitive composition layer does not exist is also hydrophilic and has the wettability with respect to water. When the hydrophobicity of the region where no ion-exchange group is present is too strong, in the plating step of <Step (5)> described later, the contact between the plating solution and the substrate becomes insufficient, and bubbles are formed on the substrate. It becomes easy. When bubbles are attached, the portion remains without being plated, so that a good metal pattern cannot be formed. In particular, when a porous body is used as the substrate, the plating solution is less likely to penetrate into the porous body. For this reason, when the hydrophobicity of the area | region which does not have an ion exchange group is too strong, it becomes difficult to plate inside a porous body.

  JP-A-6-202343 discloses a method of forming a metal pattern by forming a pattern comprising a hydrophilic region and a hydrophobic region and selectively plating the hydrophilic region. . At this time, in order to improve the selectivity of plating, the hydrophobic region is selectively fluorinated to increase the hydrophobicity of the region. By fluorination, the difference in wettability of the hydrophilic region and the hydrophobic region with respect to water increases. Thereby, the plating solution is selectively brought into contact with the hydrophilic region to enhance the selectivity of plating.

  However, for the reasons described above, in such a method, bubbles are likely to adhere to the hydrophobic region, so that satisfactory plating cannot be performed. Furthermore, since it is difficult for the plating solution to penetrate into the porous body, it is extremely difficult to plate the inside of the porous body.

  On the other hand, in the method of the present invention, it is not necessary to form a hydrophilic region and a hydrophobic region. Rather, by making all the surfaces of the insulator as the base material hydrophilic, the base material and the plating solution can be brought into sufficient contact and good plating can be performed.

  The wettability with water can be easily measured by a contact angle when a water droplet is dropped on a flat surface. In the present invention, the contact angle is preferably 60 ° or less, more preferably 40 ° or less, even in a region where no ion-exchange group is present.

  The photosensitive composition used in the production method of the present invention can contain additives depending on the purpose in addition to the compound that generates an ion-exchange group by exposure.

  For example, you may mix | blend the photosensitizer for improving resolution, film thickness permeability, etc. The photosensitizer is not particularly limited as long as it can photosensitize a compound that generates an ion-exchange group by exposure, and is appropriately selected according to the type of compound used, the light source, and the like.

  Specific examples of the photosensitizer include aromatic hydrocarbons and derivatives thereof, benzophenone and derivatives thereof, o-benzoylbenzoate and derivatives thereof, acetophenone and derivatives thereof, benzoin and benzoin ethers and derivatives thereof, xanthone and derivatives thereof. Thioxanthone and derivatives thereof, disulfide compounds, quinone compounds, halogenated hydrocarbon-containing compounds and amines, eosin B (CI No. 45400), eosin J (CI No. 45380), cyanocin (C I. No. 45410), Bengalrose, erythrosine (C.I. No. 45430), 2,3,7-trihydroxy-9-phenylxanthen-6-one, xanthene dyes such as rhodamine 6G, thionine (C I. No. 2000), Azure A (C.I.No. 52005), thiazine dyes such as Azure C (C.I.No. 52002), pyronin B (C.I.No. 45005), pyronin GY (C.I. No. 45005) and coumarin dyes such as 3-acetylcoumarin and 3-acetyl-7-diethylaminocoumarin.

  The blending ratio of such a photosensitizer is usually 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on the compound that generates or disappears an ion exchange group upon exposure.

  Moreover, when the above-mentioned naphthoquinone diazide derivative is used as the compound that generates an ion-exchange group by exposure, it is preferable to add a carbodiimide derivative or an amine derivative as a crosslinking agent. The photosensitive composition can be cured by heat treatment after the conductive portion is formed, and heat resistance can be imparted to the resulting insulator.

  The blending ratio of such a crosslinking agent is appropriately determined from the equivalent amounts of functional groups that react with each other.

  As the photosensitive composition used in the method for producing a composite member of the present invention, a photosensitive composition containing a naphthoquinone diazide derivative and a polycarbodiimide derivative is particularly preferable. When such a photosensitive composition is used, the polycarbodiimide derivative and the ion exchange group generated from the naphthoquinonediazide derivative are cross-linked with each other by performing a heat treatment after forming the conductive portion. Thereby, the contact property between the conductive portion and the insulator is improved. In this way, it is possible to obtain a composite member having high heat resistance and a conductive portion having a fine pattern.

  Further, in the photosensitive composition as described above, a hydrophilic ion-exchange group is selectively generated in the exposed portion, so that a difference in solubility occurs between the exposed portion and the unexposed portion of the photosensitive composition layer. By utilizing this difference in solubility, a pattern of the photosensitive composition can be easily formed.

  In addition, such a photosensitive composition is an optical color used for an interlayer insulating film for a build-up substrate, a color liquid crystal display device, an electroluminescence display, a color fluorescent display device, a plasma display panel, an OA sensor, a solid-state image sensor, and the like. It can use for uses, such as a light-shielding photosensitive resin composition suitable for manufacture of a filter. Since this photosensitive composition has characteristics such as chemical resistance, water resistance, heat resistance, and high adhesion to a substrate, it is a useful photosensitive composition.

  As the naphthoquinonediazide derivative contained in the photosensitive composition described above, 1,2-naphthoquinonediazidesulfonyl-substituted phenol resin, 1,2-naphthoquinonediazidesulfonyl-substituted polystyrene resin, and the like are particularly preferable. When these are contained, the film formability is good and a thin film can be formed. In particular, the 1,2-naphthoquinonediazide sulfonyl-substituted phenolic resin is most excellent in heat resistance because the phenolic hydroxyl group of the phenolic resin crosslinks and cures with the polycarbodiimide derivative.

Moreover, as a polycarbodiimide derivative contained in the photosensitive composition mentioned above, the compound represented by following General formula (1) is preferable.

(In the formula, R1 represents an organic group having 1 to 20 carbon atoms represented by a methylene group, an ethylene group, a propyl group, an isoprene group, a butadiene group, etc.)
Thus, when the polycarbodiimide derivative is composed of an aliphatic skeleton, the composition can be set to a low viscosity. Therefore, in the case of coating with a solvent by a spin coating method, a dip coating method or the like, it is particularly preferably used for thinning the organic photosensitive composition.

  Further, in the photosensitive composition as described above, the naphthoquinone diazide derivative and the polycarbodiimide derivative each take into consideration the functional group equivalent of each other to react, and the ratio of the reactive group to 1 mol of the carbodiimide group is 0.00. It is desirable to contain from 01 mol to 1 mol. When the ratio of the reactive group is less than 0.01 mol, the reactivity is poor and it becomes difficult to obtain the desired heat resistance. On the other hand, when the ratio of the reactive group exceeds 1 mol, the storage stability at room temperature is lowered, and the process of the present invention may be hindered. By adjusting to the said range, reaction temperature can be made into about 100 degreeC, and it is desirable to advance reaction after completion | finish of this process.

  The photosensitive composition used in the method for producing a composite member of the present invention may be formed into a sheet by molding a mixture of components, or may be in solution by dissolving the mixture of components in an appropriate solvent.

  In order to form the photosensitive composition layer on the insulator, the photosensitive composition layer can be formed on the surface of the insulator by attaching the sheet-like photosensitive composition to the insulator. Alternatively, the photosensitive composition in solution may be coated on the insulator to form a photosensitive composition layer on the surface of the insulator. Considering the durability of the composite member after forming the conductive portion, it is preferable to form a photosensitive composition layer by coating the insulator with a solution-like photosensitive composition.

  In addition, when a conductive portion is formed in a three-dimensional manner using a porous insulator, the porous insulator is impregnated or coated on the inner surface of the porous insulator, and the surface to the inner portion is coated. The photosensitive composition layer is formed over the entire area.

  As a coating method, any method such as a dipping method, a spin coating method, a spray method, a vacuum deposition method, and a laminating method may be used.

  In the method for producing a composite member of the present invention, it is preferable to use an insulator in which a photosensitive composition layer is previously formed in order to improve productivity.

  Examples of the insulator in which the photosensitive composition layer is formed in advance include a porous insulator in which the inner pore surface is coated with a photosensitive composition containing a naphthoquinonediazide derivative. Thus, by using a porous insulator whose inner pore surface is coated with a naphthoquinonediazide derivative, a conductive portion with a high pattern shape can be formed in a three-dimensional shape.

<Step (2)>
Next, the photosensitive composition layer 2 formed on the insulator 1 in the step (1) is subjected to pattern exposure to a desired conductive pattern as shown in FIG. The ion-exchanging group is generated or disappeared in the exposure unit 4 of 2.

  In FIG. 1B, pattern exposure is performed through the mask 3 on which the conductive pattern is formed, but the present invention is not limited to this. Using a mask on which a negative image of the conductive pattern is formed, ion-exchange groups in portions other than the conductive pattern portion may be generated or eliminated.

  In the exposure, it is not always necessary to use a mask. For example, the exposure may be performed by drawing according to a conductive pattern using a laser beam or the like. Further, the periodic pattern may be exposed using a periodic light intensity pattern such as an interference fringe generated by light interference.

  Furthermore, the exposure pattern may be not only a two-dimensional pattern but also a three-dimensional pattern. To expose a three-dimensional pattern, various Kochi three-dimensional exposure methods, such as condensing exposure light with a lens, and drawing the pattern by three-dimensionally scanning the spot of the collected light Can be used.

  In the first and second embodiments of the present invention, exposure light having a wavelength of 280 nm or more is irradiated. In order to suppress degradation of the insulator due to exposure to a low level, the wavelength of the exposure light is preferably 300 nm or more, and more preferably 350 nm or more.

  In particular, when the porous body has an aromatic compound structure, such as when exposing in the thickness direction inside the porous body, it is important to use exposure light having a long wavelength. When the porous body is composed of aromatic polyimide or the like, there are many cases where the absorption edge of polyimide absorption is 450 nm or more. In such a case, it is preferable to perform pattern exposure at a longer wavelength of 500 nm or more.

  In the third and fourth aspects of the present invention, the wavelength of the exposure light is not particularly limited.

  As the exposure light source used in the step (2), in addition to an ultraviolet light source and a visible light source, a light source that generates exposure light of a predetermined wavelength may be selected from among light sources such as β rays (electron beams) and X rays. it can. The ultraviolet light source or visible light source is specifically selected from hydrogen discharge tubes, rare gas discharge tubes, continuous spectrum light sources such as tungsten lamps and halogen lamps, various lasers, and discontinuous spectrum light sources such as mercury lamps. Use.

  In the step (2), in order to increase the binding amount of metal ions in the subsequent step (3) with respect to the ion exchange group of the photosensitive composition layer, You may swell the part which formed the ion exchange group. For this purpose, the insulator is brought into contact with the acid or alkali solution by a technique such as spraying or dipping. In particular, hydroxides such as lithium hydroxide, potassium hydroxide and sodium hydroxide as alkali solutions, alkali metal salts such as lithium carbonate, potassium carbonate and sodium carbonate, metal alkoxides such as sodium methoxide and potassium ethoxide and hydrogenation It is preferable to use at least one kind of aqueous solution such as sodium boron and soak in these solutions. These aqueous solutions may be used alone or in combination.

<Step (3)>
Next, metal ions or metal fine particles are selectively bonded to the formed ion-exchangeable group to form a conductive portion as shown in FIG. In FIG.1 (c), the exposure part 4 becomes an electroconductive part.

The ion exchange group generated in the exposed portion undergoes an exchange reaction with metal ions. An example of an exchange reaction between an ion exchange group and a metal ion is shown in the following chemical formula (2).

  In order to cause an exchange reaction between the ion-exchange group and the metal ion, it can be easily carried out simply by immersing the insulator after pattern exposure in an aqueous solution containing a metal salt, for example.

  Examples of the metal element used as the metal ion include copper, silver, palladium, nickel, cobalt, tin, titanium, lead, platinum, gold, chromium, molybdenum, iron, iridium, tungsten, and rhodium.

  These metal elements are contained in the solution as metal salts such as sulfates, acetates, nitrates, chlorides, carbonates and the like. In particular, copper sulfate is preferable. It is appropriate to mix such metal salts so that the concentration of metal ions in the solution is 0.001 to 10M, preferably 0.01 to 1M. The solvent for dissolving the metal salt may be water or an organic solvent system such as methanol or isopropanol.

  The pH of the metal salt-containing liquid used here is preferably 7 or less, and more preferably 6.5 or less. As the ion exchange group used in the present invention, those having a pKa value of 7.2 or less determined from an ion dissociation constant in water are preferably used. In this case, as the pH of the aqueous solution containing the metal salt becomes around 7, the ion exchange amount hardly changes.

  When the pH of the metal salt-containing solution exceeds 7, metal ions are adsorbed to polar groups other than the target ion-exchange group, such as phenolic hydroxyl groups and silanol groups. As a result, a good pattern cannot be obtained. For example, when a photosensitive agent is applied to a glass substrate by spin coating or the like, hydroxyl groups are exposed on the back surface where the photosensitive agent is not applied. When such a substrate is immersed in an aqueous solution containing a metal salt exceeding pH 7, metal ions are adsorbed on the hydroxyl group. For this reason, metallization occurs in the subsequent process, and the back surface where the photosensitive agent is not applied is plated.

  Therefore, it is desirable that the metal salt-containing solution used in the present invention is in the above-described range in both concentration and pH.

  In the present invention, a solution in which metal fine particles are dispersed can also be used. The ion-exchange group and the colloidal metal fine particles are selectively bonded by electrostatic interaction or the like. Therefore, the bond between the ion exchange group and the metal fine particles can be easily generated only by immersing the insulator in the solution in which the metal fine particles are dispersed.

  For example, a palladium-tin colloid used as a catalyst for electroless plating prepared by mixing palladium chloride and tin chloride in an acidic aqueous solution of hydrochloric acid, or an insulator in a dispersion of palladium halide, oxide, or acetylated complex Soak. Thereby, metal fine particles are easily bonded to the ion-exchange group in a position-selective manner.

  As described above, the composite member can be obtained by forming the conductive portion in the insulator by the method of the present invention. In order to further improve the conductivity of the conductive portion of the composite member, it is desirable to perform either or both of the following step (4) and step (5).

<Process (4)>
In order to improve the conductivity of the conductive portion 4 formed by ion exchange, as shown in FIG. 1D, metal ions bonded to the ion exchange group are brought into contact with a reducing agent to be metallized.

An example of a metallization reaction between an ion exchange group and a metal ion is shown in the following chemical formula (3).

  The reducing agent used is not particularly limited, and examples thereof include dimethylamine borane, trimethylamine borane, hydrazine, formalin, sodium borohydride, hypophosphite such as sodium hypophosphite, and the like. The conductive portion 4 can be metallized by immersing the insulator in a solution containing such a reducing agent.

<Step (5)>
In order to improve the conductivity of the conductive portion 4, electroless plating 5 is applied as shown in FIG. Thereby, the inside of the void | hole of the electroconductive part 4 can be filled up with a metal to some extent.

  The metal is most preferably copper with low electrical resistance and relatively low corrosion. Specifically, the electroconductive part obtained in the previous step is used as a catalyst core and brought into contact with the electroless plating solution.

  Examples of the electroless plating solution include those containing metal ions such as copper, silver, palladium, nickel, cobalt, platinum, gold, and rhodium.

  In addition to the metal salt aqueous solution described above, this electroless plating solution includes reducing agents such as formaldehyde, hydrazine, sodium hypophosphite, sodium borohydride, ascorbic acid, glyoxylic acid, sodium acetate, EDTA, tartaric acid, malic acid. In addition, complexing agents such as citric acid and glycine, precipitation control agents, and the like are included, and many of these are commercially available and can be easily obtained. Therefore, the member may be immersed until the desired conductive film thickness of the electroless plating solution or the filling of the porous interior is completed.

  In addition, when a porous body is used as the insulator, it is desirable to further perform the following step (6) in order to improve the electrical insulation and mechanical strength of the composite.

<Step (6)>
The pores of the porous body are filled with an impregnating resin or an inorganic substance. Examples of the impregnating resin include those made of a curable resin such as epoxy resin, polyimide, BT resin, benzocyclobutene resin, and cross-linked polybutadiene resin. Silica or the like can be used.

  If there are pores in the insulator, the inner surface of the pores may absorb moisture and the electrical insulation may be impaired. However, if the void is a closed cell which is sufficiently smaller than the size of the conductive portion, that is, the via diameter if it is a via, and the wiring width and wiring pitch if it is a wiring, it is possible to maintain a certain degree of insulation.

  Examples of the material to be filled include the above-described impregnating resin and the inorganic substance, and are not particularly limited. However, an impregnating resin is most preferable in consideration of filling properties, adhesiveness, and the like.

  In some cases, the impregnating resin may be mixed with an inorganic filler of nanometer order.

  Examples of the inorganic filler include metal oxides such as silica and alumina, metal nitrides such as silicon nitride and aluminum nitride, and ultrafine metal particles such as platinum and palladium. The inorganic filler can be preliminarily mixed with the impregnating resin and impregnated with the mixture. Or after impregnating the mixture of an inorganic filler precursor and an impregnation resin, you may produce | generate an inorganic filler in a void | hole. As such an inorganic filler precursor, silsesquioxane, polysilazane and the like are preferably used.

  In the production method of the present invention, it is necessary to avoid the formation of an ion-exchange group-containing organic compound in the photosensitive composition layer other than the target site for forming the conductive portion as much as possible. For this reason, it is preferable to perform the operation up to the plating in a yellow room where light having a short wavelength is blocked.

  In the method for manufacturing a composite member according to the present invention, an easily removable insulator such as thermal decomposability can also be used. In this case, first, a conductive portion is formed in a predetermined region of the insulator. Next, the porous body is removed by means such as heating before being impregnated with the impregnating resin by the above-described technique and cured. Thereby, a wiring board in which vias and wirings are formed in a cured product of the impregnating resin may be formed. In this case, the conductive portion is finally formed in a material different from the insulator used for forming the conductive portion.

  Note that when the insulator is pressurized and compressed during the curing of the impregnating resin, the void formed by removing the porous body of the conductive portion is crushed, and the conductive substances adhere to each other. As a result, the conductivity of the conductive column can be improved, which is preferable.

  In the composite member produced by the method of the present invention, the organic compound layer derived from the photosensitive composition remains at the interface between the insulator and the conductive part. In this case, as described with reference to FIG. 2, it is preferable to adjust the content of the organic compound per unit surface area on the insulator surface. As a result, the adhesion between the conductive portion and the insulator can be improved, and the electrical characteristics of the conductive portion can also be improved.

  That is, as shown in FIG. 2, a composite member in which the conductive portion 23 is partially formed on the surface or inside of the porous insulator 21 via the organic compound 24, and the unit surface area on the surface of the insulator 21. It is preferable that the content of per organic compound 24 satisfies the following relationship. That is, the amount of the organic compound 24 that exists between the insulator 21 and the conductive portion 23 is larger than the content of the organic compound 24 that exists other than between the insulator 21 and the conductive portion 23.

  In order to improve the moisture resistance of the composite member, prevent migration, etc., the organic compound 24 content between the insulator 21 and the conductive portion 23 is present between the insulator 21 and the conductive portion 23. The content is preferably 5 times or more, more preferably 10 times or more.

  In this case, the organic compound 24 may be derived from the photosensitive composition used in the method for producing a composite member according to the present invention, or may be other than that. In particular, it is desirable that the insulator 21 and the photosensitive composition have different structures in that the insulator is not deteriorated by light irradiation and the material selection of the insulator is not limited.

  For example, when the present invention is used for a multilayer wiring board, versatile resins such as epoxy resin, phenol resin, bismaleimide-triazine (BT) resin, polyimide, polyamide, polyallyl ether conventionally used for insulating parts , Heat resistant polymers such as polyarylate and polyethersulfone can be used. Further, if it is desired to lower the dielectric constant, materials such as polytetrafluoroethylene (PTFE) -based polymer and benzocyclobutene (BCB) resin can be selected depending on the application. Furthermore, as described above, since the insulator is not easily damaged by light degradation during exposure, the thickness and the like can be set freely.

  A multilayer wiring board can be produced using the composite member produced by the method of the present invention. This will be described with reference to FIG.

  In FIG. 4, the perspective view and sectional drawing of the composite member used for manufacture of a multilayer wiring board are shown. First, a composite member is manufactured according to the method of the present invention. As shown in FIG. 4, in the sheet-like composite members a, b, and c, a conductive portion 42 serving as a wiring pattern is formed on the surface of the porous insulator 41, inside, or both. In the sheet-like composite member d, a conductive portion 42 serving as a via pattern is formed on the surface of the porous insulator 41 and / or inside thereof. Like the composite member b, the via pattern and the wiring pattern may be formed on the same sheet.

  As shown in the composite member d in which the via pattern is formed, it is desirable that the end surface of the conductive portion 42 that is a via has an acute angle structure such as a sword mountain shape protruding from the sheet surface. Thereby, it is possible to improve the connection between the via and the wiring.

  It is also possible to coat the end face of the via with solder, but in this case also, it is more preferable to have an acute angle structure. However, since solder tends to cause voids and the like when the flux evaporates, it is preferable to form an acute angle structure on the end face of the via with a relatively hard metal such as a nickel alloy. When the via end face is flat, the end face is covered with the impregnating resin and electrical connection is likely to be hindered. The sword mountain-like structure can be formed, for example, by applying Cu / Ni eutectic acicular plating.

  A multilayer wiring board on which a three-dimensional wiring is formed is obtained by alternately laminating a plurality of composite members a, b, c formed with wiring patterns formed in this way and a composite member d formed with via patterns. can get.

  A multilayer wiring board can be manufactured by preparing a plurality of composite members in which wiring patterns and via patterns are formed in advance and laminating them in a lump. Alternatively, a porous body on which a wiring pattern or via pattern is not yet formed is overlaid on a composite member on which a wiring pattern or via pattern is formed, and then exposed and plated to form a wiring pattern, which is sequentially repeated. Thus, a multilayer wiring board can be obtained.

  It is desirable that the composite members in the multilayer wiring board are laminated by pressure bonding. When the pressure bonding is performed, an adhesive layer may be inserted between adjacent sheets.

  Further, after the pressure bonding, if a porous body is filled with an impregnation resin such as an epoxy resin, polyimide, BT resin, or benzocyclobutene resin and cured, a stronger multilayer wiring board can be formed. Of course, inorganic substances such as silica produced from silica sol, silsesquioxane, polysilazane and the like may be filled in addition to the impregnating resin. The impregnating resin may be impregnated before the pressure bonding, and the impregnating resin may be cured while being pressure bonded, but the via end face may be covered with the impregnating resin.

  By forming the wiring pattern in a composite form with a porous film-like insulator, the step between the wiring portion and the non-wiring portion can be made extremely small. In some cases, such a step can be eliminated, so that a plurality of composite members can be easily laminated. Furthermore, it is possible to reduce the film thickness of the composite member or increase the number of layers in the multilayer wiring board. In particular, when the thickness of the porous film-like insulator is as thin as about several μm, such an effect is remarkable.

  As described above, the method of manufacturing the multilayer wiring board by laminating the composite member in which the wiring pattern is formed and the composite member in which the via is formed has been described. However, the present invention is not limited to this. A multilayer wiring board can also be manufactured using a composite member in which wiring patterns and vias are formed.

  A cross-sectional view of such a composite member is shown in FIG. In the composite member shown in FIG. 5, a wiring pattern and a via are formed in one member by forming conductive portions 52 having different depths in a sheet-like porous insulator 51. By manufacturing a multilayer wiring board using such a composite member, the number of stacks can be reduced and the process can be simplified.

  At this time, in order to create conductive portions having different depths in the sheet-like porous insulator, by adjusting the absorbance with respect to the exposure wavelength of the sheet-like porous insulator (hereinafter referred to as porous insulator sheet). The penetration length of the exposure light into the porous insulator sheet is controlled so as to remain within the sheet thickness. Using such exposure light, the wiring pattern is exposed from one surface, and the via pattern is exposed from the other surface. Then, the composite member which has a wiring pattern and a via can be obtained by performing electroless plating etc. Alternatively, the via pattern may be exposed using exposure light having a wavelength that is not so much absorbed by the porous insulator. By using these methods, the inner via can be manufactured very simply. That is, since the wiring pattern and the via can basically be manufactured in the same process, the manufacturing process is simplified. If the wiring pattern is exposed on both sides of the insulator, a double-sided wiring board can be produced.

  As described above, according to the method of the present invention, a composite member in which fine vias and wirings are freely and accurately formed can be manufactured. The resulting composite member is also excellent in properties such as mechanical properties and electrical insulation.

  In the multilayer wiring board in which the composite members are laminated, as shown in FIG. 3, a layer 35 made of a conductor that does not contain an insulator component is formed on the outermost surfaces of the conductive portions 32 and 33 of each composite member. Preferably it is formed. As described above, the presence of the layer 35 made of a conductor containing no insulator component on the outermost surfaces of the conductive portions 32 and 33 of the substrate makes the contact between the conductive portions good. Therefore, it is effective for reducing the resistance of the conductive portion.

  Specifically, the layer 35 made of a conductor not including an insulator component formed on the outermost surface of the conductive portion is preferably a layer made of a metal such as low resistance copper. “Not containing an insulator component” means that the content of the insulator component in the conductor is 5% or less in terms of volume fraction. The thickness of the layer is preferably 20 μm or less, particularly 10 μm or less in consideration of the flatness of each layer. In addition, it is desired that the thickness is set to 1 to 50%, more preferably 5 to 20% of the thickness of the layer made of the conductor formed in the porous body containing the insulator component. If the thickness is too thick, the step of the conductive portion becomes large, and stacking becomes difficult. On the other hand, if it is too thin, the effect of reducing the resistance of the conductive portion is not sufficient.

  The layer 35 made of a conductor can be formed by performing electroless plating corresponding to the step (1) for a long time. Alternatively, the conductor layer 35 may be formed by forming a patterned conductive portion inside the insulator and then immersing it again in a plating bath. In order to give flexibility to the shape of the outermost surface of the conductive part, it is desirable to bond the metal foil to the end face of the conductive part.

  In order to obtain a multilayer wiring board having such a configuration, first, a conductive part including a wiring part and a via part is formed by exposing and plating the porous sheet. Thereafter, an adhesive such as an epoxy resin or polyimide (polyamic acid) is applied to the surface of the porous sheet other than the conductive portion, and adhesion of the metal foil and connection between the conductive portion and the metal foil are performed.

  The adhesive may be applied by a silk screen method or the like, but may be applied by an ink jet method or the like. At this time, it is preferable to solder-plat the end face of the conductive part.

  After bonding, the metal foils on both sides are processed by a conventional method such as a subtractive method to form a circuit pattern. A multilayer wiring board can be manufactured by injecting an appropriate impregnating resin into each composite member and then laminating with a hot press.

  Alternatively, a metal foil is bonded to one side of the porous film, and a conductive portion is formed in the porous film in a desired pattern by exposure and plating. Thereafter, a metal foil is bonded to the upper surface to connect the conductive portion and the metal foil, and the upper and lower copper foils are patterned to form a circuit pattern to obtain a composite member. A multilayer wiring board can be manufactured by multilayering this by the same method as described above.

  Furthermore, a layer made of a conductor is formed by employing various methods such as using a technique of bonding a porous film by transferring a metal wiring pattern formed in advance in a pattern instead of a metal foil. Can do.

  Of course, the layer made of such a conductor causes a step, which causes a problem in stacking. However, since it plays a role of conduction in cooperation with the conductive portion formed inside the porous body, the film thickness can be reduced. Particularly in high-frequency wiring, the electrical conductivity on the surface of the wiring affects the conductive characteristics of the entire wiring due to the skin effect. Therefore, even if the film thickness is thin, a sufficient effect can be expected. A multilayer wiring board having a structure as shown in FIG. 3 is optimal for such applications.

  The method for manufacturing a composite member according to the present invention can be applied to formation of wiring between layers of a multilayer chip of a semiconductor device in addition to formation of a multilayer wiring board or a three-dimensional wiring board. Specifically, it is the formation of interlayer wiring when stacking semiconductor chips having pads on the upper and lower sides. For example, a columnar wiring or the like is formed in the thickness direction of the porous body of the sheet-like insulator in accordance with the arrangement of the pads of the semiconductor chip, or not in particular. By inserting and laminating the sheet on which the columnar wiring is formed in this manner between two semiconductor chips, wiring between two adjacent semiconductor chips can be formed. Thereafter, the sheet may be removed by a technique such as oxygen ashing or thermal decomposition. Further, after removing the porous sheet, the wiring made porous by electrolytic plating, electroless plating, or the like can be densified.

  Furthermore, the composite member manufactured by the method of the present invention can be combined with a wiring substrate such as a glass epoxy substrate. Examples of the wiring board used include those prepared from a resin sheet obtained by impregnating a reinforcing fiber such as a glass cloth or an aramid fiber nonwoven fabric prepared by a known manufacturing method with an impregnating resin. By compounding in this way, it is possible to easily ensure the bending strength.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited only to these Examples.

(Example 1) Formation of wiring pattern on insulator surface A bismaleimide-triazine resin sheet was prepared as an insulator. On the other hand, a naphthoquinone diazide-containing phenol resin (naphthoquinone diazide content; 33 equivalent mol%) was dissolved in acetone to prepare a photosensitive composition solution having a concentration of 1 wt%. The molecular weight of the phenol resin used here is 2500. The obtained solution was spin-coated on the above resin sheet so as to have a thickness of 0.1 μm to obtain a coating film. Further, the photosensitive composition layer was formed by drying at room temperature for 30 minutes.

The sheet was exposed using CANON PLA 501 through a mask having a line width of 10 μm and a space of 30 μm under a light amount of 500 mJ / cm ² (wavelength 436 nm) to form a latent image made of indenecarboxylic acid.

  The sheet on which the pattern latent image was formed was immersed in an aqueous copper sulfate solution adjusted to 0.5 M for 5 min, and then washed with distilled water three times. The pH of the copper sulfate aqueous solution used was 4.1. The washed sheet was immersed in a 0.01 M aqueous solution of sodium borohydride for 30 minutes and then washed with distilled water to produce a composite member. In the obtained composite member, a conductive portion made of Cu as a mask having a line width of 10 μm and a space of 30 μm was formed.

  In FIG. 6, the optical microscope photograph observed from the surface of the electroconductive part in the composite member obtained by the present Example is shown. This photograph is a reflection optical microscope photograph taken at a magnification of 180 times.

  In addition, regarding the cross section of the composite member obtained in this example, an acid dyeing test using tetrabromophenol blue was performed. As a result, carboxylic acid derived from indenecarboxylic acid was present at the interface between the conductive part and the insulator. It was confirmed that

  In this composite member, the above-mentioned indenecarboxylic acid was not observed at a site other than the interface between the insulator and the conductive part.

  The composite member (conductive pattern forming sheet) thus obtained was further immersed in an electroless plating solution PS-503 for 30 minutes, and a conductive pattern was plated with copper to form a wiring pattern.

  Evaluation of adhesion between the conductive part and the insulator is as follows. In the conventional products, many multilayer wiring boards having a peel strength of plated metal at room temperature of about 1.0 kN / m are commercially available. In the composite member composed of the BT resin sheet-Cu layer obtained under the same conditions as described above, the BT resin sheet was fixed, and the peel strength of the Cu part was measured at 90 ° direction and 50 nm / min. As a result, it was 1.9 kN / m, and it was confirmed that the adhesion between the conductive portion and the insulator was better than that of the conventional product. In the composite member manufactured by the method of the present invention, it can be seen that the organic photosensitive compound functions sufficiently as an adhesive layer.

(Example 2) Formation of wiring pattern on insulator of porous body As the insulator, a PTFE porous film (pore diameter: 500 nm, film thickness: 20 μm) was used, and the photosensitive composition solution used in Example 1 was The entire surface of the film was coated by a dip method. By this operation, the inner pore surface of the porous film was coated with the naphthoquinonediazide-containing phenol resin. Thereafter, the same operation as in Example 1 was performed using a mask having a dot diameter of 50 μm and a space of 50 μm to produce a composite member (conductive pattern forming sheet). In the obtained composite member, a conductive portion having a dot diameter of 50 μm and a space of 50 μm was formed over the inside of the insulator.

(Example 3) Electroless plating treatment The conductive pattern forming sheet obtained in Example 2 was immersed in an electroless copper plating solution PS-503 for 30 minutes, and the conductive part was subjected to copper plating to form a wiring pattern. A similar pattern shape was formed on the back side of the film.

  In FIG. 7, the optical microscope photograph observed from the surface of the wiring pattern in the composite member obtained by the present Example is shown. This photograph is a reflection optical microscope photograph taken at a magnification of 180 times.

  In the composite member obtained in this example, a carboxylic acid derived from indene carboxylic acid existing at the interface between the conductive part and the insulator and other than the interface between the insulator and the conductive part was used in the same manner as in Example 1. And observed. As a result, carboxylic acid derived from indenecarboxylic acid was observed only at the interface between the insulator and the conductive part. Further, the adhesion between the conductive part and the insulator was good.

(Example 4) Double-sided printed wiring board An NMP solution containing a graft copolymer of polyamic acid and polyethylene oxide represented by the following formula and a mixture of bis (4-maleimidophenylmethane) was prepared. However, the molecular weight of the polyethylene chain is about 20,000, the weight ratio of the polyamic acid component and the polyethylene oxide component is 2: 5, and the mixing ratio of the graft copolymer and bis (4-maleimidophenylmethane) is 7: 1 by weight. It was.

  A sheet was produced from this solution by a casting method. The obtained sheet was heated from room temperature to 150 ° C. over 30 minutes under a nitrogen stream, and heated at this temperature for 1 hour. Next, the temperature was raised to 250 ° C. over 30 minutes and heated at this temperature for 1 hour. Furthermore, the temperature was raised to 350 ° C. over 30 minutes, and heat treatment was performed at this temperature for 1 hour, to obtain a polyimide porous sheet having a thickness of 10 μm.

  When the heated film was observed with a transmission electron microscope, three-dimensionally continuous pores having a pore diameter of about 0.2 μm were formed.

  On the other hand, a naphthoquinone diazide-containing phenol resin (naphthoquinone diazide content: 33 equivalent mol%) was dissolved in acetone as a photosensitive composition solution to prepare a 1 wt% solution. The molecular weight of the phenol resin used here was 2500. This solution was coated on the entire surface of the polyimide porous sheet described above by the dipping method. By this operation, the inner pore surface of the porous sheet was coated with the naphthoquinonediazide-containing phenol resin.

This polyimide porous sheet is exposed with CANON PLA 501 through a mask having a dot diameter of 50 μm and a space of 50 μm under the condition of a light amount of 3 J / cm ² (wavelength 436 nm) to form a latent image made of indenecarboxylic acid. It was.

  The sheet on which the pattern latent image was formed was immersed in an aqueous copper sulfate solution adjusted to 0.5 M for 5 minutes, and then washed with distilled water three times. The pH of the aqueous copper sulfate solution used is 4.1. The washed sheet was immersed in a 0.01 M aqueous solution of sodium borohydride for 30 minutes and then washed with distilled water. After washing, the composite member was manufactured by immersing in electroless copper plating solution PS-503 for 30 minutes and copper plating the conductive part. In the obtained composite member, a conductive portion made of Cu according to a mask having a dot diameter of 50 μm and a space of 50 μm was formed.

(Example 5) Double-sided printed wiring board A polyimide porous sheet having a thickness of 10 µm was prepared in the same manner as in Example 4 described above. In this porous polyimide sheet, continuous pores having a pore diameter of about 0.2 μm were formed three-dimensionally.

  For the obtained porous sheet, a via sheet was formed in the same manner as in Example 4 using a mask having a pattern with a via diameter of 50 μm. Thereafter, the via end face was subjected to solder plating to obtain a via sheet. Further, a wiring sheet having a line width of 30 μm was produced using the same porous sheet by the same method as described above.

  And it aligned by the arrangement | sequence of a via sheet / wiring sheet / via sheet | seat in the position which a via | veer and wiring conduct | electrically_connect, and it heated and pressurized with the hot press machine and laminated | stacked, and the multilayer wiring board was obtained.

(Example 6)
A polyimide porous sheet having a thickness of 40 μm was produced in the same manner as in Example 4 described above. In this porous polyimide sheet, continuous pores having a pore diameter of about 0.2 μm were formed three-dimensionally.

  For the obtained porous sheet, a via sheet was formed in the same manner as in Example 4 using a mask having a pattern with a via diameter of 50 μm. Thereafter, the via end face was subjected to solder plating to obtain a via sheet. In addition, a wiring sheet having a line width of 30 μm was obtained using the same porous sheet by the same method as described above. Also on this wiring sheet, the conductive part was formed by the same method as in the case of the via sheet, and then solder plating was performed.

  Polyimide varnish was applied to the surface portion of the via sheet and the wiring sheet other than the conductive portion by a silk screen method.

  On the other hand, a commercially available positive photoresist was applied to a film thickness of 2 μm on a 0.3 mm thick stainless steel plate by a spin coating method to form a photoresist film. The obtained photoresist film was exposed and developed to produce a via transfer substrate and a wiring pattern transfer substrate. It should be noted that exposure was performed using a mask having a via diameter of 55 μm in the production of the via transfer substrate, and exposure was performed using a mask having a line width of 33 μm in the production of the wiring pattern transfer substrate. Both masks have the same pitch as the vias and wiring patterns formed in the porous sheet.

The transfer substrate thus obtained and the copper electrode were opposed to each other and immersed in a copper sulfate plating bath to perform electrolytic plating (current density 2 A / dm ² , 15 min). The pH of the copper sulfate used is 4.1. A copper pattern with a film thickness of about 5 μm was deposited on the photoresist removal portion of each transfer substrate to form a metal pattern, which was used as a metal transfer original plate.

  The via sheet corresponding to the pattern shape and the metal transfer original plate are pressure-bonded at 150 ° C. so that the conductive portion formed on the porous sheet faces the metal pattern of the metal transfer original plate, and the metal portion of the transfer original plate is porous. Transferred to a sheet. For the wiring sheet, the metal portion of the transfer original plate was similarly transferred.

  Thereafter, by the same method as in Example 5, alignment was performed in the via sheet / wiring sheet / via sheet arrangement at a position where the via and the wiring were conducted, and the laminate was heated and pressed with a hot press machine. As a result, a multilayer wiring board as shown in FIG. 3 was obtained.

  When the resistance of the upper end and the lower end of the laminated sheet was measured, it was 1 mΩ.

(Example 7) Anisotropic conductive sheet The conductive pattern-formed PTFE porous sheet produced in Examples 2 and 3 was Cu / Ni-based eutectic plated on the end face of the copper column, and the height was 2 to 3 μm. A sword mountain-like structure was formed. A resin composition to be impregnated into the PTFE porous sheet on which the copper column was formed was prepared as follows.

  An equivalent amount of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride and 2,2′-bis [4- (p-aminophenoxy) phenyl] propane are reacted in dimethylacetamide to form a polyamide. An acid varnish was prepared. 30% by weight of 2,2-bis [4- (4-maleimidophenoxy) phenyl was added to the polyamic acid varnish to obtain an impregnation solution.

  The obtained impregnating solution was impregnated into a PTFE porous sheet on which a copper column was formed, and then dried with hot air to remove the solvent. Subsequently, it heated at 200 degreeC for 30 minute (s), and produced the adhesive anisotropic conductive film.

(Example 8) Wiring to porous insulator 5 g of a compound (molecular weight 10,000) represented by the pattern formation formula (II), 0.1 g of N-hydroxynaphthylimide trifluoromethanesulfonate as an acid generator and cyclohexyl An organic photosensitive composition solution was prepared by dissolving 0.04 g of amine in 100 g of methoxymethyl propionate.

  As the insulator, a PTFE porous film (pore diameter: 500 nm, film thickness: 20 μm) was prepared. The entire surface of the film was coated with the above-mentioned organic photosensitive composition solution by a dip method, and then baked at 100 ° C. for 90 seconds. Further, exposure was performed under the same conditions as in Example 1 using a mask having a line width = 50 μm and a space width = 100 μm. Next, PEB was performed at 140 ° C. for 15 minutes, and then a conductive pattern forming process similar to that in Example 1 was performed to manufacture a composite member. In the obtained composite member, a conductive portion having an L line width = 100 μm and a space width = 50 μm was formed over the inside.

Example 9
As an organic photosensitive composition solution, 0.9 g of naphthoquinonediazide-containing phenol resin (naphthoquinonediazide content; 33 equivalent mol%) and 0.5 g of poly (ethylene-carbodiimide) resin were dissolved in 100 ml of acetone to prepare a solution. . The molecular weight of the phenol resin used here is 2500. Using this solution, a composite member was produced in the same manner as in Example 1. A good pattern was formed on the obtained composite member in the same manner as in Example 1.

  When this composite member was heat-treated at 80 ° C. for 1 hour and then peel strength was evaluated, it was 2.6 kN / m.

(Example 10)
As an organic photosensitive composition solution, poly (p-nitrobenzyl-p-vinylbenzene carbonate-co-styrene) was dissolved in toluene to prepare a solution having a concentration of 1% by weight. The resin used has a molecular weight of 15,000. A wiring pattern was formed on the PTFE porous film by the same method as in Example 2 except that this solution was used. As a result, a good conductive pattern was obtained according to the mask.

Example 11
First, a diblock copolymer of poly (vinyl styrene) and polymethyl methacrylate was synthesized by a living anionic polymerization method. Weight average molecular weight Mw = 287000 (poly (vinylethylene) molecular weight = 91000, polymethylmethacrylate molecular weight = 196000), Mw / Mn = 1.10. To this diblock copolymer, 1.7% by weight of 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone as a radical generator was added to obtain a mixture, and this mixture was added to cyclohexanone. A solution having a concentration of 10% by weight was prepared.

  The obtained cyclohexanone solution was applied on a PTFE plate using an applicator and dried to prepare a film having a thickness of 15 μm. This film was heat-treated at 135 ° C. for 24 hours under a nitrogen stream. After the heat treatment, 160 KGy was irradiated with β rays having an acceleration voltage of 2 MV. After irradiation, the film was washed with ethyl lactate to produce a porous film of crosslinked poly (vinylethylene).

  When the obtained film was observed with a transmission electron microscope, three-dimensionally continuous pores having a pore diameter of about 50 nm were formed.

On the other hand, a naphthoquinone diazide-containing phenol resin (naphthoquinone diazide content; 33 equivalent mol%) was dissolved in acetone to prepare a 0.5 wt% concentration solution, which was used as a photosensitive composition solution. This acetone solution was impregnated into the porous film described above, and then dried at room temperature. Using CANON PLA501, the wiring pattern and the via pattern were respectively exposed to this sheet through a mask to form a latent image made of indenecarboxylic acid. The wiring pattern has a line width of 20 μm, a space of 30 μm, and a via diameter of 10 μm. The exposure was performed under the condition of a light amount of 500 mJ / cm ² (wavelength 436 nm).

  The sheet on which the pattern latent image was formed was immersed in an aqueous copper sulfate solution adjusted to 0.5 M for 5 min, and then washed with distilled water three times. The pH of the copper sulfate aqueous solution used was 4.1. The washed sheet was immersed in a 0.01 M aqueous solution of sodium borohydride for 30 minutes and then washed with distilled water. Furthermore, it was immersed in electroless copper plating solution PS-503 for 30 minutes, and the copper plating was given to the electroconductive part. Thereby, the porous sheet in which the wiring pattern and via pattern made of Cu were respectively formed was obtained.

  The porous sheet (wiring sheet) on which the wiring pattern was formed was further subjected to electroless plating to form a 2 μm-thick layer made of only Cu on the end face of the wiring pattern. Further, the porous sheet (via sheet) on which the via pattern was formed was subjected to Cu / Ni eutectic plating on the end face to form a sword-like projection structure having a height of 2 to 3 microns.

  After laminating one via sheet between two thus obtained wiring sheets, the resin solution was impregnated. The impregnating resin solution used was prepared by adding 50 parts by weight of methyl isobutyl ketone to 100 parts by weight of a benzocyclobutene resin solution (manufactured by Dow Chemical Co., Ltd., trade name: XU13005). The laminated body of the sheets was subjected to pressure bonding, and then the solvent was removed. Furthermore, the double-sided wiring board was produced by heat-curing at 240 degreeC under nitrogen stream for 1 hour.

  In the same manner, four wiring sheets and three via sheets were alternately laminated to produce a four-layer multilayer wiring board. In addition, a via sheet and a wiring sheet were laminated on both sides of a four-layer FR-4 glass epoxy substrate (wiring width 75 μm) to prepare a six-layer multilayer wiring board. Furthermore, an eight-layer multilayer wiring board could be fabricated using two via sheets and two wiring sheets.

  Since the multilayer wiring board produced as described above has a layer made of only Cu on the end face of the conductive portion of the wiring sheet, the resistance is lower than that in which the layer made only of Cu is not formed on the end face. . Moreover, the multilayer wiring board which has a glass epoxy board | substrate in a core layer was excellent in bending strength.

Example 12
A polyimide porous sheet having a thickness of 20 μm was produced in the same manner as in Example 4 described above. In this porous polyimide sheet, continuous pores having a pore diameter of about 0.2 μm were formed three-dimensionally.

  On the other hand, 10 g of phenol novolak resin derivative capped with tert-butoxycarbonylmethyl group, 0.5 g of DTBPI-TF (bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate) and acridine orange as an acid generator (C.I. 46005) 0.08 g was dissolved in 200 g of methyl cellosolve to prepare an organic photosensitive composition solution.

  The polyimide porous body sheet obtained as described above was impregnated in this organic photosensitive composition solution, and then dried at 80 ° C. for 10 minutes to prepare an organic photosensitive composition-coated polyimide porous body sheet.

This sheet is exposed with a low-pressure mercury lamp through a wiring pattern mask having a line width of 50 μm and a space of 50 μm under the condition of a light amount of 10 mJ / cm ² (wavelength 254 nm), and then at 100 ° C. for 5 minutes. By performing the heat treatment, a latent image made of a carboxyl group-containing phenol novolac resin was formed. The penetration depth of the pattern into the sheet under these conditions was about 5 μm.

Subsequently, a via pattern mask was placed on the back side of the sheet and exposed. In the used via pattern mask, via portions of 50 μmφ are arranged at a pitch of 100 μm. The via portion was disposed so as to penetrate the line exposure portion drawn at the lower part of the sheet. These were subjected to long wavelength exposure with CANON PLA 501 under the condition of a light amount of 500 mJ / cm ² (wavelength 546 nm), and a latent image made of a carboxyl group-containing phenol novolac resin was formed in the same manner as described above.

  In the exposed sheet, a latent image in which the via exposure portion reached the line exposure portion was formed.

  The sheet on which the pattern latent image was formed was washed with distilled water, immersed in an aqueous copper sulfate solution adjusted to 0.5 M for 5 min, and then washed with distilled water three times. The pH of the aqueous copper sulfate solution used is 4.1. The washed sheet was immersed in a 0.01 M aqueous solution of sodium borohydride for 30 minutes and then washed with distilled water. Furthermore, it was immersed in electroless copper plating solution PS-503 for 30 minutes, and the copper plating was given to the electroconductive part. As a result, a composite member having a wiring pattern made of Cu as shown in FIG. 5 was obtained.

  The present invention can be suitably used for various applications such as various optical functional devices and multilayer wiring boards, and its industrial value is tremendous.

The cross-sectional schematic which shows the manufacturing method of the composite member of this invention. Schematic which shows the composite member of this invention. Schematic which shows the multilayer wiring board of this invention. The perspective view and sectional drawing of a composite member used for manufacture of a multilayer wiring board. Sectional drawing of the composite member used for manufacture of a multilayer wiring board. 3 is a photograph showing a conductive part of the composite member obtained in Example 1. FIG. 6 is a photograph showing a wiring pattern of a composite member obtained in Example 3.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Insulator 2 ... Photosensitive composition layer 3 ... Mask 4 ... Photosensitive part 5 ... Electroless plating

Claims (3)

A conductive member having a conductive portion formed through an organic compound on a predetermined region of the porous insulator surface or at least one inside thereof,
The organic compound is formed by exposing a photosensitive composition containing a compound that has a structure different from that of the porous insulator and generates an ion-exchange group,
The conductive part coats the surface of the inner vacancies of the insulator with the photosensitive composition, selectively generates an ion-exchange group in the exposed part, and selectively binds metal ions or metal fine particles thereto. Formed by metallization in contact with a reducing agent,
Of the organic compounds present between the insulator and the conductive portion is exposed portion, the content per unit surface area in the insulator surface, in addition to between the insulator and the conductive portion is an unexposed portion The composite member, wherein the content of the organic compound present is greater than the content per unit surface area on the insulator surface.   An electronic package comprising at least one electronic component electrically connected to the wiring board made of the composite member according to claim 1.   The composite member according to claim 1, wherein the organic compound is produced by irradiating the photosensitive composition with exposure light having a wavelength of 280 nm or more.

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