WO2009119877A1

WO2009119877A1 - Method of manufacturing wiring board, method of manufacturing optoelectric composite member, and method of manufacturing optoelectric composite board

Info

Publication number: WO2009119877A1
Application number: PCT/JP2009/056454
Authority: WO
Inventors: 智章柴田; 大地酒井; 敏裕黒田; 成行八木; 敦之高橋
Original assignee: 日立化成工業株式会社
Priority date: 2008-03-28
Filing date: 2009-03-30
Publication date: 2009-10-01

Abstract

Disclosed are a method of manufacturing a wiring board including, in order of mention, step A of fabricating a circuit on a first board, step B of providing a first support over the circuit fabrication surface of the first board with a first separation layer therebetween, and step C of providing a second board or a circuit on the opposite side of the circuit fabrication surface of the first board and a method of manufacturing an optoelectric composite member including, in order of mention, a step of providing an electric wiring board on a second support, a step of providing a first support, a step of removing the second support, and a step of fabricating an optical waveguide on the separation surface of the second support. The method of manufacturing the wiring board enables fabrication of the circuit with uniform wiring width and good dimensional stability. The method of manufacturing an optoelectric composite member enables reduction of distortion of the optical waveguide during the manufacturing steps, thereby improving the dimensional stability.

Description

Wiring board manufacturing method, optoelectric composite member manufacturing method, and optoelectric composite substrate manufacturing method

The present invention relates to a method of manufacturing a wiring board capable of uniformly processing the width of wiring and forming a circuit with good dimensional stability, and a method of manufacturing a photoelectric composite member in which distortion generated in an optical waveguide in the manufacturing process is reduced The present invention relates to a method for manufacturing a photoelectric composite substrate, a photoelectric composite substrate manufactured thereby, and a photoelectric composite substrate module using the same.

The development of the information society in recent years has been remarkable, and consumer devices have been reduced in size, weight, performance, and functionality, such as personal computers and mobile phones. Industrial equipment includes wireless base stations, optical communication devices, and servers. In addition, there is a demand for improvement in functions in the same way regardless of whether it is large or small, such as routers and other network-related devices.
In addition, with the increase in the amount of information transmitted, the frequency of signals handled tends to increase year by year, and high-speed processing and high-speed transmission technology are being developed.
For this reason, built-up multilayer wiring boards have come to be used in order to cope with higher frequency, higher density wiring, and higher functionality for flexible boards, including semiconductor chip mounting boards and motherboards. .
In the formation of such high-density fine wiring, the wiring width / wiring interval = 50 μm / 50 μm is the limit of wiring that can be formed with a high yield by the subtract method of forming wiring by etching.
For finer wiring formation, a relatively thin metal layer (seed layer) is formed on the surface of the insulating layer, a plating resist is formed thereon, and wiring is formed to the required thickness by electroplating. After removing the resist, a semi-additive method in which the seed layer is removed by soft etching has begun to be used. As a method for forming the seed layer, an electroless plating method, a method of bonding a thin metal foil, and a method of forming by using a sputtering method are generally known, and the pitch tends to decrease year by year.
In addition, a wiring board in which one or more interlayer insulating layers and wirings are formed, wherein at least one wiring layer has a mixed layer containing a metal and an insulating material between the wirings and the interlayer insulating layer, and between the wirings. There has been proposed a wiring board in which a mixed layer between wirings is removed so that an insulation resistance value is 1 GΩ or more (see Patent Document 1).

In addition, in high-speed and high-density signal transmission between electronic elements and between wiring boards, signal transmission interference and attenuation become barriers in conventional transmission using electric wiring, and the limits of high speed and high density are beginning to appear. In order to overcome this, a technique for connecting between electronic elements and wiring boards with light, so-called optical interconnection, has been proposed, and various studies have been made on the combination of electrical wiring and optical wiring.
Specifically, in order to use light for short-distance signal transmission between boards in a router or a server device or in a board, an opto-electric composite board in which an optical transmission path is combined with an electric wiring board has been developed. As an optical transmission line, it is desirable to use an optical waveguide that has a higher degree of freedom in wiring and can be densified than an optical fiber, and in particular, an optical waveguide that uses a polymer material with excellent workability and economy. Is promising.

The fine wiring board provided with the fine wiring as described above is manufactured by forming a metal pattern on the insulating resin layer. However, with the thinning of the insulating layer and high-density fine wiring, accurate front and back alignment is required. Become. However, if double-sided simultaneous wiring formation is performed with a thin substrate, dimensional distortion occurs, making it difficult to align the laminated electric wiring and optical waveguide. In addition, the method described in Patent Document 1 is useful as a method for forming fine wiring on one side, but it is difficult to form simultaneous wiring on both sides, resulting in circuit processing for each side. In general, for dimensional stability, when the front and back wiring are formed in order by fixing to a support plate or support substrate, the irregularities of the wiring formed earlier are transferred to the opposite surface of the substrate and misregistered to the metal pattern on the opposite surface There is a problem that short circuit failure due to, non-uniformity of the wiring width, misalignment of the wiring on the front and back sides, etc. are likely to occur. On the other hand, the same applies to the optical waveguide, and when the optical waveguide is built up on a resin or substrate having unevenness, it leads to non-uniform wiring width and greatly affects the propagation loss. Therefore, as in Patent Document 2, a method of forming an electric wiring circuit after forming an optical waveguide is employed.

By the way, regarding the combination of optical wiring and electrical wiring, for example, a method of bonding a semiconductor chip and an optical waveguide via an adhesive sheet as described in Patent Document 3 has been proposed. However, in this method, there is a problem that assembly is complicated because the optical waveguide is separated into pieces and the adhesive film is cut out separately.
Patent Document 4 proposes that an optical circuit board (optical waveguide) and an electric circuit board are simply combined using a sheet-like adhesive.

Further, as described above, a method of combining the optical wiring and the electrical wiring can be easily conceived as a method of joining the optical waveguide and the optical wiring substrate through the adhesive layer. However, it is difficult to accurately match and join the relative positions of the optical waveguide and the optical wiring board, and there is a concern that productivity may be reduced due to a decrease in the coupling efficiency between the optical wiring and the electrical wiring. On the other hand, as in Patent Document 5, first, a flexible optical wiring film is formed, a base metal layer is formed on the back surface thereof by electroless plating or vacuum deposition, and after patterning, electrolytic plating is performed to construct an electrical wiring. However, in this method, the adhesion strength between the back surface of the flexible optical wiring film and the base metal layer (electrical wiring) is not sufficient, and the reliability may be impaired.

JP 2006-93199 A JP 2004-341454 A JP 2006-39390 A JP 2008-122908 A Japanese Patent No. 3193500

An object of the present invention is to provide a method of manufacturing a wiring board capable of uniformly processing the width of wiring and forming a circuit with good dimensional stability (first object).
In the method described in Patent Document 4, since the optical waveguide is formed on the support, the support is peeled off, the sheet-like adhesive and the optical waveguide are bonded, and the electrical wiring board is laminated. If the peeling strength when peeling the waveguide from the support is large, the optical waveguide will be stretched, and even if it can be peeled with a small peeling strength, the stress accumulated in the waveguide is released, resulting in distortion. There is a problem that the dimension of the optical waveguide becomes unstable. Accordingly, an object of the present invention is to provide a method for manufacturing an optoelectric composite member in which distortion generated in an optical waveguide in a manufacturing process is reduced and dimensional stabilization can be achieved (second object).
It is another object of the present invention to provide an optoelectric composite substrate manufacturing method excellent in productivity, an optoelectric composite substrate manufactured thereby, and an optoelectric composite substrate module using the same (third object).

As a result of intensive studies, the present inventors have
(1) The substrate on which the circuit is formed is fixed to a support through a release layer, and the circuit on the substrate is embedded in the release layer, thereby achieving the first object.
(2) In addition to the conventional method, the second object can be achieved by peeling the lower support after attaching the upper support on the electrical wiring board;
(3) After obtaining an electrical wiring substrate with a lower cladding layer, by constructing an optical waveguide having the lower cladding layer as a constituent element, the third object can be achieved;
(4) A lower clad layer is formed on the substrate surface of the substrate with metal foil, and then an optical waveguide having the lower clad layer as a constituent element and an electric wiring substrate from the metal foil substrate are sequentially constructed. To achieve the third object,
I found.

That is, the present invention
(1) Step A for forming a circuit on the first substrate, Step B for laminating the first support on the circuit forming surface of the first substrate via the first release layer, the first substrate A method of manufacturing a wiring board (first invention) having in sequence a step C of forming a second substrate or circuit on the opposite surface of the circuit forming surface;
(2) The step of laminating the electric wiring board on the second support, the step of laminating the first support, the step of peeling the second support, and the light on the peeling surface of the second support A method for producing a photoelectric composite member having the steps of forming a waveguide in this order (second invention),
(3) After forming the lower cladding layer directly on the substrate surface of the electric wiring substrate or via the adhesive layer, or forming the lower cladding layer directly or via the adhesive layer on the substrate surface of the substrate with metal foil, the metal A first step of obtaining an electric wiring substrate with a lower cladding layer by forming an electric wiring substrate by forming a metal pattern of a metal substrate of the foil-coated substrate, and sequentially forming a core pattern and an upper cladding layer on the lower cladding layer A method for manufacturing an optoelectric composite substrate having a second step of constructing an optical waveguide (third invention), and (4) forming a lower clad layer directly on the substrate surface of the substrate with metal foil or via an adhesive layer A first step, a second step in which a core pattern and an upper clad layer are sequentially formed on the lower clad layer to construct an optical waveguide, and the metal foil of the substrate with the metal foil is made into a conductor pattern and electric wiring An optoelectric composite substrate manufacturing method having a third step of constructing a substrate (fourth invention);
Is to provide.

According to the method for manufacturing a wiring board (first invention) of the present invention, when the front and back wirings are sequentially formed, the unevenness of the wiring formed previously is not transferred to the back surface of the substrate, and the wiring width is uniformly processed. Circuit formation can be performed with good dimensional stability.
Moreover, according to the manufacturing method (2nd invention) of the photoelectric composite member of this invention, the distortion which arises in an optical waveguide at a manufacturing process is reduced, and dimension stabilization can be aimed at.
Furthermore, according to the present invention (third invention), the optical waveguide is constructed while observing the conductive pattern of the already constructed electrical wiring board that is very easy to visually recognize. Therefore, a photoelectric composite substrate having a large area can be manufactured easily and with high productivity.
In addition, according to the present invention (fourth invention), the conductive pattern and the like are formed while looking at the already constructed optical waveguide, so that the optical waveguide and the electric wiring board can be combined with high positional accuracy, and thus a large A photoelectric composite substrate having an area can be easily manufactured with good productivity. In addition, when the lower clad layer is to be joined to the electric wiring board and the electric wiring board is severely uneven, an air residue is generated in the joined portion, resulting in deterioration of the quality or the joined lower clad layer. Although unevenness may be formed, which may hinder subsequent optical waveguide construction, in the present invention, since flat objects are joined together, such a problem does not occur. In other words, the present invention can cope with a case where the electric wiring board has a rugged surface as well as an electric wiring board having a flat shape having an inner layer circuit.

It is a figure explaining the manufacturing method of the wiring board of this invention (1st invention). It is a figure explaining one embodiment of the manufacturing method of the wiring board of this invention (1st invention). It is a figure explaining another embodiment of the manufacturing method of the wiring board of this invention (1st invention). It is a figure explaining another embodiment of the manufacturing method of the wiring board of this invention (1st invention). It is a figure explaining the measuring method of the unevenness | corrugation of the board | substrate of this invention (1st invention). It is a figure explaining the manufacturing method of the photoelectric composite member of this invention (2nd invention). It is a figure explaining one embodiment of the manufacturing method of the photoelectric composite member of this invention (2nd invention). It is a figure explaining another embodiment of the manufacturing method of the photoelectric composite member of this invention (2nd invention). It is a figure explaining another embodiment of the manufacturing method of the photoelectric composite member of this invention (2nd invention). It is a figure explaining another embodiment of the manufacturing method of the photoelectric composite member of this invention (2nd invention). It is a figure explaining another embodiment of the manufacturing method of the photoelectric composite member of this invention (2nd invention). It is a schematic diagram which shows the manufacturing method of the photoelectric composite board | substrate of this invention (3rd invention). It is a schematic diagram which shows the manufacturing method of the photoelectric composite board | substrate of this invention (4th invention).

Explanation of symbols

1-1; first substrate 1-2; first release layer 1-3; first adhesive layer 1-4; first support 1-5; second substrate 1-6; Release layer 1-7; second adhesive layer 1-8; second support 1-9; circuit 1-10; adhesive layer 1-11; lower clad layer 1-12; Upper clad layer 1-14; substrate 1-15; optical waveguide 1-16; substrate X
1-17; metal layer 1-101; substrate surface 1-102 on the peeling surface side of the first substrate 1 where the wiring is present; substrate surface 2-102 on the peeling surface side where the first substrate 1 has no wiring DESCRIPTION OF SYMBOLS 1; Lower support body 2-2; Electrical wiring board 2-3; Upper support body 2-4; Lower clad layer 2-5; Core pattern 2-6; Upper clad layer 2-7; 2-9; mirror part 2-10; electric circuit 2-11; adhesive or adhesive film 2-12; release sheet 2-13; lower support separating surface 2-14; upper support separating surface 3-10; 4-10; electric wiring boards 3-11, 4-11; metal foils 3-12, 4-12; boards 3-13, 4-13; boards 3-14, 4-14 with metal foil; conductor protective layer 3 -20, 4-20; adhesive layer 3-30, 4-30; optical waveguide 3-31, 4-31; lower cladding layer 3-32, 4 32; core pattern 3-33,4-33; upper cladding layer

(I) First Invention A wiring board manufactured according to the present invention (first invention) includes, for example, a first substrate 1-1 on a first support 1-4 as shown in FIG. 1 (c). The circuit is laminated via the first release layer 1-2, and the circuit 1-9 of the first substrate 1-1 is embedded in the first release layer 1-2. A first adhesive layer 1-3 is used to fix the first support 1-4 and the first substrate 1-1.
Thereafter, a circuit is formed on the surface of the first substrate 1-1 opposite to the first support 1-4 (see FIG. 1 (f)), or as shown in FIG. 2 (f) -1. The layers in which the circuit is formed are multi-layered or, as shown in FIG. 2 (f) -2, the lower cladding layer 1-11, the core pattern 1-12, and the upper cladding layer 1-13 through the adhesive layer 1-10. Are laminated in order, or a substrate is further laminated on the upper cladding layer 1-13 surface of FIG. 2 (f) -2 as shown in FIG. 2 (f) -3. As shown in FIG. 2 (f) -4, after the layers in which the circuit is formed are multilayered as shown in FIG. 2 (f) -1, the optical waveguide 1-15 is formed as shown in FIG. 2 (f) -2. Or to form. In addition, as shown in FIG. 3, the optical waveguide 1-15 is disposed in the first layer in the first substrate 1-1, and the circuit is installed above and below. At this time, a circuit is formed on the surface opposite to the optical waveguide forming surface of the substrate X on the substrate X side, and the circuit 1-9 is embedded in the first release layer 1-2 (FIG. 3 (e)). )reference).
In the present invention, the circuit means an electric circuit and an optical circuit (optical waveguide).

Hereinafter, a method for laminating the first substrate 1-1 and the first support 1-4 will be described.
(Lamination method of first substrate and first support)
As a pre-process for stacking the first substrate 1-1 on the first support 1-4, the first support 1-4 and the first substrate 1-1 are smaller than each side by 5 to 30 mm. A first adhesive layer 1-3 having the same size as the first support 1-4 is interposed between the first release layer 1-2 and the first support 1-4 with the release layer 1-2 interposed therebetween. The circuit 1-9 can be embedded in the first release layer 1-2 by bonding together, and at the same time, the first substrate 1-1 can be fixed to the first support 1-4 ( (Refer FIG.1 (c)).
The lamination method is not particularly specified, and hand bonding, laminator, vacuum laminator, press, and vacuum press are preferable. When air enters the space between the first support 1-4 and the first substrate 1-1, the heating process leads to blistering. Therefore, a vacuum laminator or a vacuum press is more preferable as a bonding method that does not allow air to enter.
Further, in order to improve the embedding property of the circuit 1-9 and to flatten the surface opposite to the first support 1-4 of the first substrate 1-1, When laminating one support 1-4, the first substrate 1-1 is supported by a hard plate from the opposite side to the first support 1-4, or the first substrate 1-1 and the first support 1-4 are More preferably, the second support 1-8 is stacked on the first substrate 1-1 before the support 1-4 is stacked. The hard plate may be a material that is less deformed by pressure than the first release layer 1-2.

Next, a method for laminating the first substrate 1-1 and the second support 1-8 will be described.
(Lamination method of first substrate and second support)
In order to laminate the first substrate 1-1 on the second support 1-8 in the step D, the first substrate 1-1 may be attached via the second peelable adhesive layer 1-7. At this time, the second support 1-8 and the second adhesive layer 1-7 may be peeled off from the first substrate 1-1. If the second support 1-8 is not laminated, the second release layer 1-6 and the second adhesive layer 71- are not necessary.
When the second adhesive layer 1-7 having no removability is used, as a pre-process for laminating the first substrate 1-1 on the second support 1-8, the first support 1-4 And the second support 1-8 are sequentially separated so that the second release layer 1-6 having a side 1 to 30 mm smaller than the first release layer 1-2 is sandwiched between the second release layers 1-8. The first substrate 1-1 is bonded between the layer 1-6 and the second support 1-8 via a second adhesive layer 1-7 having the same size as the second support 1-8. Alternatively, the second substrate 1-5 can be fixed to the second support 1-8. When only the first support 1-4 is separated after laminating the second support 1-8, it is smaller than the first release layer 1-2, and less than the second release layer 1-6. You can cut the product to a larger size.
The method for stacking is not particularly specified, and may be the same as the method for stacking the first support and the first substrate.
Further, from the viewpoint of forming the circuit 1-9 on the opposite surface to the second support 1-8 of the first substrate 1-1, the second support 1-8 of the first substrate 1-1. The side surface is preferably a flat surface, and the second release layer 1-6 at that time is more preferably less deformed by pressure than the first release layer 1-2.

Hereinafter, each component necessary for stacking the first substrate 1-1 and the second substrate 1-5 on the first support 1-4 and the second support 1-8 will be described.
(First support and second support)
The types of the first support 1-4 and the second support 1-8 are not particularly limited. For example, an FR-4 substrate, a semiconductor substrate, a silicon substrate, a glass substrate, a metal plate, etc. The non-flexible hard material is preferable.
Further, by using dimensionally stable thick supports as the first support 1-4 and the second support 1-8, the first substrate 1-1 and the second substrate 1-5 are used. Dimensional stability can be imparted to itself, and the embedding property of the circuit 1-9 can be improved. The thickness of the support having a thickness having dimensional stability is not particularly limited, but an FR-4 substrate, a semiconductor substrate, a silicon plate, a glass plate, a metal plate, and the like are preferable from the viewpoint of dimensional stability.
The thickness of the support may be appropriately changed depending on the warp, dimensional stability, and productivity of the support, but is preferably 0.1 to 10.0 mm.
Moreover, it is preferable that the said hard board may also be the same material and support body thickness as the above.

(substrate)
The substrates (first substrate 1-1, second substrate 1-5, and substrate X16) used in the present invention (first invention) are not particularly limited, but as described above, Since the surface on the second support 1-8 side of the substrate 1-1 is preferably a flat surface, the flat surface of the metal layer before the circuit formation by the subtractive method or the resin flatness before the circuit formation by the semi-additive method is used. More preferably, the surface is a resin or metal flat surface suitable for forming the optical waveguide 1-15. The presence or absence of metal layers arranged above and below the substrate shown in FIGS. 1 to 3 may be determined by a circuit formation method.
The type of the substrate is not particularly limited, and for example, an FR-4 substrate, a build-up substrate, a polyimide substrate, a semiconductor substrate, a silicon substrate, a glass substrate, or the like can be used. However, when forming fine wiring, an insulating resin layer for fine wiring is preferable.
Thermosetting resin or thermoplastic resin can be used as the material of the insulating resin layer, and as the thermosetting resin, phenol resin, urea resin, melamine resin, alkyd resin, acrylic resin, unsaturated polyester resin, diallyl phthalate resin , Epoxy resin, silicone resin, resin synthesized from cyclopentadiene, resin containing tris (2-hydroxyethyl) isocyanurate, resin synthesized from aromatic nitrile, trimerized aromatic dicyanamide resin, triallyl trimetallate Resins, furan resins, ketone resins, xylene resins, thermosetting resins containing condensed polycyclic aromatics, and the like can be used.
Examples of the thermoplastic resin include polyimide resin, polyphenylene oxide resin, polyphenylene sulfide resin, and aramid resin.
Further, by using a film as the substrate, flexibility and toughness can be imparted to the first substrate 1-1, the second substrate 1-5, the substrate X1-16, and the optical waveguide 1-15. The material of the film is not particularly limited, but from the viewpoint of having flexibility and toughness, polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyethylene, polypropylene, polyamide, polycarbonate, polyphenylene ether, polyether Preferable examples include films of sulfide, polyarylate, liquid crystal polymer, polysulfone, polyethersulfone, polyetheretherketone, polyetherimide, polyamideimide, and polyimide.
The thickness of the film may be appropriately changed depending on the intended flexibility, but is preferably 5 to 250 μm. If it is 5 μm or more, there is an advantage that toughness is easily obtained, and if it is 250 μm or less, sufficient flexibility can be obtained.

(Release layer)
The type of the release layer is not particularly limited, and for example, a release sheet for press, a release resin or adhesive, UV or heat release resin, and the like can be used.
Further, since the surface on the second support 1-8 side of the first substrate 1-1 is preferably a flat surface as described above, a film-like material is used as the second release layer 1-6. By using it, planarization can be achieved. The material of the film is not particularly limited, but from the viewpoint of having flatness, polyester such as copper foil, silver foil, gold foil, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, polyamide, polycarbonate, polyphenylene Preferred examples include ether, polyether sulfide, polyarylate, liquid crystal polymer, polysulfone, polyether sulfone, polyether ether ketone, polyether imide, polyamide imide, and polyimide. From the viewpoint of heat resistance and releasability from the substrate, copper foil, polyimide film, and aramid film are more preferable.
The thickness of the film may be appropriately changed depending on the intended flatness, but is preferably 5 to 250 μm. If it is 5 μm or more, there is an advantage that toughness is easily obtained, and if it is 250 μm or less, sufficient embedding by the second adhesive layer 1-7 can be obtained.
Furthermore, since it is necessary to embed the circuit 1-9 of the first substrate 1-1 in the first release layer 1-2, it is preferable to use a material with good circuit embeddability. As the first release layer 1-2, the same material as that of the second release layer 1-6 is preferably used, but a release sheet for press is more preferable from the viewpoint of circuit embedding property.
The thickness of the release layer may be appropriately changed depending on the intended circuit thickness, but is preferably 5 μm or more thicker than the circuit thickness.

(Adhesive layer)
Adhesion between the first substrate 1-1 or the second substrate 1-5 and the first support 1-4 or the second support 1-8 is not particularly limited, but a release layer / adhesion layer In this case, the adhesive layers 1-3 and 1-7 having removability are preferable. The layer structure at that time is shown in FIG. Suitable examples of the material for the releasable adhesive layer include single-sided slightly adhesive double-sided tapes, hot melt adhesives, and UV curable adhesives. As described above, since it is necessary to embed the circuit 1-9 of the first substrate 1-1 in the first release layer 1-2, it is preferable to use a material having a thickness capable of embedding the circuit.
Also, adhesion when a release layer that does not need to be peeled again is sandwiched, or adhesion between the first substrate 1-1, the second substrate 1-5, and the optical waveguide 1-15 (adhesion layer 1-10) For example, a heat-resistant adhesive layer is preferable, and the material of the adhesive layer that does not need to be peeled again is not particularly limited. However, from the viewpoint of heat resistance, a prepreg, a build-up material, a heat-resistant adhesive, Preferable examples include insulating resins listed for the base material. In the optical waveguide 1-15, an adhesive layer having a high transmittance is required for adhesion of a portion through which an optical signal is transmitted. The material of the adhesive layer 1-10 is not particularly limited, but (PCT / JP2008 / 05465) It is more preferable to use the adhesive described in 1. When the first substrate 1-1 or the second substrate 1-5 is bonded to the first support 1-4 or the second support 1-8 with the release layer interposed therebetween, The thickness is preferably 5 μm or more thicker than the release layer.

Next, a method for forming each layer constituting the wiring board in the present invention will be described.
(Circuit formation method)
As a method of forming a circuit, a metal layer is formed on a surface on which a circuit is formed, an etching resist is further formed, an unnecessary portion of the metal layer is removed by etching (subtract method), a plating resist is formed, and a circuit is formed. A method of forming a circuit by plating only on the necessary part of the surface on which the metal is to be formed (additive method), forming a thin metal layer (seed layer) on the surface on which the circuit is to be formed, further forming a plating resist, and then electroplating There is a method (semi-additive method) in which a thin metal layer is removed by etching after forming a necessary circuit.
Any method may be used for forming the circuit, but the semi-additive method is more preferable in order to form fine wiring with (circuit width) ≦ 20 μm.
The etching resist or plating resist used for circuit formation can be either a positive type or a negative type. However, the positive type resist is more preferable because fine wiring can be easily formed.

(Formation of seed layer in semi-additive process)
In the case of circuit formation by a semi-additive method, there are a method for forming a seed layer on a surface on which a circuit is formed, a method by vapor deposition or plating, and a method of bonding a metal layer.
(Formation of seed layer by vapor deposition or plating)
As described above, the seed layer can be formed on the surface on which the circuit is formed by vapor deposition or plating.
For example, when a base metal and a thin film copper layer are formed by sputtering as a seed layer, the sputtering apparatus used to form the thin film copper layer is a bipolar sputtering, a three-pole sputtering, a four-pole sputtering, a magnetron sputtering, a mirror. Tron sputtering or the like can be used.
The target used for sputtering is sputtered 5 to 50 nm using a metal such as Cr, Ni, Co, Pd, Zr, Ni / Cr, or Ni / Cu as a base metal in order to ensure adhesion.
Thereafter, a seed layer can be formed by sputtering 200 to 500 nm using copper as a target.
Alternatively, it is possible to form plated copper on the surface on which the circuit is formed by electroless copper plating of 0.5 to 3 μm.

(Method of bonding metal layers)
When the surface on which the circuit is formed has an adhesive function, as described above, the seed layer can also be formed by laminating the metal layer by pressing or laminating.
However, since it is very difficult to directly bond a thin metal layer, there are methods such as a method of thinning by attaching a thick metal layer and then a method of removing the carrier layer after bonding a metal layer with a carrier. is there.
For example, the former has a three-layer copper foil of carrier copper / nickel / thin film copper, the carrier copper is removed with an alkali etching solution, nickel is removed with a nickel etching solution, and the latter is made of aluminum, copper, insulating resin, etc. The peelable copper foil can be used, and a seed layer of 5 μm or less can be formed.
Alternatively, a 9 to 18 μm thick copper foil may be attached, and the seed layer may be formed by etching so that the thickness is uniformly 5 μm or less.
What is necessary is just to use what is generally used about the kind of electroplating in a semi-additive method, Although it does not specifically limit, In order to form a circuit, it is preferable to use copper as a plating metal.

(Circuit formation by additive method)
In the case of circuit formation by the additive method, as with the semi-additive method, it is formed by plating only on the necessary part of the surface on which the circuit is formed. However, the plating used in the additive method is usually electroless plating. used.
For example, after depositing an electroless plating catalyst on the surface on which the circuit is to be formed, a plating resist is formed on the surface portion where plating is not performed, and the substrate is immersed in an electroless plating solution and not covered with the plating resist Only the electroless plating is performed to form a circuit.

(Multi-layer circuit board with circuit)
When a circuit board is multilayered, an insulating layer substrate is formed on the circuit forming surface, and circuit formation is performed on the insulating layer substrate surface using at least one of the subtractive method, semi-additive method, and additive method described above. Can be done. As the substrate for the insulating layer, a build-up substrate, a prepreg, a polyimide substrate, and the like are preferably exemplified.
The method of forming the insulating layer substrate is not particularly limited. When a build-up substrate is used, the insulating layer substrate is formed using a roll laminator or a vacuum laminator, and then a circuit is formed using a semi-additive method or an additive method. be able to. When a prepreg is used, a prepreg and a metal layer are sequentially formed on the circuit formation surface, and after press lamination, the metal layer can be formed using a subtractive method or a semi-additive method. When a polyimide substrate is used, if a polyimide substrate with a metal layer is used, circuit formation is performed using a subtractive method or a semi-additive method after press lamination, roll lamination, or vacuum lamination on the circuit formation surface via an adhesive layer. If a polyimide substrate without a metal layer is used, a circuit can be formed using a semi-additive method or an additive method after laminating the polyimide substrate in the same manner as described above.

(Circuit interlayer connection)
Connections between circuits in each layer can be made as appropriate. The circuit interlayer connection method is described in detail below.
(Bahia Hall)
Since the wiring board of the present invention may have a layer having a plurality of circuits, a via hole for electrically connecting the circuits of each layer can be provided.
The via hole can be formed by providing a hole for connection in a substrate between circuit layers and filling the hole with a conductive paste, plating or the like.
Examples of the hole processing method include mechanical processing such as punching and drilling, laser processing, chemical etching processing using a chemical solution, and dry etching using plasma.

(Desmear)
As the smear removal of the via hole formed by the above-described method, a dry process or a wet process can be used.
As the dry treatment, plasma treatment, reverse sputtering treatment, or ion gun treatment can be used.
Furthermore, plasma processing includes atmospheric pressure plasma processing, vacuum plasma processing, and RIE processing, which can be selected as necessary.
As a gas used for these treatments, nitrogen, oxygen, argon, freon (CF ₄ ), or a mixed gas thereof is preferable.
An oxidizing agent such as chromate or permanganate can be used for the wet treatment.

(Interlayer connection)
As an interlayer connection method, in addition to the above-described method using via holes, a method in which a conductive layer is formed on the insulating layer with a conductive paste or plating, and is laminated on the surface of the insulating layer on which the circuit is formed by pressing or laminating. There are also.

(Formation of insulation coating)
An insulating coating can be formed on the circuit surface located on the outermost layer of the wiring board of the present invention, which is performed either before or after the first support 1-1 and the second support 1-5 are laminated. May be.
Pattern formation of the insulating coating can be performed by printing if it is a varnish-like material, but in order to ensure more accuracy, it is possible to use a photosensitive solder resist, a coverlay film, or a film-like resist. preferable.
As a material, an epoxy-based material, a polyimide-based material, an epoxy acrylate-based material, or a fluorene-based material can be used.

(Photoelectric composite substrate manufacturing method)
Hereinafter, a method for manufacturing a wiring board of the present invention using an optical waveguide as the second substrate 1-5 will be described in detail (see FIG. 3).
First, as shown in FIGS. 3A to 3C, a lower clad layer 1-11 is provided on a first substrate 1-1 fixed to a second support 1-8, and a core is formed thereon. A pattern 1-12 is formed, and an upper clad layer 1-13 is further laminated. If the first substrate 1-1 and the lower clad layer 1-11 do not have an adhesive force, they may be attached via the adhesive layer 1-10. Further, it is possible to use a method in which an optical waveguide having the lower clad layer 1-11, the core pattern 1-12, and the upper clad layer 1-13 as described above is directly attached onto a circuit with an adhesive.
The formation of the lower clad layer 1-11 on the support is not particularly limited, and may be performed by a known method. For example, a material for forming the lower clad layer 1-11 is applied on the lower support film by spin coating or the like. After prebaking, the thin film can be cured by irradiating with ultraviolet rays. Also, the formation of the core pattern 1-12 is not particularly limited. For example, a core layer having a refractive index higher than that of the lower cladding layer 1-11 is formed on the lower cladding layer 1-11, and the core pattern is formed by etching. Just do it. The method of forming the upper cladding layer 1-13 is not particularly limited, and may be formed by the same method as that of the lower cladding layer 1-11, for example.
The lower clad layer 1-11 may be coated with an adhesive or an adhesive sheet may be bonded between the lower clad layer 1-11 and the substrate from the viewpoint of adhesion to the substrate.

(Lower cladding layer and upper cladding layer)
Hereinafter, the lower clad layer 1-11 and the upper clad layer 1-13 used in the present invention will be described. As the lower cladding layer 1-11 and the upper cladding layer 1-13, a cladding layer forming resin or a cladding layer forming resin film can be used.

The clad layer forming resin used in the present invention is not particularly limited as long as it is a resin composition that has a lower refractive index than the core layer and is cured by light or heat, and includes a thermosetting resin composition and a photosensitive resin composition. It can be preferably used. More preferably, the clad layer forming resin is preferably composed of a resin composition containing (A) a base polymer, (B) a photopolymerizable compound, and (C) a photopolymerization initiator. The resin composition used for the clad layer forming resin may be the same or different in the components contained in the resin composition in the upper clad layer 1-13 and the lower clad layer 1-11. The refractive index of the resin composition may be the same or different.

The (A) base polymer used here is for forming a clad layer and ensuring the strength of the clad layer, and is not particularly limited as long as the object can be achieved, phenoxy resin, epoxy resin, (Meth) acrylic resin, polycarbonate resin, polyarylate resin, polyether amide, polyether imide, polyether sulfone, etc., or derivatives thereof. These base polymers may be used alone or in combination of two or more. Among the base polymers exemplified above, it is preferable that the main chain has an aromatic skeleton from the viewpoint of high heat resistance, and a phenoxy resin is particularly preferable. From the viewpoint of three-dimensional crosslinking and improving heat resistance, an epoxy resin, particularly an epoxy resin that is solid at room temperature is preferable. Further, compatibility with the photopolymerizable compound (B) described in detail later is important for ensuring the transparency of the resin for forming the cladding layer. From this point, the phenoxy resin and the (meth) acrylic resin are used. Is preferred. Here, (meth) acrylic resin means acrylic resin and methacrylic resin.

Among phenoxy resins, those containing bisphenol A, bisphenol A type epoxy compounds or derivatives thereof, and bisphenol F, bisphenol F type epoxy compounds or derivatives thereof as a constituent unit of the copolymer component are heat resistant, adhesive and soluble. It is preferable because of its excellent properties. Preferred examples of the bisphenol A or bisphenol A type epoxy compound include tetrabromobisphenol A and tetrabromobisphenol A type epoxy compounds. Moreover, as a derivative of bisphenol F or a bisphenol F-type epoxy compound, tetrabromobisphenol F, a tetrabromobisphenol F-type epoxy compound, etc. are mentioned suitably. Specific examples of the bisphenol A / bisphenol F copolymer type phenoxy resin include “Phenotote YP-70” (trade name) manufactured by Toto Kasei Co., Ltd.

Examples of the epoxy resin that is solid at room temperature include, for example, “Epototo YD-7020, Epototo YD-7019, Epototo YD-7007” (all trade names) manufactured by Toto Chemical Co., Ltd., and “Epicoat 1010” manufactured by Japan Epoxy Resins Co., Ltd. Bisphenol A type epoxy resin such as “Epicoat 1009, Epicoat 1008” (both trade names).

Next, (B) the photopolymerizable compound is not particularly limited as long as it is polymerized by irradiation with light such as ultraviolet rays, and the compound having an ethylenically unsaturated group in the molecule or two or more in the molecule. Examples thereof include compounds having an epoxy group.
Examples of the compound having an ethylenically unsaturated group in the molecule include (meth) acrylate, vinylidene halide, vinyl ether, vinyl pyridine, vinyl phenol, etc., among these, from the viewpoint of transparency and heat resistance, (Meth) acrylate is preferred.
As the (meth) acrylate, any of monofunctional, bifunctional, trifunctional or higher polyfunctional ones can be used. Here, (meth) acrylate means acrylate and methacrylate.
Examples of the compound having two or more epoxy groups in the molecule include bifunctional or polyfunctional aromatic glycidyl ethers such as bisphenol A type epoxy resins, bifunctional or polyfunctional aliphatic glycidyl ethers such as polyethylene glycol type epoxy resins, and water. Bifunctional alicyclic glycidyl ether such as bisphenol A type epoxy resin, bifunctional aromatic glycidyl ester such as diglycidyl phthalate, bifunctional alicyclic glycidyl ester such as tetrahydrophthalic acid diglycidyl ester, N, N- Bifunctional or polyfunctional aromatic glycidylamine such as diglycidylaniline, bifunctional alicyclic epoxy resin such as alicyclic diepoxycarboxylate, bifunctional heterocyclic epoxy resin, polyfunctional heterocyclic epoxy resin, bifunctional Or polyfunctional silicon-containing epoxy resin It is. These (B) photopolymerizable compounds can be used alone or in combination of two or more.

Next, the photopolymerization initiator of component (C) is not particularly limited. For example, as an initiator when an epoxy compound is used as component (B), aryldiazonium salt, diaryliodonium salt, triarylsulfonium salt, triallyl Examples include selenonium salts, dialkylphenazylsulfonium salts, dialkyl-4-hydroxyphenylsulfonium salts, and sulfonate esters.

In addition, as an initiator when a compound having an ethylenically unsaturated group in the molecule is used as the component (B), aromatic ketones such as benzophenone, quinones such as 2-ethylanthraquinone, benzoin ethers such as benzoin methyl ether Compounds, benzoin compounds such as benzoin, benzyl derivatives such as benzyldimethyl ketal, 2,4,5-triarylimidazole dimers such as 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- Benzimidazoles such as mercaptobenzimidazole, phosphine oxides such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, acridine derivatives such as 9-phenylacridine, N-phenylglycine, N-phenylglycine derivatives , Coumarin compound And the like. Moreover, you may combine a thioxanthone type compound and a tertiary amine compound like the combination of diethyl thioxanthone and dimethylamino benzoic acid. Of the above compounds, aromatic ketones and phosphine oxides are preferred from the viewpoint of improving the transparency of the core layer and the clad layer.
These (C) photopolymerization initiators can be used alone or in combination of two or more.

The blending amount of the (A) base polymer is preferably 5 to 80% by mass with respect to the total amount of the components (A) and (B). The blending amount of the (B) photopolymerizable compound is preferably 95 to 20% by mass with respect to the total amount of the components (A) and (B).
As a blending amount of the component (A) and the component (B), when the component (A) is 5% by mass or more and the component (B) is 95% by mass or less, the resin composition is easily formed into a film. Can do. On the other hand, when the component (A) is 80% by mass or less and the component (B) is 20% by mass or more, the (A) base polymer can be easily entangled and cured, and an optical waveguide is formed. The pattern forming property is improved and the photocuring reaction proceeds sufficiently. From the above viewpoint, the blending amounts of the component (A) and the component (B) are more preferably 10 to 85% by mass of the component (A) and 90 to 15% by mass of the component (B). More preferably, the content is 80% by mass and the component (B) is 80 to 30% by mass.
The blending amount of the (C) photopolymerization initiator is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). When the blending amount is 0.1 parts by mass or more, the photosensitivity is sufficient, while when it is 10 parts by mass or less, the absorption in the surface layer of the photosensitive resin composition does not increase during exposure, and the internal Is sufficiently cured. Furthermore, when used as an optical waveguide, it is preferable that the propagation loss does not increase due to the light absorption effect of the polymerization initiator itself. From the above viewpoint, the blending amount of the (C) photopolymerization initiator is more preferably 0.2 to 5 parts by mass.
In addition, if necessary, in the cladding layer forming resin, an antioxidant, an anti-yellowing agent, an ultraviolet absorber, a visible light absorber, a colorant, a plasticizer, a stabilizer, a filler, etc. You may add what is called an additive in the ratio which does not have a bad influence on the effect of this invention.

In the present invention, the method for forming the clad layer is not particularly limited. For example, the clad layer may be formed by applying a clad layer forming resin or laminating a clad layer forming resin film.
In the case of application, the method is not limited. For example, the resin composition containing the components (A) to (C) may be applied by a conventional method.
Moreover, the resin film for clad layer formation used for a lamination can be easily manufactured, for example by melt | dissolving the said resin composition in a solvent, apply | coating to a support film, and removing a solvent.

The material of the support film used in the production process of the clad layer forming resin film is not particularly limited, and various types can be used. From the viewpoints of flexibility and toughness as a support film, those exemplified above as the first support 1-1, the second support 1-5, and the film material of the substrate can be similarly mentioned.
The thickness of the support film may be appropriately changed depending on the intended flexibility, but is preferably 5 to 250 μm. If it is 5 μm or more, there is an advantage that toughness is easily obtained, and if it is 250 μm or less, sufficient flexibility can be obtained.
The solvent used here is not particularly limited as long as it can dissolve the resin composition. For example, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylacetamide, propylene glycol monomethyl ether, propylene A solvent such as glycol monomethyl ether acetate, cyclohexanone, N-methyl-2-pyrrolidone, or a mixed solvent thereof can be used. The solid concentration in the resin solution is preferably about 30 to 80% by mass.

The thickness of the lower cladding layer 1-11 and the upper cladding layer 1-13 (hereinafter abbreviated as the cladding layers 1-11, 1-13) is preferably in the range of 5 to 500 μm after drying. When the thickness is 5 μm or more, a clad thickness necessary for light confinement can be secured, and when the thickness is 500 μm or less, it is easy to control the film thickness uniformly. From the above viewpoint, the thickness of the cladding layers 11 and 13 is more preferably in the range of 10 to 100 μm.

The thicknesses of the cladding layers 1-11, 1-13 are the same in the lower cladding layer 1-11 formed first and the upper cladding layer 1-13 for embedding the core pattern 1-12. However, in order to embed the core pattern 1-12, the thickness of the upper clad layer 13 is preferably larger than the thickness of the core layer.

(Core layer forming resin and core layer forming resin film)
In the present invention, the method for forming the core layer laminated on the lower clad layer 1-11 to form the core pattern 1-12 is not particularly limited. For example, the core layer forming resin is applied or the core layer forming resin is formed. What is necessary is just to form by the lamination of a resin film.
As the core layer forming resin, a resin composition that is designed so that the core pattern 1-12 has a higher refractive index than the cladding layers 1-11, 1-13, and can form the core pattern 1-12 by actinic rays. A photosensitive resin composition can be used. Specifically, it is preferable to use the same resin composition as that used in the clad layer forming resin.
In the case of application, the method is not limited, and the resin composition may be applied by a conventional method.

Hereinafter, the resin film for core layer formation used for lamination is explained in full detail.
The resin film for forming the core layer can be easily produced by dissolving the resin composition in a solvent and applying the resin composition to the lower cladding layer 2 and removing the solvent. The solvent used here is not particularly limited as long as it can dissolve the resin composition. For example, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, N, N-dimethyl A solvent such as acetamide, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, N-methyl-2-pyrrolidone or a mixed solvent thereof can be used. The solid concentration in the resin solution is usually preferably 30 to 80% by mass.

The thickness of the core layer-forming resin film is not particularly limited, and the thickness of the core layer after drying is usually adjusted to be 10 to 100 μm. When the thickness of the film is 10 μm or more, there is an advantage that the alignment tolerance can be increased in the coupling with the light emitting / receiving element or the optical fiber after the optical waveguide is formed. There is an advantage that coupling efficiency is improved in coupling with a light emitting element or an optical fiber. From the above viewpoint, the thickness of the film is preferably in the range of 30 to 70 μm.

The support film used in the manufacturing process of the core layer forming resin is a support film that supports the core layer forming resin, and the material thereof is not particularly limited, but it is easy to peel off the core layer forming resin later. From the viewpoint of having heat resistance and solvent resistance, polyesters such as polyethylene terephthalate, polypropylene, polyethylene, and the like are preferable.
The thickness of the support film is preferably 5 to 50 μm. When it is 5 μm or more, there is an advantage that the strength as a support film is easily obtained, and when it is 50 μm or less, there is an advantage that a gap with the mask at the time of pattern formation becomes small and a finer pattern can be formed. From the above viewpoint, the thickness of the support film is more preferably in the range of 10 to 40 μm, and particularly preferably 15 to 30 μm.

The optical waveguide used in the present invention may be a multilayer optical waveguide in which a plurality of polymer layers having a core pattern and a cladding layer are stacked.
Since lamination of insulating substrates accompanying such multilayering and insulation coating is subject to shrinkage at the time of curing, if formed on only one side, the substrate is likely to be greatly warped.
Therefore, if necessary, the same material can be formed on the surface of the support opposite to the surface on which insulation coating or lamination is performed.
Furthermore, since the warpage varies depending on the thickness of the insulating coating and the insulating substrate, it is more preferable to adjust the thickness of the insulating coating and the insulating substrate formed on the support surface so that no warpage occurs.
In that case, it is preferable to conduct preliminary examination and determine the thicknesses of the insulating coatings on both sides.

(Electric circuit or electric wiring board)
In the present invention, the electric circuit or electric wiring board that may be formed on the optical waveguide is not particularly limited, and various electric wiring boards can be used, for example, an insulating resin layer or a substrate. In other words, a single-sided or double-sided metal layer substrate, or a resin layer with a metal layer on one or both sides can be used. An electrical wiring board is formed by laminating metal layers on both sides.
Examples of the material for the substrate and the resin layer include the same materials as those described for the substrate.
The metal forming the metal layer includes copper, gold, silver, Al, Ni, Cr, Co, Ti, Pd, Sn, Zn, Na, alloys thereof, and two or more layers of these metals. Etc.
Further, the above wiring board may be multilayered.

(II) Second Invention An optoelectric composite substrate manufactured according to the present invention (second invention) has, for example, a lower clad layer 2-2 on an electric wiring board 2-2 as shown in FIG. 4, an optical waveguide 2-8 in which a core pattern 2-5 and an upper cladding layer 2-6 are sequentially laminated. In the present invention, the term “electrical wiring board” simply refers to those in which the electric circuit layer is not formed, but the term “electrical wiring board” used after the circuit layer is formed is the electric circuit layer. Refers to an electrical wiring board on which is formed.

(Manufacturing method of photoelectric composite member)
Hereinafter, the manufacturing method of the photoelectric composite member of the present invention (second invention) will be described in detail (see FIG. 6). The method for producing a photoelectric composite member of the present invention (second invention) includes a step of laminating an electric wiring board on a second support, a step of laminating the first support, and peeling off the second support. It has a process and the process of forming an optical waveguide in the peeling surface of said 2nd support body in this order. An example in which the lower support 2-1 is used as the second support and the upper support 2-3 is used as the first support will be described.
First, as shown in FIGS. 6A and 6B, an electric wiring board 2-2 is provided on the lower support 2-1, and an electric circuit 2-10 is formed thereon. Next, the upper support 2-3 is laminated on the formation surface of the electric circuit 2-10 (see FIG. 6C), and the lower support 2-1 is peeled off (see FIG. 6D). Next, the electric circuit 2-10 is formed again on the peeling surface of the lower support 2-1, and a lower clad layer 2-4 is provided on the electric wiring board 2-2 as shown in FIG. 6 (e). A core pattern 2-5 is formed thereon, and an upper clad layer 2-6 is further laminated.
The method of forming the lower clad layer 2-4 on the electric wiring board 2-2 is not particularly limited, and may be a known method. It can be formed by coating on the plate 2-2, pre-baking, and then irradiating with ultraviolet rays to cure the thin film. Also, the formation of the core pattern 2-5 is not particularly limited. For example, a core layer having a refractive index higher than that of the lower cladding layer 2-4 is formed on the lower cladding layer 2-4, and the core pattern 2-5 is etched. 5 may be formed. The method of forming the upper cladding layer 2-6 is not particularly limited, and may be formed by the same method as that of the lower cladding layer 2-4, for example.
The lower cladding layer 2-4 is preferably flat with no step on the surface on the core layer lamination side, from the viewpoint of adhesion to the core layer. Further, the surface flatness of the clad 2-layer 4 can be ensured by using the clad layer forming resin film.

Next, the method of laminating the lower support 2-1 and the upper support 2-3 and the electric wiring board 2-2 is not particularly limited. For example, an adhesive or an adhesive film 2-11 having good removability is used. The electric wiring board 2-2 lower support body 2-1 and upper support board 2-3 are bonded together, or the product outer frame portion (outside the required pattern area) of the electric wiring board 2-2 is bonded with an adhesive. Any lamination method may be used as long as it can be separated by cutting off the adhesive portion after forming the circuit of the electric wiring board 2-2 or after forming the optical waveguide 2-8.
Next, as shown in FIG. 6E, the upper support 2-3 is peeled from the electrical wiring board 2-2 to obtain a photoelectric composite member (see FIG. 6G). The obtained composite body of the electrical wiring board 2-2 and the optical waveguide 2-8 can be used for various devices as a normal photoelectric composite member.

Hereinafter, each component of the photoelectric composite member will be described.
(Support and substrate)
The types of the lower support 2-1, the upper support 2-3, and the substrate 2-7 are not particularly limited. For example, an FR-4 substrate, a polyimide substrate, a semiconductor substrate, a silicon substrate, and a glass substrate are used. Or a flexible material that is flexible or a non-flexible hard material.
Moreover, a flexible photoelectric composite member can be obtained by using a flexible material for the substrate 2-7. The material of the material having flexibility is not particularly limited, but from the viewpoint of having flexibility and toughness, polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, polyamide, polycarbonate, Preferable examples include polyphenylene ether, polyether sulfide, polyarylate, liquid crystal polymer, polysulfone, polyether sulfone, polyether ether ketone, polyether imide, polyamide imide, and polyimide.
The thickness of the film may be appropriately changed depending on the intended flexibility, but is preferably 5 to 250 μm. If it is 5 μm or more, there is an advantage that toughness is easily obtained, and if it is 250 μm or less, sufficient flexibility can be obtained.

Further, by using a non-flexible material having a dimensional stability and thickness as the lower support 2-1 and the upper support 2-3, the dimensional stability of the optical waveguide itself can be imparted. The material of the dimensionally stable and thick substrate is not particularly limited, but FR-4 substrate, semiconductor substrate, silicon plate, glass plate, metal plate and the like are preferable from the viewpoint of dimensional stability.
Moreover, the electrical wiring board 2 can be obtained by subjecting the above-described thick substrate having dimensional stability to a release treatment, or applying the release treatment to the film surface after the film is attached. -2 can be imparted with re-peelability. From the viewpoint of heat resistance, preferred examples of the film material include polyimide and aramid.
The plate thickness may be appropriately changed depending on the warp and dimensional stability of the plate, but is preferably 0.1 to 10.0 mm.
In addition, an adhesive may be used for bonding the lower support body 2-1 or the upper support body 2-3 to the electric wiring board 2-2, and it is easy to release from the electric wiring board 2-2. When a certain adhesive is used, the entire surface may be affixed. However, when an adhesive having no releasability with respect to the electric wiring board 2-2 is used, the releasability is 5 to 30 mm smaller than the product size. By sandwiching the sheet between the electric wiring board 2 and the adhesive, only the product outer frame portion (outside the necessary pattern region) of the optical waveguide is laminated, and after the optical waveguide is formed, the laminated portion is cut off and easily separated. It is also possible. The material of the releasable sheet is not particularly limited, but from the viewpoint of releasability with respect to the electrical wiring board 2-2 and heat resistance, preferred examples include copper foil, polyimide, aramid, and release sheet for pressing. .

(Adhesive and adhesive film)
Adhesion between the lower support 2-1 or the upper support 2-3 and the electric wiring board 2-2 is not particularly limited, but when it is necessary to re-peel, an adhesive or an adhesive film having re-peelability Is preferred.
Preferable examples of the material for the adhesive or adhesive film include single-sided slightly adhesive double-sided tape, hot-melt adhesive, UV or heat-peelable adhesive.
Further, when the lower support 2-1 and the upper support 2-3 have removability from the electric wiring board 2-2, it is not necessary to use an adhesive or an adhesive film.
Further, when there is no need to bond the lower support 2-1 or the upper support 2-3 to the electric wiring board 2-2 or to separate the optical waveguide 2-8 and the electric wiring board 2-2, Adhesion that does not require re-peeling during formation (such as when a non-flexible material and a film for performing a release treatment are bonded to the electric wiring board 2-2) or the lower cladding layer 2- 4 and the electrical wiring board 2-2 have no adhesive force, and therefore it is preferable to use a heat-resistant adhesive or adhesive film, and the adhesive or adhesive film material does not need to be peeled off again. Although it does not specifically limit as a heat resistant viewpoint, A prepreg, a buildup material, a heat resistant adhesive agent etc. are mentioned suitably. An adhesive or adhesive film having a high transmittance is required for adhesion of a portion through which an optical signal is transmitted. The material of the adhesive or adhesive film is not particularly limited, but the adhesion described in (PCT / JP2008 / 05465) It is more preferable to use a film.
The thickness of the adhesive and the adhesive film is not particularly limited, but is preferably 5 μm to 3.0 mm. When the lower support 2-1 or the upper support 2-3 and the electric wiring board 2-2 are bonded to each other with the release sheet interposed therebetween, it is preferably 5 μm or more thicker than the release sheet.

(Lower cladding layer and upper cladding layer)
Hereinafter, the lower cladding layer 2-4 and the upper cladding layer 2-6 used in the present invention (second invention) will be described. As the lower cladding layer 2-4 and the upper cladding layer 2-6, a cladding layer forming resin or a cladding layer forming resin film can be used.

As the clad layer forming resin used in the present invention, the same resin as described in the first invention can be used. The resin composition used for the cladding layer forming resin may be the same or different in the components contained in the resin composition in the upper cladding layer 2-6 and the lower cladding layer 2-4. The refractive index of the resin composition may be the same or different.
The method for forming the cladding layer is not particularly limited, and the same method as that described in the first invention can be used.
Further, the thicknesses of the lower cladding layer 2-4 and the upper cladding layer 2-6 are the same as described in the first invention.

The core layer forming resin and the core layer forming resin film used in the present invention (second invention) are the same as those described in the first invention.
The optical waveguide 2-8 used in the present invention may be a multilayer optical waveguide in which a plurality of polymer layers having a core pattern 2-5 and a cladding layer are stacked.

(Electric wiring board)
The electric wiring board 2-2 used in the present invention (second invention) is not particularly limited, and various electric wiring boards used for the photoelectric composite member can be used. A resin layer or a substrate provided with a direct wiring on the substrate 2-7, a substrate with a single or double-sided metal layer, or a resin layer with a metal layer on one or both sides can be used. The electric wiring board is formed by laminating a metal layer on one side or both sides of the resin layer or the substrate.
Examples of the material of the substrate and the resin layer include the same materials as those described for the substrate 2-7.
The metal forming the metal layer includes copper, gold, silver, Al, Ni, Cr, Co, Ti, Pd, Sn, Zn, Na, alloys thereof, and two or more layers of these metals. Etc.
Further, the electrical wiring board 2-2 may be one in which an electrical wiring pattern is formed after lamination with the optical waveguide. Further, the above wiring board may be multilayered.

(III) Third and fourth inventions The method for producing an optoelectric composite substrate according to the present invention (third invention) includes forming a lower clad layer directly or via an adhesive layer on the substrate surface of the electrical wiring substrate, or An electric wiring board with a lower clad layer is formed by forming a lower clad layer directly on the substrate surface of the board with a metal foil or via an adhesive layer, and then forming an electric wiring board by forming a conductive pattern on the metal foil of the board with the metal foil. And a second step of constructing an optical waveguide by sequentially forming a core pattern and an upper clad layer on the lower clad layer. That is, there is a feature in that an electrical wiring board with a lower cladding layer is first manufactured, and then an optical waveguide is constructed by stacking components other than the lower cladding layer constituting the optical waveguide on the lower cladding layer.

In the first step of the manufacturing method of the present invention (third invention), (1) a conductor pattern 3-11a is formed on a substrate 3-12 as shown in FIG. Forming the lower cladding layer 3-31 directly or via the adhesive layer 3-20 on the surface of the substrate 3-12 of the electrical wiring substrate 3-10 on which the conductor protective layer 3-14 is formed, or (2) As shown in FIG. 12 (a′-1), directly or directly on the surface of the substrate 3-12 of the substrate 3-13 with the metal foil having the metal foil 3-11 and the substrate 3-12, the adhesive layer 3-20. Then, the lower clad layer 3-31 is formed, and then the metal foil 3-11 is processed into a conductor pattern 3-11a as shown in FIG. As in (a'-3), a conductor protective layer 3-14 is formed as necessary to obtain an electric wiring board with a lower cladding layer. It is a process. Here, the conductor protective layer is formed for the purpose of insulation protection of the conductor pattern and further protection from dust, moisture, mechanical damage, etc., and refers to, for example, a solder resist or a coverlay of a printed wiring board. .

When the lower cladding layer 3-31 is formed directly on the surface of the electric wiring substrate 3-10 or the substrate 3-13 with metal foil, a varnish of a cladding layer forming resin is formed by a known method such as a spin coating method. The method is performed by applying and removing the solvent.
On the other hand, when the lower clad layer 3-31 is formed on the substrate surface via the adhesive layer 3-20, a clad layer forming resin film is used. The resin film for forming a clad layer can be easily produced by applying a varnish of a resin for forming a clad layer onto a base film by a known method such as a spin coat method, if necessary, and removing the solvent. A method using a resin film for forming a cladding layer is preferable because the accuracy of the thickness of the lower cladding layer can be secured. There is no limitation on the method of forming the adhesive layer 3-20 on the surface of the substrate 3-12, and the adhesive composition may be directly applied to the surface of the substrate 3-12. The method of transferring the adhesive layer from the sheet adhesive to the surface of the substrate 12 is excellent in the smoothness of the adhesive layer and ensures the accuracy of the thickness of the adhesive layer. In addition, it is preferable because the problem that the resin composition for forming the adhesive layer flows does not occur when forming the adhesive layer. A method of processing the metal foil 3-11 into a conductor pattern 3-11a as shown in (a'-2) of FIG. 12 and a conductor protective layer 3-14 as shown in (a'-3) of FIG. Although the method to do is demonstrated later, a conventionally well-known method is used.

The second step in the manufacturing method of the present invention (third invention) is a step of constructing an optical waveguide. Specifically, as shown in FIG. 12 (b), on the lower cladding layer 3-31. In the process of forming the optical waveguide 3-30 by forming the core pattern 3-32 and then forming the upper cladding layer 3-33 on the core pattern 3-32 as shown in FIG. is there. The core pattern 3-32 can be formed by forming a core forming resin layer (core layer) on the lower clad layer 3-31, and exposing and developing the core layer. There is no limitation on the method of forming the core layer, and a method of directly applying the core forming resin varnish on the lower clad layer 3-31 and drying it may be used. It is preferable because the accuracy of the thickness can be secured. A desired core pattern 3-32 is formed by exposing and developing the core layer thus formed. Regarding the method of forming the upper clad layer 3-33 on the core pattern 3-32, as in the case of the lower clad layer 3-31, the varnish of the clad layer forming resin is formed by a known method such as a spin coat method. A method of forming directly on the core pattern 3-32 by applying and removing the solvent may be used, but a method using a resin film for forming a clad layer is preferable because accuracy of the thickness of the core layer can be secured.

The method for producing an optoelectric composite substrate of the present invention (fourth invention) includes a first step of forming a lower clad layer directly on the substrate surface of a substrate with a metal foil or via an adhesive layer, and on the lower clad layer. It has a 2nd process of constructing | assembling an optical waveguide by forming a core pattern and an upper clad layer one by one, and a 3rd process of constructing | assembling an electrical wiring board | substrate from a board | substrate with metal foil. That is, a lower clad layer is first formed on the surface of a substrate with a metal foil, and then an optical waveguide is constructed by stacking components other than the lower clad layer on the lower clad layer. It is characterized in that a wiring board is constructed.

As shown in FIG. 13 (a), the first step in the manufacturing method of the present invention is directly or directly on the surface of the substrate 4-13 with the metal foil having the metal foil 4-11 and the substrate 4-12. In this step, the lower cladding layer 4-31 is formed via the adhesive layer 4-20.

The second step in the manufacturing method of the present invention is a step of constructing an optical waveguide. Specifically, as shown in FIG. 13B, the core pattern 4-32 is formed on the lower cladding layer 4-31. Next, as shown in FIG. 13C, the upper cladding layer 4-33 is formed on the core pattern 4-32 to construct the optical waveguide 4-30.

The third step in the manufacturing method of the present invention is a step of constructing an electric wiring board. Specifically, as shown in FIG. 13 (d), the metal foil 4-11 is used as a conductor pattern 4-11a. This is a process of constructing the electrical wiring board 4-10. If necessary, as shown in FIG. 13E, a conductor protective layer 4-14 is formed on a necessary portion of the conductor pattern 4-11a in order to protect the conductor pattern 4-11a. Here, the conductor protective layer is formed for the purpose of insulation protection of the conductor pattern and further protection from dust, moisture, mechanical damage, etc., and refers to, for example, a solder resist or a coverlay of a printed wiring board. .

The materials used in each step in the third and fourth inventions will be described in detail.
<Electric wiring board>
The electric wiring board used in the third invention is not particularly limited as long as the electric wiring board is provided with a conductor pattern on the board and further provided with a conductor protective layer on the conductor pattern as necessary. Depending on the purpose, various materials can be used. For example, the conductive metal is copper, aluminum, gold or the like, and the substrate is a glass epoxy substrate, polyimide polyamide, polyetherimide, polyethylene terephthalate, liquid crystal polymer, or the like. Examples thereof include ceramic wiring substrates such as organic wiring substrates, alumina substrates, and aluminum nitride substrates, and semiconductor wafers such as silicon.
In order to manufacture a flexible type optoelectric composite substrate, a substrate material such as polyimide, polyamide, polyetherimide, polyethylene terephthalate, liquid crystal polymer, etc. is used. Generally, heat resistance and availability are easily obtained. From this viewpoint, a substrate using polyimide as a substrate is used.
Further, when the optical waveguide is constructed, a transparent substrate is preferable in order to make the conductor pattern easily visible through the substrate.

<Substrate with metal foil>
As the substrate with metal foil used in the present invention, various substrates can be used according to the purpose. For example, as the metal, copper, aluminum, gold, etc., as the substrate, glass epoxy substrate, polyimide polyamide, Examples thereof include organic wiring substrates using polyetherimide, polyethylene terephthalate, liquid crystal polymer, ceramic wiring substrates such as alumina substrates and aluminum nitride substrates, and semiconductor wafers such as silicon.
In order to manufacture a flexible type photoelectric composite substrate, as a substrate material, polyimide, polyamide, polyetherimide, polyethylene terephthalate, liquid crystal polymer, etc. are used, but generally heat resistance and availability are easy. From this viewpoint, polyimide is used.
Further, when the optical waveguide is constructed, a transparent substrate is preferable in order to make the conductor pattern easily visible through the substrate. In order to process a board with metal foil into an electric wiring board, patterning of the wiring is necessary. As a method for this, conventionally, a metal foil having a thickness required for metal wiring is laminated on the board via an adhesive layer. Many so-called subtractive methods have been performed in which an unnecessary portion as a conductor pattern is removed from a metal foil of a substrate with a metal foil by etching using the three-layered substrate with a metal foil.

However, in the three-layered substrate with metal foil, the presence of the adhesive layer affects the performance of the substrate, particularly the reliability against bending, so that the metal foil was directly laminated on the substrate without using the adhesive layer. Two-layer substrates with metal foil have been developed, and many attempts have been made to increase the adhesive strength between the metal foil and the substrate.
The two-layer metal foil substrate is manufactured by forming a metal thin film on the substrate by sputtering or direct plating, and is further manufactured by thickening the conductor metal by a method such as electrolytic plating. For such a two-layered board with metal foil, the conductor pattern is usually processed by the above-described subtractive method.
Moreover, as a board | substrate with 2 layers of metal foil, there exists what was manufactured by forming a metal thin film on a board | substrate by a sputtering method or a direct plating method, About such a board | substrate with 2 layers of metal foil, A conductor pattern is processed by a so-called semi-additive method in which a conductor metal is deposited only on a necessary portion as a conductor pattern by a method such as electrolytic plating to obtain a necessary thickness. In the case of these two-layered substrates with metal foil, the metal thin film need not be the same as a conductive metal such as copper, aluminum, or gold, but may be nickel, palladium, iron, or the like.
The present invention includes a method (semi-additive method) in which an electric wiring substrate is formed later by an additive method using such a two-layer substrate with a metal foil as the substrate with a metal foil. Of course, when the two-layered board with metal foil has a metal foil having a thickness required for the metal wiring, the electric wiring board is formed by a subtractive method.
The thickness of a board | substrate and metal foil is suitably determined according to a use, and there is no restriction | limiting in particular. For example, in the case of a copper-clad polyimide film, the thickness of the copper foil is about 1 μm to 50 μm, and the thickness of the substrate is about 5 μm to 100 μm. Such substrates with metal foil are commercially available, manufactured by Kaneka Co., Ltd., trade name `` Pixio '', Ube Industries, Ltd., trade name `` Yupisel '', manufactured by Nippon Steel Chemical Co., Ltd. The names "Espanex", manufactured by Toray Film Processing Co., Ltd., trade name "Metaroyal", Sheldal, trade name "Flex Base", etc.

<Adhesive layer>
As described above, when the lower clad layer is formed on the substrate surface of the substrate with the metal foil via the adhesive layer, it is better to use the sheet-like adhesive, and the adhesive layer is more smooth. Since the accuracy of the thickness of the adhesive layer can be ensured, and the problem that the resin composition for forming the adhesive layer flows does not occur when forming the adhesive layer, it is preferable.
The sheet-like adhesive may be one in which an adhesive layer is directly formed on a supporting substrate, but in order to easily peel the supporting substrate from the adhesive layer, the adhesive is bonded to the adhesive layer on the supporting substrate. An adhesive layer in which an adhesive layer is sequentially formed, and an adhesive sheet in which an adhesive layer is formed on a support substrate are preferable. In particular, the pressure-sensitive adhesive sheet is more preferable because it is not necessary to prepare a pressure-sensitive adhesive and an adhesive separately, and the manufacturing process is simplified.
As the adhesive composition for forming the adhesive layer, those usually used in the optical field can be used, but the adhesive composition was measured at 125 ° C. under the following conditions. The storage elastic modulus in is preferably 10 MPa or less. When the storage elastic modulus is 10 MPa or less, the adhesive layer acts as a stress relaxation layer when the optical waveguide is heated and expanded, so that the optical waveguide is caused by the difference in thermal expansion coefficient between the optical waveguide and the substrate. This is advantageous in that no peeling occurs. From the above viewpoint, it is more preferable that the storage elastic modulus at 125 ° C. is 5 MPa or less.
The thickness of the adhesive layer is not particularly limited but is preferably 3 to 200 μm. When the thickness is 3 μm or more, a sufficient stress relaxation effect can be obtained, and when the thickness is 200 μm or less, it is possible to meet the demand for miniaturization of the optical device and it is economically advantageous. From the above viewpoint, the thickness of the adhesive layer is more preferably 5 to 50 μm, further preferably 8 to 30 μm, and particularly preferably 10 to 25 μm.

(Conditions for measuring storage modulus)
The test piece has a length of 20 mm, a width of 4 mm, and a film thickness of 80 μm, and is measured with a temperature rising rate of 5 ° C./min, a tension mode, a frequency of 10 Hz, and an automatic static load.
The adhesive composition for forming the adhesive layer is not particularly limited as long as it satisfies the above storage elastic modulus condition. Specifically, two or more epoxy groups are included in the molecule. Or a compound having an ethylenically unsaturated group in the molecule. These compounds can be used individually by 1 type or in combination of 2 or more types.
Specific examples of suitable adhesive compositions include (a) a high molecular weight component having a functional group-containing weight average molecular weight of 100,000 or more, (b) an epoxy resin, and (c) a phenolic epoxy. Contains a resin curing agent, (d) a photoreactive monomer whose Tg of the cured product obtained by ultraviolet irradiation is 250 ° C. or higher, and (e) a photoinitiator that generates bases and radicals by ultraviolet irradiation with a wavelength of 200 to 450 nm. And the like.

Hereinafter, in the present specification, the components (a) and (c) to (e) are respectively represented by (a) a high molecular weight component, (c) an epoxy resin curing agent, (d) a photoreactive monomer, and (e) a photoinitiator. Sometimes abbreviated as agent.
In the present invention, it is preferable to use an adhesive sheet as described above when forming the adhesive layer, but when the above components (a) to (e) are used, the following is further shown. There are significant advantages. That is,
(1) (a) High molecular weight component and (b) epoxy resin can be incompatible depending on the combination, so that a so-called sea-island structure is easy to take, low elasticity, adhesiveness, workability, and reliability at high temperature Is obtained,
(2) Excellent heat resistance and reflow resistance by using (c) epoxy resin curing agent and (d) photoreactive monomer,
(3) (c) an epoxy resin curing agent and (d) a photoinitiator used in the presence of a photoreactive monomer, so that (b) an epoxy resin and (d) light in the absence of light The reactive monomer hardly reacts and is excellent in storage stability. In addition, irradiation with light accelerates the photoreaction and generates an epoxy resin curing accelerator. That is, it is possible to achieve both reactivity and storage stability.

Hereinafter, each component which comprises a preferable adhesive composition is demonstrated more concretely.
(A) The high molecular weight component having a functional group-containing weight average molecular weight of 100,000 or more includes functional groups such as a glycidyl group, an acryloyl group, a methacryloyl group, a carboxyl group, a hydroxyl group, and an episulfide group in terms of improving adhesiveness. What is contained is preferable, and a glycidyl group is particularly preferable in terms of crosslinkability. Specifically, glycidyl group-containing (meth) containing glycidyl acrylate or glycidyl methacrylate (hereinafter collectively referred to as “glycidyl (meth) acrylate”) as a raw material monomer and having a weight average molecular weight of 100,000 or more. An acrylic copolymer can be mentioned.
Moreover, it is preferable that it is incompatible with (b) epoxy resin at the point of reflow resistance. However, since compatibility is not determined only by the characteristics of (a) high molecular weight component, a combination in which both are not compatible is selected. In the present invention, the glycidyl group-containing (meth) acrylic copolymer is a phrase indicating both a glycidyl group-containing acrylic copolymer and a glycidyl group-containing methacrylic copolymer.

As such a copolymer, for example, a (meth) acrylic ester copolymer, acrylic rubber or the like can be used, and acrylic rubber is more preferable. Acrylic rubber is a rubber mainly composed of an acrylate ester and mainly composed of a copolymer such as butyl acrylate and acrylonitrile, a copolymer such as ethyl acrylate and acrylonitrile, or the like. Examples of the copolymer monomer include butyl acrylate, ethyl acrylate, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, acrylonitrile and the like.

When selecting a glycidyl group as a functional group, it is preferable to use glycidyl (meth) acrylate or the like as a copolymer monomer component. Such a glycidyl group-containing (meth) acrylic copolymer having a weight average molecular weight of 100,000 or more can be produced by appropriately selecting a monomer from the above monomers, or a commercially available product (for example, Nagase ChemteX Corporation). HTR-860P-3, HTR-860P-5, etc.) are also available.

(A) In the high molecular weight component, since the number of functional groups affects the crosslink density, it varies depending on the resin used, but when the high molecular weight component is obtained as a copolymer of a plurality of monomers, it contains a functional group used as a raw material. The amount of the monomer is preferably 0.5 to 6% by mass of the copolymer.

When the glycidyl group-containing acrylic copolymer is used as the component (a), the amount of the glycidyl group-containing monomer such as glycidyl (meth) acrylate used as the raw material and the amount of the glycidyl group-containing repeating unit are 0 of the copolymer. 0.5 to 6% by mass is preferable, 0.5 to 5% by mass is more preferable, and 0.8 to 5% by mass is particularly preferable. When the amount of the glycidyl group-containing repeating unit is within this range, the glycidyl group gradually crosslinks, so that an adhesive force can be secured and gelation can be prevented. Moreover, since it becomes incompatible with (b) epoxy resin, it becomes excellent in stress relaxation property.

Other functional groups can be incorporated into glycidyl (meth) acrylate or the like to form a monomer. In this case, the mixing ratio is determined in consideration of the glass transition temperature (hereinafter referred to as “Tg”) of the glycidyl group-containing (meth) acrylic copolymer, and Tg is preferably −10 ° C. or higher. This is because when the Tg is −10 ° C. or higher, the tackiness of the adhesive layer in the B-stage state is appropriate, and no problem is caused in handling.

(A) As a high molecular weight component having a functional group-containing weight average molecular weight of 100,000 or more, when the monomer is polymerized and a glycidyl group-containing acrylic copolymer is used, the polymerization method is not particularly limited, For example, methods such as pearl polymerization and solution polymerization can be used.
In the present invention, the (a) high molecular weight component has a weight average molecular weight of 100,000 or more, preferably 300,000 to 3,000,000, more preferably 400,000 to 2,500,000, and 500,000 to 2,000,000. Is particularly preferred. When the weight average molecular weight is within this range, the strength, flexibility, and tackiness of the sheet or film are appropriate, and the flowability is appropriate, so that followability to the unevenness of the substrate can be ensured. . In the present invention, the weight average molecular weight is a value measured by gel permeation chromatography and converted using a standard polystyrene calibration curve.

The (b) epoxy resin used in the adhesive composition is not particularly limited as long as it is cured and has an adhesive action, and is described in, for example, the epoxy resin handbook (edited by Masaki Shinbo, Nikkan Kogyo Shimbun). Epoxy resin can be widely used. Specifically, for example, a bifunctional epoxy resin such as a bisphenol A type epoxy resin, a novolac type epoxy resin such as a phenol novolac type epoxy resin or a cresol novolac type epoxy resin, or the like can be used. Moreover, what is generally known, such as a polyfunctional epoxy resin, a glycidyl amine type epoxy resin, a heterocyclic ring-containing epoxy resin, or an alicyclic epoxy resin, can be applied.

As such bisphenol A type epoxy resin, which is a kind of epoxy resin, Epicoat 807, 815, 825, 827, 828, 834, 1001, 1004, 1007, 1009 manufactured by Yuka Shell Epoxy Co., Ltd., manufactured by Dow Chemical Co., Ltd. DER-330, 301, 361, YD8125, YDF8170, etc. manufactured by Tohto Kasei Co., Ltd. may be mentioned. Examples of the phenol novolac type epoxy resin include Epicoat 152,154 manufactured by Yuka Shell Epoxy Co., Ltd., EPPN-201 manufactured by Nippon Kayaku Co., Ltd., DEN-438 manufactured by Dow Chemical Co., Ltd., and o-cresol novolak type epoxy resin. Examples of the resin include EOCN-102S, 103S, 104S, 1012, 1025, 1027 manufactured by Nippon Kayaku Co., Ltd., YDCN701, 702, 703, 704 manufactured by Toto Kasei Co., Ltd., and the like. As the polyfunctional epoxy resin, Epon 1031S manufactured by Yuka Shell Epoxy Co., Ltd., Araldite 0163 manufactured by Ciba Specialty Chemicals Co., Ltd., Denacol EX-611, 614, 614B, 622, 512, 521, 421, 411 manufactured by Nagase Kasei Co., Ltd. , 321 and the like. As the amine type epoxy resin, Epiquat 604 manufactured by Yuka Shell Epoxy Co., Ltd., YH-434 manufactured by Tohto Kasei Co., Ltd., TETRAD-X, TETRAD-C manufactured by Mitsubishi Gas Chemical Co., Ltd., ELM manufactured by Sumitomo Chemical Co., Ltd. -120 and the like. Examples of the heterocyclic ring-containing epoxy resin include ERL4234, 4299, 4221, 4206 and the like manufactured by UCC, such as Araldite PT810 manufactured by Ciba Specialty Chemicals. These epoxy resins can be used alone or in combination of two or more. Moreover, in this invention, in order to provide high adhesive force, a bisphenol A type epoxy resin and a phenol novolak type epoxy resin are preferable.

The amount of the (b) epoxy resin used in the adhesive composition is preferably 5 to 250 parts by mass with respect to 100 parts by mass of the (a) high molecular weight component. (B) When the usage-amount of an epoxy resin exists in this range, elastic modulus and the flow control at the time of shaping | molding can be ensured, and the handleability in high temperature is fully obtained. (B) The amount of the epoxy resin used is more preferably 10 to 100 parts by mass, and particularly preferably 20 to 50 parts by mass. As already stated, it is preferable that the (b) epoxy resin is not compatible with the (a) high molecular weight component.

The (c) phenolic epoxy resin curing agent used in the adhesive composition is excellent in impact resistance under high temperature and high pressure when combined with an epoxy resin, and retains sufficient adhesive properties even under severe thermal moisture absorption. It is effective because it can.
Examples of such component (c) include phenol resins such as phenol novolak resin, bisphenol A novolak resin, and cresol novolak resin. More specifically, for example, trade names: Phenolite LF2882, Phenolite LF2822, Phenolite TD-2090, Phenolite TD-2149, Phenolite VH-4150, Phenolite VH4170, manufactured by Dainippon Ink and Chemicals, Inc. These may be used alone or in combination of two or more.

In order to impart moisture resistance reliability to the adhesive composition, the amount of component (c) used is such that the equivalent ratio of phenolic hydroxyl groups per epoxy group of (b) epoxy resin is 0.5 to 1. The range is preferably 5, and more preferably 0.8 to 1.2. If the equivalent ratio is within this range, the resin is sufficiently cured (crosslinked), and the heat resistance and moisture resistance of the cured product can be improved.

(D) The photoreactive monomer whose Tg of the cured product obtained by ultraviolet irradiation is 250 ° C. or higher is used for the adhesive composition, and improves the heat resistance after ultraviolet irradiation of the adhesive sheet described below, The adhesive strength and reflow resistance during heating can be improved.
(D) As a method for measuring the Tg of the photoreactive monomer, (d) a photoinitiator is added to the photoreactive monomer, and a cured product irradiated with ultraviolet rays is molded to a size of about 5 × 5 mm to prepare a sample. . Tg is determined by measuring the prepared sample in a compression mode using EXSTRA6000 manufactured by Seiko Instruments Inc. When Tg is 250 ° C. or higher, the heat resistance is excellent, and it can withstand heat of 250 ° C. or higher in the reflow crack resistance evaluation. Therefore, the reflow crack resistance is good. Tg is more preferably 260 ° C. or higher corresponding to lead-free solder. Moreover, since the thing with too high Tg tends to become inferior in the normal temperature sticking property of the adhesive sheet after ultraviolet irradiation, 350 degreeC is preferable as an upper limit.

(D) Specific examples of the photoreactive monomer include pentaerythritol triacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, trimethylolpropane triacrylate, isocyanuric acid ethylene oxide (EO) modified triacrylate, ditrile Examples thereof include polyfunctional acrylates such as methylolpropane tetraacrylate and pentaerythritol tetraacrylate. These photoreactive monomers can be used alone or in combination of two or more. Of the polyfunctional acrylates, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and the like are preferable from the viewpoint of residual monomers after ultraviolet irradiation. Specific examples include trade names: A-DPH and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd.
In addition, when using several (d) photoreactive monomer, the Tg is Tg when the mixture is measured by the said measuring method, and it is not required that Tg of each monomer is 250 degreeC or more.

The amount of the (d) photoreactive monomer used in the adhesive composition is preferably 5 to 100 parts by mass with respect to 100 parts by mass of the (a) high molecular weight component. If this usage amount is 5 parts by mass or more, the polymerization reaction of the photoreactive monomer due to ultraviolet irradiation is likely to occur, so that the peelability of the adhesive sheet from the support substrate tends to be improved. Conversely, if it is 100 parts by mass or less, the low elasticity of the high molecular weight component functions, the film does not become brittle, and the heat resistance and moisture resistance of the cured product tend to be improved. Therefore, 10 to 70 parts by mass is more preferable, and 20 to 50 parts by mass is particularly preferable.

In the adhesive composition, (e) a photoinitiator that generates a base and a radical upon irradiation with ultraviolet rays having a wavelength of 200 to 450 nm is generally called an α-aminoketone compound. Such compounds are described, for example, in J. Org. Photopolym. Sci. Technol, Vol. 13, No. 20001, etc., and reacts as shown in the following formula when irradiated with ultraviolet rays.

The α-aminoketone compound does not have radicals before being irradiated with ultraviolet rays, so that the polymerization reaction of the photoreactive monomer does not occur. In addition, curing of the thermosetting resin is not accelerated due to steric hindrance. However, the α-aminoketone compound is dissociated by ultraviolet irradiation, and a polymerization reaction of the photoreactive monomer occurs with the generation of radicals. Further, the dissociation of the α-aminoketone compound reduces the steric hindrance so that activated amines are present. For this reason, it is presumed that the amine has a curing accelerating action of the thermosetting resin, and the heating accelerating action is subsequently exerted by heating. By such an action, there is no radical or activated amine before irradiation with ultraviolet rays, so that an adhesive sheet having excellent storage stability at room temperature can be provided. In addition, since the curing rate of the photoreactive monomer and epoxy resin varies depending on the radical and amine structure generated by ultraviolet irradiation, depending on the components (b) to (d) used, (e) a photoinitiator (base generator) Can be determined.

Examples of the (e) photoinitiator (base generator) include 2-methyl-1 (4- (methylthio) phenyl-2-morpholinopropan-1-one (Irgacure 907 manufactured by Ciba Specialty Chemicals), 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1-one (Irgacure 369 manufactured by Ciba Specialty Chemicals), hexaarylbisimidazole derivative (halogen, alkoxy group, nitro group, cyano, A substituent such as a group may be substituted with a phenyl group), benzoisoxazolone derivatives, and the like.
In addition to the photoinitiator (base generator), a method of generating a base by photo-Fries rearrangement, photo-Claisen rearrangement, Curtius rearrangement, or Stevens rearrangement can be used.
The photoinitiator (base generator) may be a low molecular compound having a molecular weight of 500 or less, or a compound introduced into a main chain and side chain of a polymer. The molecular weight in this case is preferably a weight average molecular weight of 1,000 to 100,000, more preferably 5,000 to 30,000 from the viewpoints of adhesiveness and fluidity as an adhesive.

In the adhesive composition, the amount of (e) photoinitiator used is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of (a) high molecular weight component. If it is 0.1 part by mass or more, the reactivity is good and the residual monomer is reduced, and if it is 20 parts by mass or less, the molecular weight increase due to the polymerization reaction functions moderately, the low molecular weight component is small, and the reflow resistance is affected. The possibility of exerting is reduced. Accordingly, the amount is more preferably 0.5 to 15 parts by mass, and further preferably 1 to 5 parts by mass.

Next, in addition to the components (a) to (e), components that can be contained in the adhesive layer will be described. For the purpose of improving flexibility and reflow crack resistance, (f) a high molecular weight resin compatible with the epoxy resin can be added to the adhesive resin composition. As such a high molecular weight resin, (a) those which are incompatible with the high molecular weight component are preferable from the viewpoint of improving reliability, and examples thereof include phenoxy resin, high molecular weight epoxy resin, and ultra high molecular weight epoxy resin. These may be used alone or in combination of two or more. (B) When using an epoxy resin that is compatible with (a) a high molecular weight component, when (f) a high molecular weight resin compatible with the epoxy resin is used, (b) the epoxy resin is As a result, it may be possible to make the (b) epoxy resin and the (a) high molecular weight component incompatible with each other.
(F) It is preferable that the usage-amount of high molecular weight resin compatible with an epoxy resin shall be 40 mass parts or less with respect to a total of 100 mass parts of (b) epoxy resin and (c) epoxy resin hardening | curing agent. Within this range, the Tg of the adhesive layer can be secured.

In addition, various coupling agents can be added to the adhesive composition in order to improve interfacial bonding between different materials. Examples of the coupling agent include silane, titanium, and aluminum.
The silane coupling agent is not particularly limited. For example, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-ureidopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane and the like can be used, and these can be used alone or in combination of two or more. Specifically, there are NUCA-189 and NUCA-1160 manufactured by Nippon Unicar Co., Ltd.

The amount of the coupling agent used is from 0.01 to 100 parts by mass with respect to 100 parts by mass of the high molecular weight component having a weight average molecular weight containing a functional group of 100,000 or more in view of its effect, heat resistance and cost. The amount is preferably 10 parts by mass.

An ion scavenger can be further added to the adhesive composition in order to adsorb ionic impurities and improve moisture resistance reliability. Such an ion scavenger is not particularly limited, for example, triazine thiol compound, bisphenol-based reducing agent, etc., a compound known as a copper damage preventive agent for preventing copper ionization and dissolution, zirconium-based And inorganic ion adsorbents such as antimony bismuth-based magnesium aluminum compounds.
The amount of the ion scavenger used is from the viewpoint of the effect of addition, heat resistance, cost, etc. to (a) 100 parts by mass of the high molecular weight component having a functional group-containing weight average molecular weight of 100,000 or more. 1 to 10 parts by mass is preferred.

The adhesive sheet can be obtained by dissolving or dispersing the adhesive composition in a solvent to obtain a varnish, applying the composition onto a support substrate, heating the composition, and removing the solvent.
That is, first, a knife coating method, a roll coating method, a spray coating method, a gravure coating method is performed by dissolving an adhesive composition in an organic solvent or the like on a protective film (also called a release sheet). According to a generally known method such as a bar coating method or a curtain coating method, it is applied and dried to form an adhesive layer. Then, a support base material is laminated | stacked and the adhesive sheet which consists of a release sheet (protective film), an adhesive layer, and a support base material can be obtained. Alternatively, the adhesive composition can be applied directly on the supporting substrate by the same method and dried to obtain an adhesive sheet. In this case, you may laminate | stack a protective film as needed.

Examples of the protective film or support substrate used for the adhesive sheet include plastic films such as polytetrafluoroethylene film, polyethylene film, polypropylene film, and polymethylpentene film, and polyester such as polyethylene terephthalate. Here, as will be described later, the adhesive sheet is irradiated with ultraviolet rays, the ultraviolet-curing adhesive is polymerized and cured, and the adhesive force at the interface between the adhesive and the supporting substrate is lowered to form a supporting group. Allows stripping of material. For this reason, the support substrate is preferably one having ultraviolet transparency.

The solvent for varnishing is not particularly limited as long as it is an organic solvent, but can be determined in consideration of the volatility during film production from the boiling point. Specifically, for example, a solvent having a relatively low boiling point such as methanol, ethanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, methyl ethyl ketone, acetone, methyl isobutyl ketone, toluene, xylene, etc. This is preferable in that the curing of the resin does not proceed. For the purpose of improving the coating properties, it is preferable to use a solvent having a relatively high boiling point such as dimethylacetamide, dimethylformamide, N-methylpyrrolidone, cyclohexanone. These solvents can be used alone or in combination of two or more.
The thickness of the supporting substrate in the adhesive sheet is not particularly limited, but is preferably 5 to 250 μm. If it is 5 micrometers or more, workability | operativity will improve, and if it is 250 micrometers or less, it is economical and preferable. From the above viewpoints, the thickness of the supporting substrate is more preferably 10 to 200 μm, further preferably 20 to 150 μm, and particularly preferably 25 to 125 μm.

The total thickness of the adhesive layer and the supporting substrate in the adhesive sheet is usually 10 to 250 μm. The workability is good when the support substrate is set to be the same as or slightly thicker than the adhesive layer. As a specific combination, the adhesive layer / support substrate (μm) is 5/25, 10/30, 10 / There are 50, 25/50, 50/50, 50/75, etc., which can be appropriately determined according to the conditions and apparatus used.
Moreover, in order to obtain a desired thickness, the adhesive sheet has two or more separately prepared adhesives on the adhesive layer side of the adhesive sheet in order to improve fluidity during heating. It can also be pasted together. In this case, it is necessary to select a bonding condition so that peeling between the adhesive layers does not occur.
When the adhesive sheet having the structure as described above is irradiated with ultraviolet rays, the adhesive strength of the support base material is greatly reduced after the ultraviolet irradiation, and the adhesive sheet of the adhesive sheet is retained while holding the adhesive layer on the substrate. The supporting substrate can be easily peeled off.

<Clad layer forming resin>
As the clad layer forming resin used for the lower clad layer and the upper clad layer, the cured product of the clad forming resin film has a lower refractive index than the cured product of the core layer forming resin film described later, and The resin is not particularly limited as long as it is a resin that is cured by light or heat, and a thermosetting resin or a photosensitive resin can be used, but (a) a base polymer, (b) a photopolymerizable compound, and (c) photopolymerization. It is preferable that it is comprised with the resin composition containing an initiator.
(A) As the base polymer, the same (A) base polymer as described in the first invention can be used.

As the base polymer (A), an epoxy resin, particularly an epoxy resin that is solid at room temperature is preferable from the viewpoint of three-dimensional crosslinking and improved heat resistance.
Examples of the epoxy resin that is solid at room temperature include, for example, “Epototo YD-7020, Epototo YD-7019, Epototo YD-7007” (all trade names) manufactured by Toto Chemical Co., Ltd., and “Epicoat 1010” manufactured by Japan Epoxy Resins Co., Ltd. Bisphenol A type epoxy resin such as “Epicoat 1009, Epicoat 1008” (both trade names).
(A) The molecular weight of the base polymer is usually 5,000 or more in terms of number average molecular weight from the viewpoint of film formability. The number average molecular weight is preferably 10,000 or more, more preferably 30,000 or more.
The upper limit of the number average molecular weight is not particularly limited, but is usually 1,000,000 or less from the viewpoint of (i) compatibility with the photopolymerizable compound and exposure and developability.
The upper limit of the number average molecular weight is preferably 500,000 or less, more preferably 200,000 or less.
The number average molecular weight is a value measured by gel permeation chromatography (GPC) and converted to standard polystyrene.

The blending amount of the (a) base polymer is usually about 10 to 80% by mass with respect to the total amount of the base polymer of the component (a) and the photopolymerizable compound of the component (a).
When the blending amount is 10% by mass or more, there is an advantage that it is easy to form a thick film of about 50 to 500 μm necessary for the construction of the optical waveguide. On the other hand, when the blending amount is 80% by mass or less, the photocuring reaction occurs. Proceed sufficiently.
From the above viewpoint, the amount of component (a) is preferably 20 to 70% by mass, more preferably 25 to 65% by mass.

Next, (a) the photopolymerizable compound is not particularly limited as long as it is polymerized by irradiation with light such as ultraviolet rays, and a compound having two or more epoxy groups in the molecule or an ethylenically non-polymerizable compound in the molecule. Examples thereof include compounds having a saturated group.
Specific examples of compounds having two or more epoxy groups in the molecule include bisphenol A type epoxy resins, tetrabromobisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD type epoxy resins, naphthalene type epoxy resins, etc. Polyfunctional aromatic glycidyl ethers such as bifunctional aromatic glycidyl ether, phenol novolac type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene-phenol type epoxy resin, tetraphenylolethane type epoxy resin, polyethylene glycol type epoxy resin, Bifunctional aliphatic glycidyl ether such as polypropylene glycol type epoxy resin, neopentyl glycol type epoxy resin, hexanediol type epoxy resin, hydrogenated bisphenol A type Bifunctional aromatic glycidyl ethers such as bifunctional alicyclic glycidyl ethers such as poxy resins, polyfunctional aliphatic glycidyl ethers such as trimethylolpropane type epoxy resins, sorbitol type epoxy resins and glycerin type epoxy resins, and diglycidyl esters of phthalic acid , Bifunctional alicyclic glycidyl esters such as tetrahydrophthalic acid diglycidyl ester and hexahydrophthalic acid diglycidyl ester, bifunctional aromatic glycidyl such as N, N-diglycidylaniline and N, N-diglycidyltrifluoromethylaniline Amine, N, N, N ′, N′-tetraglycidyl-4,4-diaminodiphenylmethane, 1,3-bis (N, N-glycidylaminomethyl) cyclohexane, N, N, O-triglycidyl-p-amino Polyfunctionality such as phenol Bifunctional cycloaliphatic epoxy resins such as aromatic glycidylamine, alicyclic diepoxy acetal, alicyclic diepoxy adipate, alicyclic diepoxycarboxylate, vinylcyclohexene dioxide, and bifunctional heterocycles such as diglycidylhydantoin And a bifunctional or polyfunctional silicon-containing epoxy resin such as an epoxy resin, a polyfunctional heterocyclic epoxy resin such as triglycidyl isocyanurate, and an organopolysiloxane type epoxy resin.

These compounds having two or more epoxy groups in the molecule are usually those having a molecular weight of 100 to 2000 and liquid at room temperature. The molecular weight is preferably 150 to 1,000, more preferably 200 to 800.
Moreover, these compounds may be used independently, may be used together 2 or more types, and also can be used in combination with another photopolymerizable compound.
The molecular weight can be measured using a gel permeation chromatography (GPC) method or a mass spectrometry method.
Specific examples of the compound having an ethylenically unsaturated group in the molecule include (meth) acrylate, vinylidene halide, vinyl ether, vinyl pyridine, vinyl phenol, etc. Of these, transparency and heat resistance From the viewpoint, (meth) acrylate is preferable, and any of monofunctional, bifunctional, trifunctional or higher can be used.

Monofunctional (meth) acrylates include methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, lauryl (meth) acrylate, isostearyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid , Paracumylphenoxyethylene glycol (meth) acrylate, 2-tetrahydropyranyl (meth) acrylate, isobornyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate Etc.

Bifunctional (meth) acrylates include ethoxylated 2-methyl-1,3-propanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 1,6-hexanediol di (meth). Acrylate, 2-methyl-1,8-octanediol diacrylate, 1,9-nonanediol di (meth) acrylate, 1,10-nonanediol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, propoxy Ethoxylated bisphenol A diacrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol Cold di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, tricyclodecane di (meth) acrylate, ethoxylated cyclohexanedimethanol di (meth) acrylate, 2-hydroxy-1-acryloxy-3-methacryloxypropane, 2-hydroxy-1,3-dimethacryloxypropane, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [3-phenyl-4-acryloylpolyoxyethoxy) fluorene Bisphenol A type, phenol novolak type, cresol novolak type, glycidyl ether type epoxy (meth) acrylate, and the like.

Furthermore, as tri- or more functional (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, ethoxylated glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, propoxylated pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, caprolactone modified ditri Examples include methylolpropane tetraacrylate and dipentaerythritol hexa (meth) acrylate.
These may be used alone or in combination of two or more.
Here, (meth) acrylate means acrylate and methacrylate.

The blending amount of the (a) photopolymerizable compound is usually about 20 to 90% by mass with respect to the total amount of the base polymer of the component (a) and the photopolymerizable compound of the component (a).
When the blending amount is 20% by mass or more, the base polymer can be easily entangled with the photopolymerizable compound and cured, while when it is 90% by mass or less, a sufficiently thick clad layer can be easily formed. Can be formed.
From the above viewpoint, the amount of component (a) is preferably 25 to 85% by mass, more preferably 30 to 80% by mass.

Next, the photopolymerization initiator of the component (c) is not particularly limited. For example, as an initiator for an epoxy compound, aryl diazonium salts such as p-methoxybenzenediazonium hexafluorophosphate, diphenyliodonium hexafluorophosphonium salt, diphenyl Diaryliodonium salts such as iodonium hexafluoroantimonate salt, triphenylsulfonium hexafluorophosphonium salt, triphenylsulfonium hexafluoroantimonate salt, diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate salt, diphenyl-4-thiophenoxyphenyl Sulfonium hexafluoroantimonate salt, diphenyl-4-thiophenoxyphenylsulfonium pentafluorohydroxyantimonate Triarylsulfonium salts such as triphenylselenonium hexafluorophosphonium salt, triphenylselenonium borofluoride, triarylselenonium salts such as triphenylselenonium hexafluoroantimonate salt, dimethylphenacylsulfonium hexafluoroantimonate salt Dialkylphenazylsulfonium salts such as diethylphenacylsulfonium hexafluoroantimonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, dialkyl-4-hydroxyphenylsulfonium such as 4-hydroxyphenylbenzylmethylsulfonium hexafluoroantimonate Salt, α-hydroxymethylbenzoin sulfonate, N-hydroxyimide sulfonate, α-sulfonate Kishiketon, sulfonic acid esters such as β- sulfo Niro carboxymethyl ketone.

In addition, as an initiator for a compound having an ethylenically unsaturated group in the molecule, benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4 '-Diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2,2-dimethoxy-1,2 -Diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy- 2-Methyl-1-propan-1-one, 1,2-methyl-1- [4- (methylthio) phenyl] -2-morph Aromatic ketones such as linopropan-1-one, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2 Quinones such as 1,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone Benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether, benzoin compounds such as benzoin, methyl benzoin and ethyl benzoin; benzyldimethyl ketal and the like 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluoro) Phenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer 2,4,5-triarylimidazole dimer such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide Phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, - phenyl acridine, 1,7-bis (9,9'-acridinyl) acridine derivatives such as heptane, N- phenylglycine, N- phenylglycine derivatives, coumarin-based compounds.
Further, in the 2,4,5-triarylimidazole dimer, when the aryl group is substituted, the substituents of the two aryl groups may be the same and symmetrical dimers, or differently. It may be an asymmetric dimer.
Moreover, you may combine a thioxanthone type compound and a tertiary amine compound like the combination of diethyl thioxanthone and dimethylamino benzoic acid.
From the viewpoint of improving the transparency of the core layer and the clad layer, aromatic ketones and phosphine oxides are preferable among the photopolymerization initiators.
These (c) photopolymerization initiators may be used alone or in combination of two or more.

(C) The amount of the photopolymerization initiator is usually about 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the base polymer of component (a) and the photopolymerizable compound of component (a).
If it is 0.1 parts by mass or more, the photosensitivity is sufficient, while if it is 10 parts by mass or less, only the surface of the optical waveguide is selectively cured, and curing does not become insufficient, Propagation loss does not increase due to absorption of the photopolymerization initiator itself.
From the above viewpoint, the blending amount of the component (c) is preferably 0.5 to 5 parts by mass, more preferably 1 to 4 parts by mass.
In addition, if necessary, the clad layer forming resin of the present invention may contain an antioxidant, an anti-yellowing agent, an ultraviolet absorber, a visible light absorber, a colorant, a plasticizer, a stabilizer, and a filler. So-called additives such as an agent may be added at a rate that does not adversely affect the effects of the present invention.

The resin for forming the clad layer is used as a resin varnish for forming the clad layer by dissolving a resin composition containing (a) a base polymer, (b) a photopolymerizable compound, and (c) a photopolymerization initiator in a solvent. You can also
As described above, it is preferable to use a resin film for forming a clad layer for forming the lower clad layer and the upper clad layer. It can be easily manufactured by coating on a material film and removing the solvent.

In the production process of the clad layer forming resin film, the base film used as necessary is a support for supporting the clad layer forming resin film, and the material thereof is not particularly limited. For example, the clad layer forming resin Polyester such as polyethylene terephthalate (PET), polypropylene, polyethylene, and the like are preferably used from the viewpoint that the film can be easily peeled and has heat resistance and solvent resistance.
The base film may be subjected to a release treatment, an antistatic treatment, or the like in order to facilitate later peeling of the clad layer forming resin film.
The thickness of the base film is usually 5 to 50 μm. When the thickness of the substrate film is 5 μm or more, there is an advantage that the strength as a support is easily obtained, and when it is 50 μm or less, there is an advantage that the winding property in the case of manufacturing in a roll shape is improved. From the above viewpoints, the thickness of the base film is preferably 10 to 40 μm, more preferably 15 to 30 μm.

Further, a protective film may be bonded to the resin film for forming a clad layer in consideration of film protection and rollability in the case of manufacturing into a roll.
As a protective film, the thing similar to what was mentioned as an example of the said base film can be used, and the mold release process and the antistatic process may be performed as needed.

The solvent used in the resin varnish for forming the clad layer is not particularly limited as long as it can dissolve the resin composition containing the components (a) to (c). For example, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve , Toluene, N, N-dimethylacetamide, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, N-methyl-2-pyrrolidone, or a mixed solvent thereof can be used.
The solid content concentration in the resin varnish for forming the cladding layer is usually 30 to 80% by mass, preferably 35 to 75% by mass, and more preferably 40 to 70% by mass.

The thickness of the clad layer-forming resin film is not particularly limited, but the thickness of the clad layer after drying is usually adjusted to 5 to 500 μm. When the thickness of the cladding layer is 5 μm or more, the thickness of the cladding layer necessary for light confinement can be secured, and when it is 500 μm or less, the thickness of the cladding layer can be easily controlled uniformly. From the above viewpoint, the thickness of the cladding layer is preferably 10 to 100 μm, more preferably 20 to 90 μm.
The thickness of the clad layer may be the same or different between the lower clad layer formed first and the upper clad layer for embedding the core pattern. The thickness of the layer is preferably larger than the thickness of the core layer.

<Core layer forming resin>
Next, the core layer forming resin used in the present invention is designed such that the cured product has a higher refractive index than the clad layer, and a resin composition capable of forming a core pattern with ultraviolet rays can be used. Resin compositions are preferred.
Specifically, it is preferable to use the same resin composition as the cladding layer forming resin.
That is, it is a resin composition containing the (a) base polymer, (b) a photopolymerizable compound, and (c) a photopolymerization initiator, and, if necessary, the above optional components.

Therefore, the cured product of the core layer forming resin film is designed to have a higher refractive index than the cured product of the optical waveguide forming resin film used for the cladding layer. The resin for core layer formation is used as a resin varnish for core layer formation by dissolving a resin composition containing (a) a base polymer, (b) a photopolymerizable compound and (c) a photopolymerization initiator in a solvent. You can also.
The core layer-forming resin film can be easily produced by applying the core layer-forming resin varnish on the base film as necessary and removing the solvent. In the production process of the core layer forming resin film, the base film used as necessary is a support for supporting the core layer forming resin film, and the material thereof is not particularly limited. The same base film used in the production process can be used.
For example, polyesters such as polyethylene terephthalate (PET), polypropylene, polyethylene, and the like are preferably used from the viewpoint that it is easy to peel off the resin film for forming the core layer and has heat resistance and solvent resistance. Can do.

Moreover, it is preferable to use a highly transparent flexible base film in order to improve the transmittance of the exposure light beam and reduce the side wall roughness of the core pattern. The haze value of the highly transparent base film is usually 5% or less, preferably 3% or less, more preferably 2% or less.
As such a base film, Toyobo Co., Ltd. product name "Cosmo Shine A1517" and "Cosmo Shine A4100" are available.
The base film may be subjected to a release treatment, an antistatic treatment or the like in order to facilitate later peeling of the core layer forming resin film.

The thickness of the base film is usually 5 to 50 μm. When the thickness of the base film is 5 μm or more, there is an advantage that the strength as a support is easily obtained, and when it is 50 μm or less, the gap with the mask at the time of pattern formation becomes small, and a finer pattern is formed. There is an advantage that you can. From the above viewpoint, the thickness of the base film is preferably 10 to 40 μm, more preferably 15 to 30 μm.

In addition, a protective film may be bonded to the core layer forming resin film as necessary, such as protection of the core layer forming resin film and rollability when manufacturing in a roll shape. As a protective film, the thing similar to the base film used in the resin film for clad layer formation can be used, and the mold release process and the antistatic process may be performed as needed.

The solvent used in the resin varnish for forming the core layer is not particularly limited as long as it can dissolve the resin composition containing the components (a) to (c). For example, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve , Toluene, N, N-dimethylacetamide, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, N-methyl-2-pyrrolidone, or a mixed solvent thereof can be used.
The solid content concentration in the core layer-forming resin varnish is usually 30 to 80% by mass, preferably 35 to 75% by mass, and more preferably 40 to 70% by mass.

The thickness of the resin film for forming the core layer is not particularly limited, but the thickness of the core layer after drying is usually adjusted to be 10 to 100 μm. When the thickness of the core layer is 10 μm or more, there is an advantage that the alignment tolerance can be increased in the coupling with the light emitting / receiving element or the optical fiber after the construction of the optical waveguide. When the thickness is 100 μm or less, the acceptance after the construction of the optical waveguide is obtained. There is an advantage that coupling efficiency is improved in coupling with a light emitting element or an optical fiber. From the above viewpoint, the thickness of the core layer is preferably 29 to 90 μm, more preferably 30 to 80 μm.
The core layer can also be easily manufactured by applying a resin varnish for forming a core layer on the clad layer by spin coating or the like and removing the solvent.

Hereinafter, the manufacturing method of the photoelectric composite substrate of the present invention (third invention) will be described with reference to FIG. First, in the first step, (1) as shown in FIG. 12A, a conductor pattern 3-11a is formed on a substrate 3-12, and a conductor protective layer 3-14 is further formed as necessary. The lower clad layer 3-31 is formed on the surface of the substrate 12 of the electrical wiring substrate 3-10 directly or via the adhesive layer 3-20, or (2) as shown in (a′-1) of FIG. Further, the lower cladding layer 3-31 is formed on the surface of the substrate 3-12 of the metal foil-attached substrate 3-13 having the metal foil 3-11 and the substrate 3-12, either directly or via the adhesive layer 3-20. Then, as shown in FIG. 12 (a′-2), the metal foil 3-11 is processed into a conductor pattern 3-11a, and further, as shown in FIG. 12 (a′-3). In this step, the conductor protective layer 3-14 is formed to obtain an electric wiring board with a lower cladding layer.

As described above, when the lower clad layer 3-31 is directly formed on the surface of the substrate 3-12, the varnish of the clad layer forming resin is applied by a known method such as a spin coat method, and the solvent is removed. To do so.
On the other hand, when the lower clad layer 3-31 is formed on the surface of the substrate 3-12 via the adhesive layer 3-20, a clad layer forming resin film is used. The resin film for forming a clad layer can be easily produced by applying a varnish of a resin for forming a clad layer onto a base film by a known method such as a spin coat method, if necessary, and removing the solvent. A method using a resin film for forming a cladding layer is preferable because the accuracy of the thickness of the lower cladding layer can be secured. The adhesive layer 3-20 may be formed by directly applying an adhesive composition to the surface of the substrate 3-12. As described above, as described above, a sheet-like adhesive having an adhesive layer on a support substrate, In particular, it is preferable to use an adhesive sheet having an adhesive layer on a supporting substrate.
When the adhesive sheet is used, after the protective film of the adhesive layer is peeled off, the adhesive layer is attached to the electric wiring substrate 3-10 or the substrate 3-12 of the substrate 3-13 with metal foil. Lamination is performed on the surface, and then the supporting substrate is peeled to form the adhesive layer 3-20. When the adhesive sheet having the above-described configuration is irradiated with ultraviolet rays, the adhesive strength with the supporting base material is greatly reduced, and the supporting base material is easily peeled off while the adhesive layer is held on the substrate 3-12. can do. The heating temperature at the time of lamination is preferably 50 to 130 ° C., and the pressing pressure is preferably about 0.1 to 1.0 MPa (1 to 10 kgf / cm 2), but these conditions are particularly limited. There is no. In addition, it is preferable that the protective film and the supporting substrate are not subjected to an adhesive treatment in order to facilitate peeling from the adhesive layer, and may be subjected to a release treatment as necessary.

A resin film for forming a cladding layer is attached to the adhesive layer formed on the surface of the substrate 3-12 in this way. The laminator described above can be used for pasting. At this time, if a protective film is provided on the opposite side of the base film in the resin film for forming the clad layer, the protective film is peeled off, and the resin film for forming the clad layer is then heat bonded to the adhesive layer. And cured by light or heating to form a clad layer. Here, it is preferable to laminate | stack under reduced pressure from the viewpoint of adhesiveness and followable | trackability, The conditions are the same as the case where the above-mentioned adhesive agent layer is laminated | stacked.
In the above method, the method in which the adhesive layer 3-20 is formed on the surface of the substrate 3-12 and then bonded to the resin film for forming the clad layer has been described. However, this order may be reversed.

As shown in FIG. 12 (a'-2), as a method of forming the conductor pattern 3-11a from the metal foil 3-11, a subtractive method of removing unnecessary portions as the conductor pattern from the metal foil having a required thickness. And a semi-additive method in which a metal is deposited on a necessary portion as a conductor pattern on a relatively thin metal foil by electrolytic plating or the like to obtain a necessary thickness.

In the case of the method of forming a conductor pattern by the subtractive method, first, a photocurable film is formed on the surface of the metal foil, exposed through a photomask, developed, and then a resist pattern is formed with an etching resist. Then, the portion not covered with the etching resist is removed by etching to form a conductor pattern, and finally the etching resist is removed to construct an electric wiring board. The photocurable film formed on the surface of the metal foil is composed of a thermosetting resin such as an epoxy resin, a photocuring agent, a curing accelerator, a pigment, a fluidity adjusting agent, a viscosity adjusting agent, etc., if necessary. The varnish that has been mixed and dispersed in can be applied directly to the surface of the metal foil and dried to form it, or the varnish can be applied to a carrier film and dried to form a semi-cured dry film. It can also be formed by laminating a metal foil.
Such a varnish-like etching resist material is commercially available, and there is OPT ER N-350 (trade name, manufactured by Nippon Paint Co., Ltd.). A dry film-like etching resist material is commercially available. And Fotec H-N930 (trade name, manufactured by Hitachi Chemical Co., Ltd.). In order to form a resist pattern and then etch away portions not covered with the etching resist, there are cupric chloride solution, ferric chloride solution, ammonium persulfate solution, etc. as etchants, and these etchants Can be sprayed to etch away portions not covered with the etching resist, thereby forming a conductor pattern.

In the case of a method of forming a conductor pattern by the semi-additive method, after applying a photoresist material to a metal foil, photolithography is performed to form a plating resist layer (resist pattern), and then electrolysis is performed using the metal foil as a power supply film. After conducting plating to deposit a conductor on the exposed portion of the metal foil without the resist layer to form a conductor layer (conductor pattern), then removing the plating resist layer to expose the metal foil, Etching is performed as a mask to remove the metal foil exposed by removing the plating resist layer, thereby constructing an electric wiring board.

The photoresist material is not particularly limited, and various commercially available materials can be used. For example, a liquid positive resist containing a novolac resin as a main component and containing a solvent such as a photosensitizer, ethyl lactate, and normal butyl acetate can be used. Such a liquid positive resist is available as, for example, commercially available OFPR (manufactured by Tokyo Ohka Kogyo Co., Ltd.). A photoresist film may be attached as a photoresist material. The photoresist film is not particularly limited, and various commercially available materials can be used. For example, when using SUNFORT (R) ASG-253 manufactured by Asahi Kasei, a commercially available film laminator is used to apply the film onto a polyimide film at a pressure of about 0.4 MPa while heating at 110 ° C. At the time of development, an unexposed portion can be removed using an aqueous sodium carbonate solution.

After the formation of the resist layer, electrolytic plating is performed using the metal foil as a power supply film to deposit a conductor layer on the exposed portion of the metal foil. In the case of plating copper, the electrolytic plating solution may be a sulfate bath or a sulfamine bath. In the case of plating silver, gold or an alloy thereof, a cyan bath can be used. After the electrolytic plating, the resist layer is removed to expose the metal foil. For example, the photoresist may be peeled or dissolved by dipping in a stripping solution. Specifically, for example, when the above-mentioned film resist manufactured by Asahi Kasei is used, the resist is removed using an aqueous solution of about 2 to 3% sodium hydroxide or potassium hydroxide, or an organic amine-based stripping solution. It can be carried out. For example, in the case of a liquid resist mainly composed of a so-called novolac resin, a stripping solution containing an organic solvent such as propylene glycol methyl ether acetate or alkylbenzene sulfonic acid can be used. After the resist layer is formed, the metal foil exposed by removing the resist layer is removed by etching to leave the metal foil and the conductor layer only in the conductor pattern region.

The etching solution is determined depending on the metal of the metal foil film and the metal of the conductor layer, and it is preferable to use an etching solution having a selectivity that removes the metal foil but not the conductor layer. Since there is a difference in thickness between the layers, the metal foil can be completely removed without adjusting the conductor layer by adjusting the etching time, so even the metal foil can be removed by etching. Any liquid may be used. Of course, when the metal foil and the conductor layer are the same metal, the metal foil is completely removed by adjusting the etching time without completely removing the conductor layer.
For example, when the metal foil is made of nickel and the conductor layer is made of copper, an FeCl ₃ aqueous solution, HNO ₃ , or an acid containing HNO ₃ can be used as the etching solution. In particular, in the case of HNO ₃ , nickel can be dissolved, but copper is not dissolved, which is particularly desirable.
For example, when the metal foil is made of copper and the conductor layer is also made of copper, an aqueous solution such as FeCl ₃ , CuCl ₂ , (NH 4) ₂ S ₂ O ₈ , aqueous ammonia, or the like can be used.
For example, when the metal foil is made of silver, the etching solution can be HNO ₃ , a mixed solution of H ₂ SO ₄ and H ₂ O ₂ , an Fe (NO ₃ ) ₃ aqueous solution, or the like.
For example, when the metal foil is made of iron, HNO ₃ or the like can be used as the etching solution. For example, when the metal foil is made of palladium, an NH ₃ I aqueous solution or the like can be used as the etching solution.

In the case of forming the conductor protective layer 3-14 on the conductor pattern 3-11a, a photocurable film is formed on the surface of the conductor pattern 3-11a, exposed through a photomask, developed, and developed. As shown in (e), a conductor protective layer 14 for insulating and protecting the conductor pattern is formed. The photocurable film formed on the surface of the conductor pattern is diluted with a thermosetting resin such as epoxy resin, a photocuring agent, a curing accelerator, and if necessary, a pigment, a fluidity adjusting agent, a viscosity adjusting agent, etc. A varnish that is mixed and dispersed in an agent can be directly applied to the surface of the conductor pattern and dried to form it. Also, the varnish is applied to a carrier film and dried to form a semi-cured dry film. It can also be formed by laminating to a substrate. Such a varnish-like solder resist material is commercially available, Provicoat 5000 (trade name, manufactured by Nippon Paint Co., Ltd.), and a dry film-like solder resist material is commercially available. SR-2300G-50 (trade name, manufactured by Hitachi Chemical Co., Ltd.).

The core pattern can be formed by providing a core forming resin layer (core layer) on the lower clad layer, and exposing and developing the core layer. There is no limitation on the method of forming the core layer, and a method of directly applying the core-forming resin varnish on the lower clad layer and drying it may be used, but the method of using the core layer-forming resin film is the thickness of the core layer. This is preferable because the accuracy of the above can be ensured.
When the core layer-forming resin film is composed of a core layer-forming resin layer and a base film, it is easy to handle, but it may be composed of a core layer-forming resin layer alone.
In the core layer forming resin film, when a protective film is provided on the opposite side of the base film, the core layer forming resin film is laminated after the protective film is peeled off. In this case, the protective film and the base film are preferably not subjected to an adhesion treatment in order to facilitate peeling from the core layer, and may be subjected to a release treatment as necessary.

A desired core pattern is formed by exposing and developing the core layer thus provided. Specifically, ultraviolet rays are irradiated in an image form through a photomask pattern.
Examples of the ultraviolet light source include known light sources that effectively emit ultraviolet light, such as a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, and a xenon lamp.

Next, when the base film remains on the core layer, the base film is peeled off, and the unexposed portion is removed and developed by wet development or the like to form a core pattern.
In the case of wet development, using an organic solvent-based developer or alkali developer suitable for the composition of the core layer-forming resin film or the core layer-forming resin varnish, spraying, rocking immersion, brushing, scraping, etc. Develop by the method of.

Examples of organic solvent developers include N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, γ-butyrolactone, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl Examples include ether and propylene glycol monomethyl ether acetate.
In order to prevent ignition, these organic solvents may be added with water in an amount of usually 1 to 20 parts by mass with respect to 100 parts by mass of the organic solvent.

As the alkaline developer, an alkaline aqueous solution, an aqueous developer, or the like can be used, and the base of the alkaline aqueous solution is not particularly limited. For example, alkali hydroxide such as lithium, sodium or potassium hydroxide; lithium Carbonates such as sodium, potassium or ammonium carbonates or bicarbonates; alkali metal phosphates such as potassium phosphate and sodium phosphate; alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; borax Sodium salts such as sodium metasilicate; tetramethylammonium hydroxide, triethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3-propanediol, 1,3-diaminopropanol-2-morpholine, etc. Possession of Bases and the like.

The pH of the alkaline aqueous solution used for development is preferably 9 to 11, and the temperature is adjusted according to the developability of the core-forming resin composition layer.
Further, in the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like may be mixed.
Among these, lithium carbonate, sodium carbonate, and potassium carbonate aqueous solution are particularly preferable because they are less irritating to the human body and less burden on the environment.

If necessary, an organic solvent can be used in combination with the alkaline aqueous solution. The organic solvent herein is not particularly limited as long as it is miscible with an alkaline aqueous solution. For example, alcohol such as methanol, ethanol, isopropanol, butanol, ethylene glycol, propylene glycol; acetone, 4-hydroxy-4-methyl -2-Ketones such as pentanone; polyhydric alcohol alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, etc. Is mentioned.
These can be used alone or in combination of two or more.

As the post-development processing, the core pattern of the optical waveguide may be cleaned using a cleaning liquid composed of water and the above organic solvent as necessary. An organic solvent can be used individually or in combination of 2 or more types. The concentration of the organic solvent is usually preferably 2 to 90% by mass, and the temperature is adjusted according to the developability of the core-forming resin composition.

Examples of the development method include a dip method, a battle method, a spray method such as a high-pressure spray method, brushing, and scraping. The high-pressure spray method is most suitable for improving the resolution.
Moreover, you may use together 2 or more types of image development methods as needed.
As processing after development, the core pattern may be further cured and used by heating at about 60 to 250 ° C. or exposure at about 0.1 to 1,000 mJ / cm ² as necessary.

Subsequently, a clad layer forming resin layer is provided on the core pattern, and the upper clad layer is formed by curing the resin layer. As described above, the varnish of the clad layer forming resin composition can be applied directly, but it is preferable to use an upper clad layer forming resin film. In that case, an operation of laminating the resin film for forming the upper clad layer for embedding the core pattern and an operation of forming the upper clad layer by curing the resin layer for forming the clad layer of the resin film for forming the upper clad layer are performed.
In this case, the thickness of the upper clad layer is preferably larger than the thickness of the core layer as described above.
Curing is performed by light or heat in the same manner as described above.

In the clad layer forming resin film, when a protective film is provided on the opposite side of the base film, after peeling the protective film, the clad layer forming resin film is heat-pressed and cured by light or heating, A cladding layer is formed. In this case, the base film may be peeled off or may be left bonded if necessary.
In the case where it is still bonded, the clad layer forming resin layer is preferably formed on a base film subjected to an adhesion treatment.
On the other hand, the protective film is preferably not subjected to adhesion treatment in order to facilitate peeling from the clad layer forming resin film, and may be subjected to mold release treatment as necessary.

In the optoelectric composite substrate obtained by the manufacturing method of the present invention, it is possible to easily achieve the coupling between the electric wiring substrate portion and the optical waveguide portion by mounting an optical path conversion mirror, a light receiving element and the like. Moreover, a photoelectric composite module can be easily obtained by mounting an optical element such as a surface emitting laser or a diode on the photoelectric composite substrate obtained by the manufacturing method of the present invention.

Hereinafter, the manufacturing method of the photoelectric composite substrate of the present invention (the fourth invention) will be described with reference to FIG. First, as shown in FIG. 13 (a), the first ′ step is directly or directly on the surface of the substrate 4-12 of the metal foil-attached substrate 4-13 having the metal foil 4-11 and the substrate 4-12. In this step, the lower clad layer 4-31 is formed via the adhesive layer 4-20.
When the lower clad layer 4-31 is directly formed on the surface of the substrate 4-12, a varnish of a clad layer forming resin is applied by a known method such as a spin coat method and the solvent is removed.
On the other hand, when the lower clad layer 4-31 is formed on the surface of the substrate 4-12 via the adhesive layer 4-20, a clad layer forming resin film is used. The resin film for forming a clad layer can be easily produced by applying a varnish of a resin for forming a clad layer onto a base film by a known method such as a spin coat method, if necessary, and removing the solvent. A method using a resin film for forming a cladding layer is preferable because the accuracy of the thickness of the lower cladding layer can be secured.

There is no restriction on the method of forming the adhesive layer 4-20 on the surface of the substrate 4-12, and the adhesive composition may be directly applied to the surface of the substrate, but it is a sheet having an adhesive layer on the supporting base material. The method of using an adhesive and transferring the adhesive layer from the sheet adhesive to the surface of the substrate 4-12 is excellent in the smoothness of the adhesive layer and can ensure the accuracy of the thickness of the adhesive layer. In addition, since the problem that the resin composition for forming the adhesive layer flows does not occur when forming the adhesive layer, it is preferable. As the sheet-like adhesive, an adhesive sheet having an adhesive layer on a supporting substrate is particularly preferable.
When using an adhesive sheet, after peeling off the protective film of the adhesive layer, the adhesive layer is laminated on the surface of the substrate 4-12 of the substrate 4-13 with metal foil, The support base material is peeled off to form the adhesive layer 4-20. When the adhesive sheet having the above-described configuration is irradiated with ultraviolet rays, the adhesive strength with the supporting base material is greatly reduced, and the supporting base material can be easily peeled while the adhesive layer is held on the substrate. it can.
The heating temperature at the time of lamination is preferably 50 to 130 ° C., and the pressing pressure is preferably about 0.1 to 1.0 MPa (1 to 10 kgf / cm ² ). There is no limit. In addition, it is preferable that the protective film and the supporting substrate are not subjected to an adhesive treatment in order to facilitate peeling from the adhesive layer, and may be subjected to a release treatment as necessary.

A resin film for forming a clad layer is laminated on the adhesive layer thus formed. At this time, if a protective film is formed on the opposite side of the base film in the resin film for forming the clad layer, the protective film is peeled off and then the resin film for forming the clad layer is heated to the adhesive layer. The clad layer is formed by pressure bonding and curing by light or heating. Here, it is preferable to laminate | stack under reduced pressure from the viewpoint of adhesiveness and followable | trackability, The conditions are the same as the case where the above-mentioned adhesive agent layer is laminated | stacked.
In the above method, the method in which the adhesive layer 4-20 is formed on the surface of the substrate 4-12 and then bonded to the resin film for forming the clad layer has been described. However, this order may be reversed.

The second step in the manufacturing method of the present invention (fourth invention) is a step of constructing an optical waveguide. Specifically, as shown in FIG. 13B, on the lower cladding layer 4-31. In the process of forming the optical waveguide 4-30 by forming the core pattern 4-32 and then forming the upper cladding layer 4-33 on the core pattern 4-32 as shown in FIG. is there.
The core pattern 4-32 can be formed by forming a core forming resin layer (core layer) on the lower clad layer 4-31, and exposing and developing the core layer.
The method for forming the core layer is the same as described in the third invention.

The third step in the manufacturing method of the present invention (fourth invention) is a step of constructing an electric wiring board from a substrate with metal foil. Specifically, as shown in FIG. This is a step of constructing the electric wiring board 4-10 using 4-11 as the conductor pattern 4-11a. This step is the same as the step of forming the metal foil of the substrate with metal foil in the third invention as a conductor pattern (first step of the third invention), and the method, conditions and the like are the same as those of the third invention.

In the optoelectric composite substrate obtained by the manufacturing method of the present invention (fourth invention), the coupling between the electric wiring substrate portion and the optical waveguide portion is easily achieved by mounting an optical path conversion mirror, a light receiving element, and the like. be able to.
Moreover, a photoelectric composite module can be easily obtained by mounting an optical element such as a surface emitting laser or a diode on the photoelectric composite substrate obtained by the manufacturing method of the present invention.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
(1) Production of optical waveguide [production of resin film for forming clad layer]
(A) As a base polymer, 48 parts by mass of phenoxy resin (trade name: Phenototo YP-70, manufactured by Toto Kasei Co., Ltd.), (B) As a photopolymerizable compound, alicyclic diepoxycarboxylate (trade name: KRM) -2110, molecular weight: 252, Asahi Denka Kogyo Co., Ltd.) 50 parts by mass, (C) Triphenylsulfonium hexafluoroantimonate salt (trade name: SP-170, Asahi Denka Kogyo Co., Ltd.) as a photopolymerization initiator 2 parts by weight, 40 parts by weight of propylene glycol monomethyl ether acetate as an organic solvent are weighed in a wide-mouthed plastic bottle, and stirred for 6 hours under the conditions of a temperature of 25 ° C. and a rotation speed of 400 rpm using a mechanical stirrer, shaft and propeller. A clad layer forming resin varnish A was prepared. After that, using a polyflon filter (trade name: PF020, manufactured by Advantech Toyo Co., Ltd.) with a pore diameter of 2 μm, the mixture is filtered under pressure at a temperature of 25 ° C. and a pressure of 0.4 MPa, and further the degree of vacuum using a vacuum pump and a bell jar. Degassed under reduced pressure for 15 minutes under the condition of 50 mmHg.
The clad layer forming resin varnish A obtained above is applied to a release PET film (trade name: PUREX A31, Teijin DuPont Films Co., Ltd., thickness: 25 μm) with a coating machine (Multicoater TM-MC, Co., Ltd.). It is applied using Hirano Tech Seed, dried at 80 ° C. for 10 minutes, then at 100 ° C. for 10 minutes, and then a release PET film (trade name: Purex A31, Teijin DuPont Films Co., Ltd., thickness: 25 μm as a protective film) ) Was attached so that the release surface was on the resin side, and a resin film for forming a clad layer was obtained. At this time, the thickness of the resin layer can be arbitrarily adjusted by adjusting the gap of the coating machine. In this embodiment, the thickness after curing is 25 μm for the lower cladding layer and 70 μm for the upper cladding layer. Adjusted.

[Production of resin film for core layer formation]
(A) As a base polymer, 26 parts by mass of a phenoxy resin (trade name: Phenototo YP-70, manufactured by Toto Kasei Co., Ltd.), (B) 9,9-bis [4- (2-acryloyl) as a photopolymerizable compound Oxyethoxy) phenyl] fluorene (trade name: A-BPEF, Shin-Nakamura Chemical Co., Ltd.) 36 parts by mass, and bisphenol A type epoxy acrylate (trade name: EA-1020, Shin-Nakamura Chemical Co., Ltd.) 36 mass Parts, (C) 1 part by mass of bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (trade name: Irgacure 819, manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, and 1- [4 -(2-Hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one (trade name: Ile (Cure 2959, manufactured by Ciba Specialty Chemicals) 1 part by weight, and 40 parts by weight of propylene glycol monomethyl ether acetate as the organic solvent were used to form the resin varnish B for forming the core layer in the same manner and under the same conditions as in the above production example. Prepared. Thereafter, pressure filtration and degassing under reduced pressure were performed under the same method and conditions as in the above production example.
The core layer-forming resin varnish B obtained above is applied to the non-treated surface of a PET film (trade name: Cosmo Shine A1517, manufactured by Toyobo Co., Ltd., thickness: 16 μm) in the same manner as in the above production example. After coating and drying, a release PET film (trade name: PUREX A31, Teijin DuPont Films Co., Ltd., thickness: 25 μm) is applied as a protective film so that the release surface is on the resin side, and a core layer forming resin A film was obtained. In this example, the gap of the coating machine was adjusted so that the film thickness after curing was 50 μm.

(2) Production of Wiring Board Next, a method for producing a wiring board combined with an optical waveguide will be described below with reference to FIG.
[Lamination of second support 1-8 and first substrate 1-1]
The first substrate 1-1 is a polyimide surface with a 150 mm square single-sided copper foil. Product name: Iupicel N, Ube Nitto Kasei Kogyo Co., Ltd., copper foil thickness: 5 μm, polyimide thickness 12.5 μm) A 140 mm square copper foil (trade name: 3EC-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd., thickness: 18 μm), which is the second release layer 1-6, is installed in the center, and the second adhesive layer 1 is formed thereon. -7, 150 mm square prepreg (trade name: GEA-679FG, manufactured by Hitachi Chemical Co., Ltd., thickness: 40 μm) and the second support 1-8, copper-clad laminate (MCL-E679F, Hitachi Chemical) Made by Kogyo Co., Ltd., thickness: 0.6 mm), evacuated to 4 kPa or less, then heated and laminated under the conditions of pressure 2.5 MPa, temperature 180 ° C., pressurization time 1 hour, The substrate 1-1 is attached to the second support 1-8. Laminated. (See Fig. 2 (a))

[Circuit formation by subtractive method]
Thereafter, a photosensitive dry film resist (trade name: Photec, manufactured by Hitachi Chemical Co., Ltd., thickness: 25 μm) is applied to the polyimide copper foil surface with single-sided copper foil, and a roll laminator (HLM-1500, manufactured by Hitachi Chemical Technoplant Co., Ltd.). ) Under a pressure of 0.4 MPa, a temperature of 50 ° C., and a laminating speed of 0.2 m / min, and then a width of 50 μm from the photosensitive dry film resist side with an ultraviolet exposure machine (EXM-1172, manufactured by Oak Manufacturing Co., Ltd.). The negative photomask was irradiated with ultraviolet light (wavelength 365 nm) of 120 mJ / cm ^2, and the unexposed photosensitive dry film resist was removed with a dilute solution of 0.1 to 5 mass% sodium carbonate at 35 ° C. Then, using a ferric chloride solution, the exposed copper foil was removed by etching to remove the photosensitive dry film resist, and exposure was performed using a 1-10 mass% sodium hydroxide aqueous solution at 35 ° C. A portion of the photosensitive dry film resist was removed. As a result, a second support 1-8 with the first substrate 1-1 having the circuit 1-9 formed on one side was obtained. (See Fig. 1 (b))

[Lamination of first support 1-4]
The first release layer 1-2 of the second support 1-8 with the first substrate 1-1 on which the circuit 1-9 is formed on one side formed as described above is 130 mm on the circuit 1-9 formation surface. A corner release sheet (trade name: Aflex, manufactured by Asahi Glass Co., Ltd., thickness: 30 μm) is installed in the center, and a 150 mm square build-up material (product name) is the first adhesive layer 1-3 from above. : AS-ZII, manufactured by Hitachi Chemical Co., Ltd., thickness: 40 μm), vacuumed to 500 Pa or less, then thermocompression bonded under conditions of pressure 0.4 MPa, temperature 110 ° C., pressurization time 30 seconds, build A copper-clad laminate (MCL-E679F, manufactured by Hitachi Chemical Co., Ltd., thickness: 0.6 mm) as the first support 1-4 is further formed on the up material surface, and heated under the same conditions as above. The first support 1-4 was laminated by pressure bonding (see FIG. 2C).

[Separation of second support]
Each side of the product formed above was cut by 12 mm, and only the second support 1-8 was separated. (See FIG. 1 (d)) Thus, a polyimide with a single-sided circuit laminated on the first support 1-4 was obtained.

[Production of adhesive film]
An adhesive film described in Example 1 of PCT / JP2008 / 05465 was produced. That is, (a) YDCN-703 (trade name, manufactured by Toto Kasei Co., Ltd., cresol novolak type epoxy resin, epoxy equivalent 210) 55 parts by mass as an epoxy resin, (b) Millex XLC-LL (Mitsui Chemicals, Inc.) as a curing agent Product name, phenol resin, hydroxyl group equivalent 175, water absorption rate 1.8% by mass, heating weight loss rate 4% at 350 ° C. 45% by mass, silane coupling agent NUC A-189 (trade name, manufactured by Nihon Unicar Co., Ltd.) 1.7 parts by mass of γ-mercaptopropyltrimethoxysilane) and 3.2 parts by mass of NUC A-1160 (trade name, γ-ureidopropyltriethoxysilane, manufactured by Nippon Unicar Co., Ltd.), (d) Aerosil R972 (silica) as filler The surface is coated with dimethyldichlorosilane and hydrolyzed in a 400 ° C reactor. , A filler having an organic group such as a methyl group on its surface, Nippon Aerosil Co., Ltd., trade name, silica, average particle size 0.016 μm) 32 parts by mass, cyclohexanone is added to the mixture, and the mixture is further stirred. And kneaded for 90 minutes. 280 parts by mass of (c) acrylic rubber HTR-860P-3 (trade name, manufactured by Nagase ChemteX Corporation, weight average molecular weight: 800,000) containing 3% by mass of glycidyl acrylate or glycidyl methacrylate as a polymer compound, and (e ) Curazole 2PZ-CN (trade name, 1-cyanoethyl-2-phenylimidazole, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as a curing accelerator was added in an amount of 0.5 parts by mass, stirred, mixed and vacuum degassed. This adhesive varnish was applied onto a 75 μm-thick polyethylene terephthalate (PET) film (Purex A31) subjected to a release treatment, and heated and dried at 140 ° C. for 5 minutes to form a coating film having a thickness of 10 μm. Next, a 25 μm release-treated polyethylene terephthalate (PET) film (Purex A31) was attached as a second protective film so that the release surface was on the resin side to obtain an adhesive film.

[Manufacture of wiring board combined with optical waveguide]
As the adhesive layer 1-10, the release PET film (Purex A31), which is a protective film for the adhesive film obtained above, is peeled off, and a roll laminator (HLM-1500, manufactured by Hitachi Chemical Technoplant Co., Ltd.) is used with a pressure of 0. Lamination was performed on the polyimide surface of the first substrate 1-1 under the conditions of 4 MPa, temperature of 50 ° C., and laminating speed of 0.2 m / min. Thereafter, ultraviolet light (wavelength 365 nm) is irradiated from the adhesive film side by 1 J / cm ² with an ultraviolet exposure machine (EXM-1172, manufactured by Oak Manufacturing Co., Ltd.), and a release PET film as a second protective film of the adhesive film (Purex A31) was peeled off.
Next, the release PET film (Purex A31), which is a protective film of the resin film for forming a clad layer obtained above, is peeled off, and on the adhesive film of the first substrate 1-1 obtained above, Affixing was performed under the same laminating conditions as described above, and the lower clad layer 1-11 was irradiated with 1.5 J / cm ² of ultraviolet light (wavelength 365 nm) with an ultraviolet exposure machine (manufactured by Oak Manufacturing Co., Ltd., EXM-1172). The lower cladding layer 1-11 was formed by heat treatment at a temperature of 10 ° C. for 10 minutes.
Next, the core layer-forming resin film was laminated on the lower clad layer 1-11 under the same lamination conditions as above to form a core layer.

Next, ultraviolet light (wavelength 365 nm) was irradiated with 0.8 J / cm ² through the negative photomask having a width of 50 μm with the above-described ultraviolet exposure machine, and then after exposure at 80 ° C. for 5 minutes, heating was performed. Thereafter, the PET film as the support film was peeled off, and the core pattern 1-12 was developed using a developer (propylene glycol monomethyl ether acetate / N, N-dimethylacetamide = 7/3, mass ratio). Then, it wash | cleaned using the washing | cleaning liquid (isopropanol), and heat-dried at 100 degreeC for 10 minute (s).
Next, using a vacuum pressurization type laminator (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd.) as a flat plate type laminator, after evacuating to 500 Pa or less, under conditions of pressure 0.4 MPa, temperature 50 ° C., pressurization time 30 seconds. The resin film for forming a clad layer was laminated as the upper clad layer 1-13 by thermocompression bonding.
Further, after irradiation with ultraviolet rays (wavelength 365 nm) at 3 J / cm ² , heat treatment was performed at 160 ° C. for 1 hour to cure the upper clad layer and produce an optical waveguide 1-15. (See Fig. 2 (e) -2)
A 45 ° mirror is formed by using a dicing saw (DAC552, manufactured by DISCO Corporation) from the upper clad layer 1-13 side of the obtained first substrate 1-1 and optical waveguide 1-15 with circuit 1-9. Thus, a wiring board combined with the optical waveguide was obtained.

[Separation of the first support]
Each side of the first substrate 1-1 with the first support 1-3 formed above is further cut by 10 mm each to separate the first support 1-3 (FIG. 2F-2). reference).
With respect to the obtained wiring board combined with the optical waveguide, the amount of deviation from the design value of the circuit on the outermost layer of the first substrate 1-1 was measured as follows. The results are shown in Table 1.

(Measurement method of deviation)
The measurement was performed before separating the first support 1-3. The X and Y coordinates of 30 alignment markers placed in the circuit on the outermost layer of the first substrate 1-1 were measured, and the diagonal markers were connected using the alignment markers at the four corners. The intersection was determined as the scaling factor origin (hereinafter abbreviated as S / F origin), and the average value obtained by dividing the distance between the four alignment markers by the design value was determined as the scaling factor (hereinafter abbreviated as S / F). For example, the alignment markers at the four corners of the design value are A, B, C, and D, and the measured alignment markers at the four corners are A ′, B ′, C ′, and D ′, and A (or A ′) and C ( Or C ′), when B (or B ′) and D (or D ′) are located on the diagonal line, the intersection of the straight line connecting A and C and the straight line connecting B and D is S of the design value. / F origin, and the intersection of the straight line connecting A ′ and C ′ and the straight line connecting B ′ and D ′ is the S / F origin of the measured value. Also, A'-B 'distance / AB distance, B'-C' distance / BC distance, C'-D 'distance / CD distance, and D'-A'. The average value of the inter-distance / DA distance is S / F. Thereafter, the measured X and Y coordinates are corrected to the position of the S / F origin of the actual measurement S / F origin, and the design value obtained by multiplying the design value by S / F. The amount of deviation from the X and Y coordinates was calculated. This deviation corresponds to the minimum deviation when the optical waveguide 1-15 or another circuit is aligned.
Further, the shrinkage ratio of the optical waveguide was calculated from (1-S / F) × 100 (%) determined above.
In Table 1, X represents the amount of displacement in the horizontal direction, Y represents the amount of displacement in the vertical direction, and XY represents the distance of displacement. From the results shown in Table 1, the maximum deviation was 7.5 μm, and the shrinkage was 0.04%.

After the second support 1-8 is separated, the first substrate 1-1 is cut using the dicing saw described above, and the first substrate that is the opposite surface to the first support from the cross section The unevenness of the 1-1 polyimide substrate was measured. Next, the measurement method is shown.

(Measurement method of unevenness)
As shown in FIG. 5, the substrate 1-101 on the separation surface side where the circuit is on the first substrate 1-1 and the substrate 1- 1 on the separation surface side where the circuit is not on the first substrate 1-1. The height difference of 102 was measured. As a result, it was 0.5 μm.
Furthermore, the core width of the optical waveguide varied from a minimum value of 49.9 μm to a maximum value of 50.2 μm.

Example 2
In Example 1, the first substrate 1-1 is a polyimide substrate with a single-sided copper foil, and the circuit formation after separating the second support 1-8 is described in Example 2 of JP-A-2006-93199. The semi-additive method was used under the conditions described below.
(Semi-additive process conditions)
Apparatus: Plasma reactor apparatus model PR-501A (trade name, manufactured by Yamato Scientific Co., Ltd.)
Etching depth: 1.5 μm
Power: 300W
Gas and flow rate: CF ₄ ; 20 SCCM, oxygen; 50 SCCM
Substrate temperature: Room temperature (25 ° C)
Degree of vacuum: 100Pa
Etching rate: 300 nm / min
An optical waveguide 1-15 was formed in the same manner as in Example 1 before the first support 1-1 was laminated. Further, a single-sided polyimide substrate on which a circuit was previously formed by the subtractive method was bonded to the polyimide surface, and then the adhesive film surface and the optical waveguide 1-15 were bonded. Other steps were performed in the same manner as in Example 1 (FIG. 2 (f) -3).

With respect to the obtained wiring board combined with the optical waveguide, the displacement amount of the circuit position in the outermost layer of the first substrate 1-1 was measured in the same manner as in Example 1. The results are shown in Table 2.
From the results in Table 2, the maximum deviation was 7.2 μm, and the shrinkage was 0.05%.

Next, in the same manner as in Example 1, the substrate 1-101 on the separation surface side where the circuit is located on the first substrate 1-1 and the separation surface side where the circuit is absent on the first substrate 1-1. The difference in height of the substrate 1-102 was measured. As a result, it was 0.5 μm.
Further, the core width of the optical waveguide varied from a minimum value of 50.0 μm to a maximum value of 50.3 μm.

Example 3
In Example 1, instead of an optical waveguide as the second substrate 1-5, a prepreg (trade name: GEA-679FG, manufactured by Hitachi Chemical Co., Ltd., thickness: 40 μm) is used on the circuit formation surface of the first substrate 1-1. ), Copper foil (trade name: 3EC-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd., thickness: 18 μm) are sequentially formed, vacuumed to 4 kPa or less, pressure 2.5 MPa, temperature 180 ° C., pressurization time 1 Heat lamination was performed under conditions of time. Further, a circuit was formed on the copper foil using the subtractive method (see FIG. 2 (f) -1).

For the obtained wiring board, in the same manner as in Example 1, the amount of deviation of the circuit position in the outermost layer of the first substrate 1-1 was measured. The results are shown in Table 3.
From the results in Table 3, the maximum deviation was 9.6 μm, and the shrinkage was 0.05%.

Example 4
In Example 3, an optical waveguide 1-15 was further formed on the circuit formation surface of the second substrate 1-5 under the same conditions as in Example 1 (see FIG. 2 (f) -4).
As in Example 1, the substrate 1-101 on the separation surface side where the circuit is located on the first substrate 1-1 and the substrate 1- 1 on the separation surface side where the circuit is not present on the first substrate 1-1. The height difference of 102 was measured. As a result, it was 1.5 μm.
Further, the core width of the optical waveguide varied from a minimum value of 50.1 μm to a maximum value of 50.2 μm.

Example 5
In the first embodiment, after forming the circuit 1-9 as the process A, the optical waveguide 1-15 and the polyimide substrate (substrate X16) are formed on the circuit 1-9 forming surface under the same conditions as in the second embodiment. One substrate 1-1 was obtained. Subsequent steps B and thereafter were performed in the same manner as in Example 3 except that the second substrate 1-5 was not formed (see FIG. 3).
As in Example 1, the substrate 1-101 on the separation surface side where the circuit is located on the first substrate 1-1 and the substrate 1- 1 on the separation surface side where the circuit is not present on the first substrate 1-1. The height difference of 102 was measured. As a result, it was 1.0 μm.
Further, when the core width of the optical waveguide was measured, there was a variation from a minimum value of 49.7 μm to a maximum value of 50.3 μm.

Comparative Example 1
In Example 1, the first release layer 1-2, the first adhesive layer 1-3, the first support 1-4, the second release layer 1-6, and the second adhesive layer 1-7. The second substrate 1-8 was not used, and a polyimide substrate circuit was formed in the same manner except that the circuit formation was simultaneously performed using the subtractive method.
With respect to the obtained wiring board combined with the optical waveguide, the displacement amount of the circuit position in the outermost layer of the first substrate 1-1 was measured in the same manner as in Example 1. The results are shown in Table 4.
From the results of Table 4, the maximum deviation was 32.3 μm, and the shrinkage was 0.15%.

As in Example 1, the substrate surface 1-101 on the release surface side of the portion where the circuit is located on the first substrate 1-1, and the substrate surface on the release surface side of the portion where the circuit is not present on the first substrate 1-1. The height difference of 1-102 was measured. As a result, it was 3.0 μm. Furthermore, the core width of the optical waveguide varied from a minimum value of 48 μm to a maximum value of 53 μm.

Example 6
(Production of optoelectric composite member)
Hereinafter, a method for producing the photoelectric composite member will be described with reference to FIGS.
[Lamination of lower support]
150 mm square polyimide foil with double-sided copper foil Trade name: Iupicel N, Ube Nitto Kasei Kogyo Co., Ltd., copper foil thickness: 5 μm, polyimide thickness 12.5 μm) on a copper foil surface of 140 mm square copper foil (trade name: 3EC-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd., thickness: 18 μm), and a 150 mm square prepreg (trade name: GEA-679FG, manufactured by Hitachi Chemical Co., Ltd., thickness: 40 μm) After constructing a copper-clad laminate (MCL-E679F, manufactured by Hitachi Chemical Co., Ltd., thickness: 0.6 mm), vacuuming to 4 kPa or less, pressure 2.5 MPa, temperature 180 ° C., pressurization time 1 hour The electrical wiring 2-2 was laminated on the lower support 2-1 by heating lamination under conditions. (See FIG. 6 (a)) Thereafter, circuit formation was performed on one side of the polyimide with double-sided copper foil using a subtractive method. As a result, a lower support body 2-1 with an electric wiring board 2-2 for single-sided electric wiring was obtained. (See FIG. 6 (b))

[Lamination of upper support]
A 130 mm square release sheet (trade name: Aflex, manufactured by Asahi Glass Co., Ltd., thickness: 30 μm) is placed in the center on the electrical wiring surface of the lower support 2-1 with the electrical wiring board 2-2 formed above. A 150 mm square build-up material (trade name: AS-ZII, manufactured by Hitachi Chemical Co., Ltd., thickness: 40 μm) is evacuated to 500 Pa or less, pressure 0.4 MPa, temperature 110 ° C., pressure After thermocompression bonding under conditions of 30 seconds, a copper-clad laminate (MCL-E679F, manufactured by Hitachi Chemical Co., Ltd., thickness: 0.6 mm) is further formed on the build-up surface, and the same conditions as above The upper support 2-3 was laminated by thermocompression bonding. (See FIG. 6C) A detailed layer structure is shown in FIG.

[Separation of lower support]
Each side of the product formed above was cut by 12 mm, and only the lower support 2-1 was separated. (Refer to FIG. 6 (d)) Thereafter, a circuit was formed on the copper foil surface of the polyimide with copper foil, which was the peel surface, using a subtractive method. As a result, polyimide with double-sided electrical wiring laminated on the upper support 2-3 was obtained.

[Production of optoelectric composite members]
A release PET film (Purex A31), which is a protective film for the adhesive film obtained in Example 1, was peeled off, and a pressure laminator (manufactured by Hitachi Chemical Technoplant Co., Ltd., HLM-1500) was used. Pressure 0.4 MPa, temperature 50 Lamination was performed on the polyimide surface of the lower support 2-1 under the conditions of 0 ° C. and a laminating speed of 0.2 m / min. Thereafter, ultraviolet light (wavelength 365 nm) is irradiated from the adhesive film side by 1 J / cm ² with an ultraviolet exposure machine (EXM-1172, manufactured by Oak Manufacturing Co., Ltd.), and a release PET film as a second protective film of the adhesive film (Purex A31) was peeled off.
Next, the release PET film (Purex A31), which is a protective film of the resin film for forming the lower cladding layer obtained above, is peeled off, and on the adhesive film of the lower support 2-1 obtained above, Affixing under the same laminating conditions as described above, the lower clad layer 2-4 was irradiated with 1.5 J / cm ² of ultraviolet light (wavelength 365 nm) with an ultraviolet exposure machine (EXM-1172 manufactured by Oak Manufacturing Co., Ltd.), and then 80 The lower clad layer 2-4 was formed by heat treatment at a temperature of 10 ° C. for 10 minutes.
Next, the core layer-forming resin film was laminated on the lower clad layer 4 under the same lamination conditions as described above to form a core layer.

Next, ultraviolet light (wavelength 365 nm) was irradiated with 0.8 J / cm ² through the negative photomask having a width of 50 μm with the above-described ultraviolet exposure machine, and then after exposure at 80 ° C. for 5 minutes, heating was performed. Thereafter, the PET film as the support film was peeled off, and the core pattern 2-5 was developed using a developer (propylene glycol monomethyl ether acetate / N, N-dimethylacetamide = 7/3, mass ratio). Then, it wash | cleaned using the washing | cleaning liquid (isopropanol), and heat-dried at 100 degreeC for 10 minute (s).
Next, a vacuum pressurization laminator (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd.) is used as a flat plate laminator. After vacuuming to 500 Pa or less, the pressure is 0.4 MPa, the temperature is 50 ° C., and the pressurization time is 30 seconds. The resin film for forming a clad layer was laminated as an upper clad layer 2-6 by thermocompression bonding.
Further, after irradiation with ultraviolet rays (wavelength 365 nm) at 3 J / cm ² , heat treatment was performed at 160 ° C. for 1 hour to cure the upper clad layer and produce an optical waveguide 2-8. (See Fig. 6 (e))
A 45 ° mirror is formed by using a dicing saw (DAC552, manufactured by Disco Corporation) from the side of the upper clad layer 2-6 of the obtained optical waveguide 2-8 with the electric wiring board 2-2, and the photoelectric composite A member was obtained. (See FIG. 6 (f))

[Separation of upper support]
Each side of the electric wiring board 2-2 with the upper support 2-3 formed as described above was further cut by 10 mm each to separate the upper support 2-3. (See FIG. 6 (g) and FIG. 7 (b))
With respect to the obtained photoelectric composite member, the distortion generated in the optical waveguide was evaluated by the amount of deviation of the core position of the optical waveguide 2-8 from the design value. The results are shown in Table 5.

(Measurement method of deviation)
The measurement was performed before separating the upper support 2-3. The X and Y coordinates of 30 alignment markers arranged in a 125 mm square of the optical waveguide 2-8 were measured and calculated in the same manner as in Example 1.

Example 7
In Example 6, after separating the upper support 2-3, an FR-4 plate having a thickness of 0.6 mm, on which a circuit was formed using the subtractive method, was formed using the adhesive prepared in Example 1. -4 After being bonded to the plate under the above conditions, the adhesion surface was evacuated to 500 Pa or less using a vacuum pressure laminator (MVLP-500 manufactured by Meiki Seisakusho Co., Ltd.) from the upper clad side, Thermocompression bonding was performed on the optical waveguide 2-8 under the conditions of 4 MPa, temperature of 100 ° C., and pressurization time of 30 seconds. Otherwise, an optoelectric composite member was produced in the same manner. (See Figure 8)
With respect to the obtained photoelectric composite member, the amount of deviation of the core position of the optical waveguide 2-8 was measured in the same manner as in Example 6. The results are shown in Table 6.
From the results shown in Table 6, the maximum deviation was 6.9 μm, and the shrinkage was 0.05%.

Example 8
In Example 6, instead of polyimide with double-sided copper foil, polyimide with single-sided copper foil (trade name: Iupicel N, manufactured by Ube Nitto Kasei Kogyo Co., Ltd., copper foil thickness: 5 μm, polyimide thickness 12.5 μm) The polyimide surface and the lower support 2-1 were attached using a single-sided slightly adhesive Kapton double-sided tape (product number: 4309, manufactured by Sumitomo 3M Co., Ltd.). The strongly adhesive surface was on the lower support 2-1 side, and the slightly adhesive surface was a polyimide surface. Further, after separating the upper support 2-3, an FR-4 plate having a thickness of 0.6 mm, which has been subjected to double-side etching from the upper clad side, is obtained using the adhesive obtained in the production of the adhesive film. After being bonded to each other under the above conditions, a vacuum pressurization type laminator (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd.) was used to evacuate to 500 Pa or less, then pressure 0.4 MPa, temperature 100 ° C., pressurization time 30 An optoelectric composite member was produced in the same manner except that it was thermocompression bonded to the upper clad side of the optical waveguide 2-8 under the condition of seconds. (See Figure 9)
With respect to the obtained photoelectric composite member, the amount of deviation of the core position of the optical waveguide 2-8 was measured in the same manner as in Example 6. The results are shown in Table 7.
From the results shown in Table 7, the maximum deviation was 7 μm, and the shrinkage was 0.05%.

Example 9
In Example 6, the upper support 2-3 is a copper-clad laminate (trade name: MCL-E-679FB, manufactured by Hitachi Chemical Co., Ltd., thickness: 0.6 mm) using a subtractive method for a double-sided circuit. A 150 mm square build-up material (trade name: AS-ZII, manufactured by Hitachi Chemical Co., Ltd., thickness: 40 μm) is thermocompression bonded to the circuit processed surface under the above conditions, and then the above conditions are satisfied. Then, the photoelectric composite member was manufactured in the same manner except that it was bonded to the electric wiring board 2-2 and the upper support 2-3 was not separated. (See Figure 10)
With respect to the obtained photoelectric composite member, the amount of deviation of the core position of the optical waveguide 2-8 was measured in the same manner as in Example 6. The results are shown in Table 8.
From the results shown in Table 4, the maximum deviation was 5.7 μm, and the shrinkage was 0.05%.

Example 10
The lower support 2-1 and the electric wiring board 2-2 are laminated in the same manner as in the sixth embodiment, and after forming a circuit, the optical waveguide 2-8 is formed on the electric wiring board 2-2 under the same conditions as in the sixth embodiment. Formed. Thereafter, a mirror was formed under the above conditions. Next, as a step of laminating the upper support 2-1, a 150 mm square prepreg (trade name: GEA-679FG, manufactured by Hitachi Chemical Co., Ltd., thickness: 40 μm), a 130 mm square copper foil (trade name: 3EC- VLP, manufactured by Mitsui Mining & Smelting Co., Ltd., thickness: 18 μm, 150 mm square copper foil (trade name: 3EC-VLP, manufactured by Mitsui Kinzoku Mining Co., Ltd., thickness: 18 μm), 150 mm square prepreg (trade name: GEA -679FG, manufactured by Hitachi Chemical Co., Ltd., thickness: 40 μm), copper-clad laminate (MCL-E679F, manufactured by Hitachi Chemical Co., Ltd., thickness: 0.6 mm) were sequentially constructed and evacuated to 4 kPa or less. Thereafter, heat lamination was performed under the conditions of a pressure of 2.5 MPa, a temperature of 180 ° C., and a pressurization time of 1 hour to form a lower support body 2-1 with electric wiring in which an optical waveguide 2-8 was arranged in the inner layer. A detailed layer structure is shown in FIG. The product workpiece was cut by 12 mm on each side to separate the lower support 2-1, and then the copper foil surface of the polyimide with copper foil, which was the release surface, was formed using a subtractive method.
Further, after forming the optical waveguide 8 on the circuit forming surface of the copper foil surface of polyimide with copper foil by the same method as in Example 6, the product work is further cut by 10 mm on each side to separate the upper support 2-3. Then, a circuit was formed by using a subtractive method on a 140 mm square copper foil, which is a peeled surface after separation of the upper support 2-3. Next, a mirror part was formed on the outermost optical waveguide 2-8 under the above conditions, and the product workpiece was further cut by 10 mm on each side to obtain a photoelectric composite member. FIG. 11B shows a layer configuration diagram.
For the obtained optical / electrical composite member, after forming the outer optical waveguide 2-8, the amount of deviation of the core position of the optical waveguide 2-8 was measured in the same manner as in Example 6. Table 9 shows the results of the inner optical waveguide 2-8, and Table 10 shows the results of the outer optical waveguide 2-8.
From the results of Table 9, the maximum deviation was 7.2 μm and the shrinkage was 0.08%. From the results shown in Table 10, the maximum deviation was 11.2 μm, and the shrinkage was 0.05%.

Comparative Example 2
A photoelectric composite member was produced in the same manner as in Example 6 except that the upper support 2-3 and the lower support 2-1 were not attached.
With respect to the obtained photoelectric composite member, the amount of deviation of the core position of the optical waveguide 2-8 was measured in the same manner as in Example 6. The results are shown in Table 11.
From the results shown in Table 11, the maximum deviation was 75 μm, and the shrinkage was 1.0%.

Example 11
Each step was carried out as follows to produce a photoelectric composite substrate.
(1) Production of adhesive sheet (a) As a high molecular weight component, HTR-860P-3 (trade name, manufactured by Nagase ChemteX Corporation, glycidyl group-containing acrylic rubber, weight average molecular weight 800,000, Tg: −7 ° C. ) 100 parts by mass, (b) As an epoxy resin, YDCN-703 (trade name, manufactured by Toto Kasei Co., Ltd., o-cresol novolac type epoxy resin, epoxy equivalent 210), 5.4 parts by mass, YDCN-8170C (Toto Kasei ( Co., Ltd. trade name, bisphenol F type epoxy resin, epoxy equivalent 157) 16.2 parts by mass, (c) epoxy resin curing agent, Phenolite LF2882 (Dainippon Ink Chemical Co., Ltd. trade name, bisphenol A novolak) Resin, 15.3 parts by mass of hydroxyl group equivalent 118 g / eq), NUCA-189 (Nihon Unica) as silane coupling agent Trade name, γ-mercaptopropyltrimethoxysilane) 0.1 parts by mass, and NUCA-1160 (Nihon Unicar Co., Ltd., product name, 3-ureidopropyltriethoxysilane) 0.3 parts by mass, d) 30 parts by mass of A-DPH (trade name, dipentaerythritol hexaacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd. as a photoreactive monomer, and (e) Irgacure 369 (Ciba Specialty Chemicals Co., Ltd.) as a photobase generator. Product name, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1-one: I-369) 1.5 parts by mass, cyclohexanone as an organic solvent was added and mixed with stirring. Vacuum degassed. This adhesive resin composition varnish was applied onto a 75 μm-thick surface-release-treated polyethylene terephthalate (manufactured by Teijin Ltd., Teijin Tetron Film: A-31), and dried by heating at 80 ° C. for 30 minutes. An adhesive sheet was obtained. This adhesive sheet is laminated with an 80 μm-thick UV transparent support substrate (manufactured by Thermo Co., Ltd., low density polyethylene terephthalate / vinyl acetate / low density polyethylene terephthalate three-layer film: FHF-100). Thus, an adhesive sheet composed of a protective film (the surface release-treated polyethylene terephthalate), an adhesive layer, and an ultraviolet transmissive supporting substrate was prepared.
The storage elastic modulus of the adhesive resin composition obtained by irradiating the adhesive sheet with ultraviolet light of 365 nm at 500 mJ / cm ² and then curing at 160 ° C. for 1 hour is measured with a dynamic viscoelasticity measuring device (Rheology Co., Ltd.). Manufactured by DVE-V4) (sample size: length 20 mm, width 4 mm, film thickness 80 μm, heating rate 5 ° C./min, tensile mode 10 Hz, automatic static load). As a result, 400 MPa at 25 ° C., It was 1 MPa at 125 ° C. and 5 MPa at 260 ° C.

(2) Formation of lower clad layer on substrate surface of substrate with metal foil Peel off protective film of adhesive sheet prepared in (1) above, substrate with copper foil (length 150 mm, width 150 mm, substrate: polyimide) (Thickness: 25 μm), copper foil thickness: 18 μm, roll laminator (manufactured by Hitachi Chemical Technoplant Co., Ltd., HLM-1500) on the polyimide surface of Toray Film Processing Co., Ltd. Was used so that the adhesive layer was in contact with the substrate under the conditions of a temperature of 60 ° C., a pressure of 0.5 MPa, and a feed rate of 0.2 m / min. The thickness of the adhesive layer was 10 μm. Subsequently, the adhesive sheet is irradiated with ultraviolet rays (365 nm) at 250 mJ / cm ² from the support substrate side to reduce the adhesive force between the adhesive layer and the support substrate interface, and the support substrate is peeled off to perform adhesion. The agent layer was exposed.
Thereafter, the protective film of the clad layer forming resin film prepared in Example 1 is peeled off so that the clad layer forming resin layer is in contact with the adhesive layer, and a roll laminator (manufactured by Hitachi Chemical Technoplant Co., Ltd., HLM-1500) is roll-laminated under the conditions of 80 ° C., 0.5 MPa, feed rate of 0.5 m, and further irradiated with ultraviolet rays (wavelength 365 nm) at 1 J / cm ² , and then the support base of the resin film for forming the clad layer The material was peeled off and heat-treated at 80 ° C. for 10 minutes to form a lower clad layer, and a substrate with a copper foil having the lower clad layer on the substrate surface was obtained.

(3) Formation of Conductor Pattern Photo-curable H-N930 (Hitachi, 30 μm thick photo-curable film on the copper foil surface of the copper foil substrate having the lower clad layer prepared in (2) above. (Trade name, manufactured by Kasei Kogyo Co., Ltd.) was laminated. The photomask of the conductor pattern was overlaid on the etching resist dry film, and exposure was performed under a vacuum of 60 mmHg. Thereafter, development was performed to form an etching resist, and then a cupric chloride solution was sprayed and sprayed to remove unnecessary copper foil, thereby forming a conductor pattern.

(4) Formation of conductor protective layer (solder resist layer) SR-2300G-50 (trade name, manufactured by Hitachi Chemical Co., Ltd.), a dry film for solder resist, has a thickness of 50 μm on a substrate on which a conductor pattern is formed. Was laminated. A photomask having a conductor pattern to be protected was placed on a dry film for a solder resist, and exposed under a vacuum of 60 mmHg. Thereafter, development was performed, a solder resist layer was formed, and dried to construct an electric wiring board.

(5) Formation of core pattern A roll laminator (HLM-1500, manufactured by Hitachi Chemical Technoplant Co., Ltd.) is used on the lower clad layer of the electric wiring board with the lower clad layer produced in (4) above, and the pressure is 0. The core layer-forming resin film produced in Example 1 was laminated under the conditions of 4 MPa, temperature of 50 ° C., and laminating speed of 0.2 m / min, and then a vacuum pressure laminator (Meiki Seisakusho Co., Ltd.) as a flat plate laminator. MVLP-500) was used, and after vacuuming to 500 Pa or less, the core layer was formed by thermocompression bonding under conditions of a pressure of 0.4 MPa, a temperature of 50 ° C., and a pressurization time of 30 seconds.

Next, ultraviolet rays (wavelength 365 nm) were irradiated with 0.6 J / cm ² with a UV photomask through a negative photomask having a width of 50 μm, followed by heating at 80 ° C. for 5 minutes. Thereafter, the PET film as the support film was peeled off, and the core pattern was developed using a developer (propylene glycol monomethyl ether acetate / N, N-dimethylacetamide = 8/2, mass ratio). Then, it wash | cleaned using the washing | cleaning liquid (isopropanol), and heat-dried at 100 degreeC for 10 minute (s).
Subsequently, the above-mentioned resin film for forming a clad layer was laminated under the same laminating conditions as those for laminating the lower clad layer. Further, after irradiating with ultraviolet rays (wavelength 365 nm) at 3 J / cm ² , the support base of the resin film for forming the cladding layer is peeled off, and heat treatment is performed at 180 ° C. for 1 hour to form an upper cladding layer. It was constructed.
When the refractive index of the core layer and the clad layer was measured with a prism coupler (Model 2010) manufactured by Metricon, the core layer was 1.584 and the clad layer was 1.550 at a wavelength of 830 nm. In addition, the propagation loss of the manufactured optical waveguide was determined by using a cut-back method using a surface-emitting laser (850 nm, manufactured by EXFO, FLS-300-01-VCL) as a light source, and Q82214, manufactured by Advantest Corporation as a light receiving sensor. Measurement waveguide length: 10, 5, 3, 2 cm, incident fiber: GI-50 / 125 multimode fiber (NA = 0.20), outgoing fiber: SI-114 / 125 (NA = 0.22)) However, it was 0.1 dB / cm.

Example 12
The substrate with metal foil in (2) in Example 11 is replaced with a flexible electrical wiring substrate (length 48 mm, width 4 mm, base material: Kapton EN, 25 μm, copper circuit thickness: 12 μm) having electrical wiring, and The same operation as in Example 11 was performed except that (3) and (4) in Example 1 were not performed.

The photoelectric composite substrates obtained in Examples 11 and 12 were extremely excellent in coupling efficiency because the positional deviation between the optical wiring and the electrical wiring was 10 μm / 100 mm or less.

Example 13
(1) Construction of optical waveguide On the lower clad layer of the substrate with copper foil having the lower clad layer produced in Example 11, a similar roll laminator was used, pressure 0.4 MPa, temperature 50 ° C., laminating speed 0. The core layer-forming resin film produced in Example 1 was laminated under the condition of 2 m / min, and then a vacuum / pressure laminator (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd.) was used as a flat plate laminator, and 500 Pa or less. Then, the core layer was formed by thermocompression bonding under conditions of a pressure of 0.4 MPa, a temperature of 50 ° C., and a pressurization time of 30 seconds.
Next, ultraviolet rays (wavelength 365 nm) were irradiated with 0.6 J / cm ² with a UV photomask through a negative photomask having a width of 50 μm, followed by heating at 80 ° C. for 5 minutes. Thereafter, the PET film as the support film was peeled off, and the core pattern was developed using a developer (propylene glycol monomethyl ether acetate / N, N-dimethylacetamide = 8/2, mass ratio). Then, it wash | cleaned using the washing | cleaning liquid (isopropanol), and heat-dried at 100 degreeC for 10 minute (s).
Next, the clad layer forming resin film produced in Example 1 was laminated under the same laminating conditions as the lower clad layer. Further, after irradiating with ultraviolet rays (wavelength 365 nm) at 3 J / cm ² , the support base of the resin film for forming the cladding layer is peeled off, and heat treatment is performed at 180 ° C. for 1 hour to form an upper cladding layer. It was constructed.
When the refractive index of the core layer and the clad layer was measured with a prism coupler (Model 2010) manufactured by Metricon, the core layer was 1.584 and the clad layer was 1.550 at a wavelength of 830 nm. In addition, the propagation loss of the manufactured optical waveguide was determined by using a cut-back method using a surface-emitting laser (850 nm, manufactured by EXFO, FLS-300-01-VCL) as a light source, and Q82214, manufactured by Advantest Corporation as a light receiving sensor. Measurement waveguide length: 10, 5, 3, 2 cm, incident fiber: GI-50 / 125 multimode fiber (NA = 0.20), outgoing fiber: SI-114 / 125 (NA = 0.22)) However, it was 0.1 dB / cm.

(2) Conductor pattern formation A photo-curable film for photo resist, FOTECH H-N930 (trade name, manufactured by Hitachi Chemical Co., Ltd.) was laminated on the surface of the copper foil of the substrate with copper foil. . The photomask of the conductor pattern was overlaid on the etching resist dry film, and exposure was performed under a vacuum of 60 mmHg. Thereafter, development was performed to form an etching resist, and then a cupric chloride solution was sprayed and sprayed to remove unnecessary copper foil, thereby forming a conductor pattern.
(3) Formation of conductor protective layer (solder resist layer) SR-2300G-50 (trade name, manufactured by Hitachi Chemical Co., Ltd.), a dry film for solder resist, has a thickness of 50 μm on a substrate on which a conductor pattern is formed. Was laminated. A photomask having a conductor pattern to be protected was placed on a dry film for a solder resist, and exposed under a vacuum of 60 mmHg. Thereafter, development was performed, a solder resist was formed, and dried to construct an electric wiring board.
The optoelectric composite substrate obtained by the above process had a positional deviation between the optical wiring and the electrical wiring of 10 μm / 100 mm or less, and was extremely excellent in coupling efficiency.

According to the method for manufacturing a wiring board of the present invention, a wiring board having only an electric circuit has a fine wiring because a fine wiring board with less unevenness of the base material in the manufacturing process and reduced defects due to short circuit or opening can be obtained. Reliable wiring boards (motherboards, semiconductor chip mounting boards), semiconductor packages, and flexible boards can be manufactured. For wiring boards combined with optical waveguides, distortions that occur in the optical waveguides during the manufacturing process are remarkably reduced, dimensional stability can be achieved, and the core width can be formed uniformly with little unevenness on the substrate. It can be applied to a wide range of fields such as optical interconnection with low propagation loss.
According to the method for manufacturing an optoelectric composite member of the present invention, distortion generated in an optical waveguide in a manufacturing process is remarkably reduced and dimensional stabilization can be achieved. Therefore, the method can be applied to a wide range of fields such as optical interconnection between boards or within a board. Is possible.
According to the method for producing an optoelectric composite substrate of the present invention, an excellent optoelectric composite substrate can be efficiently produced without causing a problem of alignment. The optoelectric composite substrate manufactured by the method of the present invention can be applied to a wide range of fields such as optical interconnection, especially when a very precise core pattern is required or a large area optoelectronic composite substrate is required. It is effective for.

Claims

Step A for forming a circuit on the first substrate, Step B for laminating a first support on the circuit forming surface of the first substrate via a first release layer, Circuit formation for the first substrate A method for manufacturing a wiring board, which includes a step C of forming a second substrate or circuit on the opposite surface of the surface in order.
The method for manufacturing a wiring board according to claim 1, wherein in the step B, a circuit formed on the first substrate is embedded in the first release layer.
Before the step A, the method further includes a step D of laminating the first substrate on a second support, and in the step A, on the surface opposite to the second support forming surface of the first substrate. The method for manufacturing a wiring board according to claim 1, further comprising a step E of forming a circuit and removing the second support from the first substrate before the step C. 4.
A step of laminating an electric wiring board on the second support, a step of laminating the first support, a step of peeling the second support, and forming an optical waveguide on the peel surface of the second support The manufacturing method of the photoelectric composite member which has the process to perform in this order.
After laminating the electrical wiring board on the second support and before forming the optical waveguide, a circuit is formed on the electrical wiring board to obtain an electrical wiring board on which an electrical circuit layer is formed. The manufacturing method of the photoelectric composite member of Claim 4.
A substrate with a metal foil after forming a lower clad layer directly or via an adhesive layer on the substrate surface of an electric wiring substrate or after forming a lower clad layer directly or via an adhesive layer on a substrate surface of a metal foil substrate The first step of obtaining an electric wiring board with a lower cladding layer by constructing an electric wiring board by forming a conductive pattern of the metal foil, and forming an optical waveguide by sequentially forming a core pattern and an upper cladding layer on the lower cladding layer A method of manufacturing an optoelectric composite substrate having a second step of construction.
An optical waveguide is constructed by sequentially forming a core pattern and an upper clad layer on the lower clad layer in the first step of forming a lower clad layer directly on the substrate surface of the substrate with metal foil or via an adhesive layer. The manufacturing method of the photoelectric composite board | substrate which has a 2nd process and the 3rd process of forming metal wiring of the board | substrate with metal foil into a conductor pattern, and constructing | assembling an electrical wiring board.
In the step D, the first substrate is formed on the second substrate through a second release layer. In the step E, the second release layer and the second support are formed. The method for manufacturing a wiring board according to claim 3, wherein the wiring board is removed from the first substrate.
9. The wiring board according to claim 1, further comprising a step F of removing the first support and the first release layer from the first substrate after the step C. Production method.
The method of manufacturing a wiring board according to any one of claims 1 to 3, 8, and 9, wherein in the step A, the first substrate is a substrate with a metal layer, and the circuit is formed by patterning the metal foil. .
The method of manufacturing a wiring board according to any one of claims 1 to 3 and 8 to 10, wherein the second substrate is an optical waveguide.
The method for manufacturing a wiring board according to any one of claims 1 to 3 and 8 to 11, wherein the second substrate is a multilayer substrate.
The method for manufacturing a wiring board according to any one of claims 1 to 3 and 8 to 12, wherein the second substrate is an opto-electric hybrid board in which an electric circuit or an electric wiring board is formed on an optical waveguide.
In the step A, the first substrate is an opto-electric hybrid substrate in which an optical waveguide and an electric wiring board are sequentially formed on the substrate X, and the circuit is formed on a surface opposite to the optical waveguide forming surface of the substrate X. The method for manufacturing a wiring board according to any one of claims 1 to 3 and 8 to 13, wherein
Electrical wiring in which an electrical circuit layer is formed by forming a circuit on the electrical wiring board on the release surface of the second support after peeling the second support and before forming an optical waveguide The method for producing an optoelectric composite member according to claim 4, comprising a step of forming a plate.
16. The method for producing an optoelectric composite member according to claim 4, further comprising a step of laminating an electric wiring board on the optical waveguide after forming the optical waveguide.
The light according to any one of claims 4, 5, 15, and 16, further comprising a step of peeling the first support after forming the optical waveguide or after laminating an electric wiring board on the optical waveguide. A method for producing an electrical composite member.
18. The photoelectric composite member according to claim 17, further comprising a step of forming an electric wiring board or an optical waveguide on the peeling surface of the first support after peeling the first support from the electric wiring board. Method.
The method for producing an optoelectric composite member according to any one of claims 4, 5, and 15 to 18, wherein the first support is an electric wiring board or an optical waveguide.
The method for producing an optoelectric composite member according to any one of claims 4, 5, and 15 to 19, wherein the electric wiring board is a single-sided or double-sided metal layered substrate.
21. The method for producing an optoelectric composite member according to claim 4, wherein the electric wiring board is a resin layer with a metal layer on one side or both sides.
The electrical wiring board is an insulating resin layer or substrate, and further includes a step of laminating a metal layer on one or both surfaces of the insulating resin layer or substrate. The manufacturing method of the photoelectric composite member of description.
The electric circuit layer is formed by patterning the electric wiring board using any one of a subtractive method, a semi-additive method, and an additive method. The manufacturing method of the photoelectric composite member as described in any one of Claims 1-3.
The method for producing an optoelectric composite member according to any one of claims 20 to 23, wherein the electric circuit layer or the electric wiring board is laminated in a plurality of layers.
The optical waveguide is formed by forming a lower clad layer on an electric wiring board or a multi-layered electric wiring board, and then laminating a core layer forming resin on the lower clad layer to form a core pattern, The method for producing an optoelectric composite member according to any one of claims 4, 5 and 15 to 24, wherein the method is carried out by forming an upper clad layer on the core pattern.
The optical waveguide is formed by laminating an optical waveguide having a lower clad layer, a core pattern, and an upper clad layer on an electric wiring board or an electric wiring board laminated in a plurality of layers. The method for producing an optoelectric composite member according to any one of 4, 5, and 15 to 25.
The method for producing an optoelectric composite member according to any one of claims 4, 5, and 15 to 26, wherein the electrical wiring board is a rigid wiring board or a flexible wiring board.
The method for producing an optoelectric composite member according to any one of claims 4, 5, and 15 to 27, further comprising a step of forming an optical path conversion mirror in the optical waveguide.
In the second step, a core layer forming resin film is laminated on the lower clad layer to form a core layer, and then a core pattern is formed by exposure and development, and then an upper clad layer forming resin is formed on the core pattern. The manufacturing method of the photoelectric composite board | substrate of Claim 6 or 7 consisting of laminating | stacking a film.
30. The electrical wiring board is constructed according to claim 6 or 29, wherein after forming a resist pattern with an etching resist on a metal foil of a substrate with a metal foil, an electric wiring board is constructed by forming a conductor pattern by etching and then removing the etching resist. A method for manufacturing a photoelectric composite substrate.
After forming a resist pattern with a plating resist on a metal foil of a substrate with a metal foil, a conductor pattern is formed by pattern plating, and then an electric wiring board is constructed by performing plating resist removal and exposed metal foil etching Item 30. A method for producing a photoelectric composite substrate according to Item 6 or 29.
30. The photoelectric composite according to claim 7, wherein the third step comprises forming a resist pattern on the metal foil with an etching resist, forming a conductor pattern by etching, and then removing the etching resist. A method for manufacturing a substrate.
The third step comprises forming a resist pattern on a metal foil with a plating resist, forming a conductor pattern by pattern plating, and then performing plating resist removal and exposed metal foil etching. 29. A method for producing an optoelectric composite substrate according to 29.
34. The method for producing an optoelectric composite substrate according to claim 6, further comprising forming a conductor protective layer on the conductor pattern.
The method for producing a photoelectric composite substrate according to any one of claims 6, 7, and 29 to 34, wherein the photoelectric composite substrate is a flexible type.
An optoelectric composite substrate manufactured using the manufacturing method according to any one of claims 6, 7, and 29 to 35.
An optoelectric composite module using the optoelectric composite substrate according to claim 36.