JP2012155190A - Method for manufacturing optical waveguide and optical waveguide obtained by the same, and method for manufacturing opto-electric composite substrate and opto-electric composite substrate obtained by the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing an optical waveguide and an opto-electric composite substrate with improved visibility of a core pattern, and to provide the optical waveguide and the opto-electric composite substrate obtained by the same.SOLUTION: The present invention provides a method for manufacturing an optical waveguide 1 and an opto-electric composite substrate including a first process for forming a substantially rectangular parallelepiped member made of a chromogenic clad layer 10 having a substantially rectangular parallelepiped shape and a core layer 30 mounted on an upper surface or a lower surface of the chromogenic clad layer 10 and having a substantially rectangular parallelepiped shape and a second process for forming an upper clad layer 40 for covering an upper surface and side surfaces of the substantially rectangular parallelepiped member, and the optical waveguide 1 and the opto-electric composite substrate manufactured by the method.

Description

  The present invention relates to an optical waveguide or a photoelectric composite substrate that has a color-developing clad layer having the same pattern as the core pattern of an optical waveguide and that allows easy visual recognition of the core pattern.

  With the increase in information capacity, development of optical interconnection technology that uses optical signals not only for communication fields such as trunk lines and access systems but also for information processing in routers and servers is underway. 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 the optical transmission line, it is desirable to use an optical waveguide that has a higher degree of freedom of wiring and can be densified than an optical fiber, and among them, an optical waveguide that uses a polymer material that is excellent in processability and economy. Promising.

As this optical waveguide, for example, as described in Patent Document 1, there is an optical waveguide in which a core pattern and an upper cladding are sequentially formed on a lower cladding. However, since the optical waveguide produced by such a manufacturing method is both a core material and a clad, both of which have a purpose of allowing light to pass well and are often transparent materials, the core pattern is actually used as an optical waveguide when being manufactured and processed. It was very difficult to identify where it was. For this reason, when conducting the waveguide manufacturing work, there is a drawback that workability is poor. In addition, when connecting an optical fiber or a semiconductor laser to the completed optical waveguide or mounting various optical elements, there is a drawback that it is difficult to work because it is not known where the core is.
As a method for solving such a problem, there is a method of coloring one or both of the clad and the core as described in Patent Document 2. However, in this method, when the clad is colored, it is necessary to distinguish between the portion with the core pattern and the color shade due to the difference in thickness of the clad, and it is difficult to clearly distinguish the boundary portion. Further, when the core is colored, since the colored portion is a waveguide portion of the optical signal, there is a concern that the optical propagation loss is reduced.

JP 2004-341454 A JP-A-8-75938

  The present invention has been made to solve the above-described problems, and provides an optical waveguide and a photoelectric composite substrate having improved core pattern visibility, and an optical waveguide and an photoelectric composite substrate obtained thereby. For the purpose.

As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by disposing a color-developing clad layer either above or below the core pattern, and have completed the present invention.
That is, the present invention
[1] a first step of forming a substantially rectangular parallelepiped-shaped member comprising a substantially rectangular parallelepiped color-forming clad layer and a substantially rectangular solid-shaped core layer mounted on an upper surface or a lower surface of the color-forming clad layer; A method of manufacturing an optical waveguide, comprising: a second step of forming an upper cladding layer covering an upper surface and side surfaces of a substantially rectangular parallelepiped member;
[2] The method for producing an optical waveguide according to [1], wherein the color-forming clad layer is a multilayer film having one or more layers, and at least one layer of the multilayer film has color-developing properties.
[3] The first step includes a step (A) of laminating the photosensitive color-forming clad layer and the photosensitive core layer on a substrate, and the color-developing property after the step (A). The patterning of the colored layer is performed by simultaneously exposing the clad layer and the core layer of the film and then developing and removing uncured portions of the color-forming clad layer and uncured portions of the core layer. And a step (B) of forming the substantially rectangular parallelepiped member composed of a conductive clad layer and the patterned core layer.
[4] The method for producing an optical waveguide according to [3], wherein the color-forming clad layer is laminated on the base material via an adhesive layer.
[5] The first step is a step of forming a lower clad layer on a substrate and laminating the photosensitive core layer and the photosensitive color-forming clad layer on the lower clad layer ( C) and after step (C), the color-forming clad layer and the core layer are simultaneously subjected to pattern exposure, and then the uncured portion of the color-forming clad layer and the core layer are not cured. And a step (D) of forming the substantially rectangular parallelepiped member comprising the patterned clad layer and the patterned core layer by developing and removing a portion [1] ] Or the manufacturing method of the optical waveguide as described in [2].
[6] The second step includes a step (E) of laminating the upper clad layer from the patterned substantially rectangular parallelepiped shaped member side after the step (B) or (D). The method for producing an optical waveguide according to [3] or [5],
[7] The second step includes, after the step (E), a step (F) of patterning the upper cladding layer to form the patterned upper cladding layer [6] [6] ], The manufacturing method of the optical waveguide according to
[8] An optical waveguide produced by the method according to any one of [1] to [7],
[9] The optical waveguide according to [8], wherein the optical waveguide has an optical path conversion mirror,
[10] A first substantially rectangular parallelepiped-shaped member comprising a substantially rectangular parallelepiped color-forming clad layer and a substantially rectangular solid-shaped core layer mounted on an upper surface or a lower surface of the color-forming clad layer. And a second step of forming an upper clad layer covering the upper surface and side surfaces of the rectangular parallelepiped member,
[11] The photoelectric composite substrate according to [10], wherein the color-developing clad layer is one or more multilayer films, and at least one of the multilayer films has color-development characteristics. Method,
[12] After the step (A ^* ) of laminating the photosensitive color-forming clad layer and the photosensitive core layer on the electrical wiring board, and after the step (A ^* ) Patterning by simultaneously exposing the color-forming clad layer and the core layer to pattern exposure and then developing and removing uncured portions of the color-forming clad layer and uncured portions of the core layer A step (B ^* ) of forming the substantially rectangular parallelepiped member comprising the formed color-developing clad layer and the patterned core layer. The photoelectric composite substrate according to [10], Production method,
[13] The method for producing an optoelectric composite substrate according to [12], wherein the color-forming clad layer is laminated on the electric wiring board via an adhesive layer,
[14] In the first step, a lower cladding layer is formed on the electric wiring board, and the photosensitive core layer and the photosensitive coloring layer are laminated on the lower cladding layer. After the step (C ^* ) and the step (C ^* ), the color-forming clad layer and the core layer are simultaneously subjected to pattern exposure, and then the uncured portion of the color-forming clad layer and the core layer Forming (D ^* ) the substantially rectangular parallelepiped member comprising the patterned chromogenic cladding layer and the patterned core layer by developing and removing an uncured portion. A method for producing an optoelectric composite substrate as set forth in [10],
[15] The second step includes a step (E ^* ) of laminating the upper clad layer from the patterned core layer side after the step (B ^* ) or (D ^* ). [12] or the method for producing a photoelectric composite substrate according to [14],
[16] The second step includes a step (E ^* ) of laminating the upper clad layer from the patterned substantially rectangular parallelepiped shaped member side after the step (B ^* ) or (D ^* ). [12] or [14], a method for producing an optoelectric composite substrate,
[17] The second step includes a step (F ^* ) of patterning the upper cladding layer to form the patterned upper cladding layer after the step (E ^* ). [15] or the method for producing an optical waveguide according to [16],
[18] An optoelectric composite substrate in which the optical waveguide according to [8] or [9] and an electrical wiring board are combined,
[19] An optoelectric composite substrate produced by the method according to any one of [12] to [17],
[20] The photoelectric composite substrate according to [19], wherein the photoelectric composite substrate has an optical path conversion mirror.

  According to the manufacturing method of the present invention, an optical waveguide and an optoelectric composite substrate having a color-forming clad layer on either the upper or lower side of the patterned core layer, and the position of the core pattern being easily visible by the color development of the clad layer are obtained. .

It is a figure explaining an example of the manufacturing method of the optical waveguide of this invention. It is a figure explaining an example of the manufacturing method of the photoelectric composite board | substrate of this invention. It is a figure explaining another example of the manufacturing method of the optical waveguide of the present invention.

The optical waveguide manufacturing method of the present invention forms a substantially rectangular parallelepiped-shaped member comprising a substantially rectangular parallelepiped color-forming clad layer and a substantially rectangular solid-shaped core layer mounted on the upper surface or the lower surface of the color-forming clad layer. The method includes a first step and a second step of forming an upper clad layer that covers an upper surface and a side surface of the substantially rectangular parallelepiped member.
Here, the substantially rectangular parallelepiped means “a rectangular parallelepiped having a rectangular or trapezoidal vertical section”. Note that the cubic shape is a special shape of a rectangle and is included in the rectangle. Depending on the exposure amount and development conditions, the right and left sides of the rectangle in the vertical section or the hypotenuse of the trapezoid may be curved, or the corners of the rectangle or trapezoid may be rounded. To do. Further, even when the thickness and width of the core pattern and the lower clad pattern are partially different, the cross section perpendicular to the wiring forming surface and perpendicular to the wiring direction is rectangular or trapezoidal, so that it is a substantially rectangular parallelepiped in a broad sense.
Color development refers to a phenomenon in which color develops when a substance absorbs electromagnetic radiation. It may be light emission by light emission of absorbed electromagnetic radiation, or a part of electromagnetic radiation may be absorbed and colored in a complementary color of the absorption wavelength, or a combination thereof.
The wavelength of color development may be any wavelength as long as it is detectable, and is preferably electromagnetic radiation in the range from ultraviolet to infrared. In addition, when the color-forming clad material absorbs all the wavelengths of the irradiated electromagnetic radiation, if the color-forming clad material is colored with electromagnetic radiation ranging from ultraviolet to infrared, the black color-forming clad material Can be visually recognized. In this case, it is assumed that the color-forming clad material is colored black.
Further, the color-forming clad layer refers to a clad layer that can be distinguished from the color-forming clad pattern and the surrounding lower clad, upper clad, base material, electric wiring board, and adhesive layer.

(Optical waveguide and photoelectric composite substrate)
An optical waveguide and an optoelectric composite substrate obtained by the method for manufacturing an optical waveguide and an optoelectric composite substrate of the present invention will be described.
In the optical waveguide 1 manufactured according to the present invention, for example, as shown in FIGS. 1D and 3D, a clad 11 containing a color former is provided in the same pattern as the core pattern 31 in order to provide color development. 1 and may have a patterned upper cladding layer 41 or an adhesive layer 70 as shown in FIG. 1 (f) and FIG. 3 (e). The photoelectric composite substrate 2 manufactured according to the present invention is a composite of the electrical wiring board 60 and the optical waveguide, and the optical waveguide 1 is built up on the electrical wiring board 60. Further, as shown in FIG. 2 (i), an adhesive layer 70 may be formed on the electric wiring board 60, and an optical waveguide may be formed on the adhesive layer 70. The adhesive layer 70 may be made of a cladding layer forming material. It may be used.

First Step of Manufacturing Method of Optical Waveguide The first step of the manufacturing method of the optical waveguide 1 according to the present invention is to form the photosensitive color-forming clad layer 10 and the photosensitive core layer 30 on the substrate 50. After the laminating step (A) and the step (A), the color-forming clad layer 10 and the core layer 30 are simultaneously subjected to pattern exposure, and then the uncured portion of the color-forming lower clad layer 10 and A step of forming the substantially rectangular parallelepiped member comprising the patterned color-forming clad layer 11 and the patterned core layer 31 by developing and removing the uncured portion of the core layer 30 (B Or forming a lower clad layer on the substrate 50, and laminating the photosensitive core layer 30 and the photosensitive color-forming clad layer 10 on the lower clad layer ( C) and the color development after step (C) The clad layer 10 and the core layer 30 are simultaneously subjected to pattern exposure, and then the uncured portion of the color-forming clad layer 10 and the uncured portion of the core layer 30 are developed and removed. It is preferable to include a step (D) of forming the substantially rectangular parallelepiped member comprising the formed color-forming clad layer 11 and the patterned core layer 31.
In addition, in the step (A), the color-forming clad layer 10 may be laminated on the base material 50 via an adhesive layer 70 as necessary.
Hereinafter, the patterned color-forming clad layer is referred to as “color-forming clad pattern”, and the patterned core layer is referred to as “core pattern”.

Second Step of Manufacturing Method of Optical Waveguide The second step following the first step according to the present invention is the step of (B) or (D) in the first step, followed by the core pattern 31 and the coloring clad pattern. Preferably, the method includes a step (E) of laminating the upper clad layer 40 from the side of the substantially rectangular parallelepiped member consisting of 11, and after this step (E), the upper clad layer is exposed to the whole surface, and the exposed upper clad layer It is further preferable to include any step (F) of the step of forming (F ₁ ) and the step of forming the patterned upper clad layer by pattern exposure of the upper clad layer (F ₂ ).
Hereinafter, the patterned upper clad layer is referred to as an “upper clad pattern”.

Each process of the manufacturing method of the optical waveguide of this invention is demonstrated based on drawing below. FIG. 1 is a diagram illustrating an example of a method for manufacturing an optical waveguide 1 according to the present invention.
Process (A)
First, as shown in FIG. 1A, an auxiliary bonding clad 71 to be an adhesive layer 70 is laminated on the upper surface of a carrier film 51 to be a base material 50 as desired. At this time, the base material 50 with the adhesive layer 70 may be used. Next, the color-forming clad layer 10 is laminated on the upper surface of the adhesion auxiliary clad 71 (FIG. 1B). However, if the carrier film 51 and the color-forming clad layer 10 have sufficient adhesion, the color-forming clad layer 10 may be directly laminated on the upper surface of the carrier film 51. The method for laminating the color-forming clad layer 10 is not particularly limited, and may be a known method. For example, a coating composition for forming the color-forming clad layer 10 or a resin film for forming the color-forming clad layer 10 is used. What is necessary is just to form by a laminate.
Next, as shown in FIG. 1C, a core layer 30 is laminated on the upper surface of the color-forming clad layer 10. The method for stacking the core layer 30 is not particularly limited and may be a known method.
As a preferred method of the step (A), for example, a material for forming the color-forming clad layer 10 is applied onto the substrate 50 or the adhesive layer 70 by spin coating or the like, prebaked, and then the color-forming clad layer 10. The core layer 30 can be formed by applying a material for forming the core layer 30 by spin coating or the like.
Further, after forming the color-forming clad layer 10 forming resin film and the core layer 30 forming resin film by laminating or the like, they are bonded to the upper surface of the base material 50 or the adhesive layer 70, or the base material 50 or adhesive The color developing clad layer 10 forming resin film and the core layer 30 forming resin film may be sequentially bonded to the upper surface of the layer 70. Here, as a method of forming the color-forming clad layer 10 forming resin film used for laminating, for example, the color-forming clad layer forming resin composition is dissolved in a solvent, applied to the carrier film 51, and the solvent is added. It can be easily manufactured by removing. Similarly, the resin film for forming the core layer 30 used for laminating can be easily manufactured by dissolving the resin composition for forming the core layer 30 in a solvent, applying it to the carrier film 51, and removing the solvent.

Process (B)
Next, the laminate of the resulting color-forming clad layer 10 and the core layer 30 is subjected to pattern exposure at the same time, and then the uncured portion of the color-forming clad layer 10 and the uncured portion of the core layer 30 Is removed by development to form a substantially rectangular parallelepiped member composed of a patterned core layer (core pattern) 31 with a color-forming clad pattern 11 shown in FIG.
When the auxiliary adhesion cladding layer 71 is used as the adhesive layer 70 on the substrate 50, the adhesion auxiliary cladding layer 71 is usually left on the substrate 50 without being subjected to pattern exposure, but may be subjected to pattern exposure as necessary. Also good.

Process (C)
First, the lower clad layer 20 is laminated on the upper surface of the carrier film 51 to be the base material 50 and cured. At this time, the lower auxiliary cladding layer 20 may use the auxiliary adhesion cladding layer 71. Usually, the lower clad layer 20 is left on the substrate 50 without being subjected to pattern exposure, but may be subjected to pattern exposure as needed to form a lower clad pattern.
Next, the core layer 30 is laminated on the upper surface of the lower cladding layer 20. The method for laminating the core layer is not particularly limited, and may be a known method. For example, the core layer may be formed by applying a resin composition for forming the core layer 30 or laminating a resin film for forming the core layer 30.
Next, the color-forming clad layer 10 is laminated on the upper surface of the core layer 30. The lamination method of the color-forming clad layer 10 is not particularly limited and may be a known method.
As a preferred method of the step (C), for example, a material for forming the core layer 30 is applied onto the lower cladding layer 20 by spin coating or the like, prebaked, and then the coloring layer 10 is formed on the upper surface of the core layer 30. This material can be formed by applying the material by spin coating or the like.
Further, after forming the color-developing clad layer 10 forming resin film and the core layer 30 forming resin film by laminating or the like, they are bonded to the upper surface of the lower clad layer 20 from the core layer 30 side, or the lower clad layer The resin film for forming the core layer 30 and the resin film for forming the color-developing clad layer 10 may be sequentially bonded to the upper surface of 20. Here, a resin film for forming a color-forming clad layer 10 used for laminating, for example, a resin composition for forming a color-forming clad layer 10 is dissolved in a solvent, applied to the carrier film 51, and easily removed by removing the solvent. Can be manufactured. Similarly, the resin film for forming the core layer 30 used for laminating can be easily manufactured by dissolving the resin composition for forming the core layer 30 in a solvent, applying it to the carrier film 51, and removing the solvent.

Process (D)
Next, the laminated body of the obtained core layer 30 and the color-forming clad layer 10 is simultaneously subjected to pattern exposure, and then the uncured portion of the core layer 30 and the uncured portion of the color-forming clad layer 10 Is removed by development to form a substantially rectangular parallelepiped member composed of the core pattern 31 with the color-developing clad pattern 11. As a method for developing and removing at this time, the core layer 30 and the chromogenic cladding layer 10 may be patterned with the same developer, and the core layer 30 and the chromogenic cladding layer 10 may be stepped using different developers. It may be patterned.

Process (E)
Next, as shown in FIG. 1 (e), the color-forming clad pattern 11 and the core pattern 31, which are substantially rectangular parallelepiped members, are formed from the core pattern side from the core pattern side in the case of step (A), and the color development. The upper cladding layer 40 is laminated so as to cover the side surface of the conductive cladding pattern 11. In the case of the step (C), the upper clad layer 40 is laminated from the color-forming clad pattern 11 side so as to cover the upper and side surfaces of the color-forming clad pattern 11 and the side surface of the core pattern 31. In the present invention, the method of forming the upper clad layer 40 is not particularly limited, and for example, the upper clad layer 40 may be formed by applying a resin composition for forming the upper clad layer 40 or laminating a resin film for forming the upper clad layer.
In the case of coating, the method is not limited. For example, a resin composition containing the components described later may be coated by a conventional method. The resin film for forming the upper clad layer 40 used for laminating is, for example, dissolved in a solvent in the resin composition for forming the upper clad layer 40 in the same manner as the resin film for forming the clad layer, and applied to the carrier film 51. It can be easily produced by removing the solvent. FIG. 1E shows a case where the resin film for forming the upper clad layer 40 with the carrier film 51 is used. If desired, the carrier film 51 may be left on the upper surface of the upper clad layer 40 for the purpose of protecting the surface of the upper clad layer 40. May be removed. Thus, the optical waveguide 1 is obtained.

Process (F)
After the step (E), the entire surface of the upper cladding layer is exposed to form an exposed upper cladding layer 40 (F ₁ ), and the upper cladding layer 40 patterned by pattern exposure of the upper cladding layer 40. More preferably, any step (F) of the step (F ₂ ) of forming 40 is included.
In the optical waveguide 1 obtained by the method of the present invention, as shown in FIG. 1 (d), since the color-forming clad pattern 11 is formed with the same pattern as the core pattern 31, the color development of the color-forming clad pattern 11 is detected. By doing so, it becomes possible to visually recognize the core pattern 31.

The optoelectric composite substrate 2 of the present invention is obtained by combining the optical waveguide 1 obtained by the above-described method of the present invention and the electric wiring board 60. The optical waveguide 1 is directly formed on the electric wiring board 60. Is preferred.
That is, the preferable method for manufacturing the optoelectric composite substrate 2 of the present invention is a substantially rectangular parallelepiped color-forming clad layer 10 on the electric wiring board 60, and a substantially mounted upper or lower surface of the color-forming clad layer 10. Including a first step of forming a substantially rectangular parallelepiped member composed of a rectangular parallelepiped core layer 30 and a second step of forming an upper clad layer 40 covering the upper surface and side surfaces of the substantially rectangular parallelepiped member. To do.

First Step of Manufacturing Method of Photoelectric Composite Substrate The first step according to the method of manufacturing the photoelectric composite substrate 2 of the present invention is the photosensitive coloring layer 10 and the photosensitive clad layer 10 on the electric wiring board 60. and step (a ^*) of laminating said core layer 30, after the step (a ^*), and simultaneously pattern exposing the cladding layer 10 and the core layer 30 of the chromogenic, then cladding layer 10 of the chromogenic Developing and removing the uncured portion of the core layer 30 and the uncured portion of the core layer 30 to form the substantially rectangular parallelepiped member comprising the color-forming clad pattern 11 and the core pattern 31 (B ^* ); Preferably, the lower clad layer 20 is formed on the electric wiring board 60, and the photosensitive core layer 30 and the photosensitive color-developing clad layer 10 are laminated on the lower clad layer 20. step (C ^*) , After the step (C ^*), and simultaneously pattern exposing the cladding layer 10 and the core layer 30 of the chromogenic, then cured portion and the core layer 30 is not cured of the cladding layer 10 of the chromogenic A step (D ^* ) of forming the substantially rectangular parallelepiped member composed of the patterned color-forming clad layer 10 and the patterned core layer 30 by developing and removing the unexposed portion. preferable.
As a method for developing and removing at this time, the core layer 30 and the chromogenic cladding layer 10 may be patterned with the same developer, and the core layer 30 and the chromogenic cladding layer 10 may be stepped using different developers. It may be patterned.
In addition, in the step (A ^* ), the color-forming clad layer 10 may be laminated on the base material 50 with an adhesive layer 70 as necessary.

Second step of manufacturing method of optoelectric composite substrate The second step following the first step according to the present invention is the step (B ^* ) or the step (D ^* ) in the first step, the core pattern 31 side, Alternatively, it is preferable to include a step (E ^* ) of laminating the upper clad layer 40 from the substantially rectangular parallelepiped member made of the core pattern 31 and the chromogenic clad pattern 11, and after this step (E ^* ), the upper clad layer Either the step of exposing the entire surface to form an upper clad layer after exposure (F ₁ ^* ) or the step of pattern exposing the upper clad layer to form the patterned upper clad layer (F ₂ ^* ) More preferably, the step (F ^* ) is included.

Each step of the method for manufacturing an optoelectric composite substrate of the present invention will be described below with reference to the drawings. FIG. 2 is a diagram for explaining an example of a method for producing the photoelectric composite substrate 2 of the present invention.
Process (A ^* ) to (D ^* )
In the method shown in FIG. 2, the carrier film 51 shown in FIG. 1A is changed to the electric wiring board 60, and the lower clad layer 20 is laminated on the upper surface of the electric wiring board 60 as in FIG. Next, a substantially rectangular parallelepiped member made up of the core pattern 31 and the color-forming clad pattern 11 is formed on the upper surface of the lower cladding layer 20, and the upper surface and side surfaces of the approximately rectangular parallelepiped member are covered with the upper cladding layer 40, as in FIG. Further, the upper clad pattern 41 is formed to obtain the optoelectric composite substrate 2. Further, when the optical waveguide 1 is formed in the same manner as in FIG. 1 using the carrier film 51 in FIG. 1A as the electric wiring board 60, the light in which the positions of the color-forming clad pattern 11 and the core pattern 31 in FIG. An electric composite substrate can be obtained. As shown in FIG. 2G, the optoelectric composite substrate 2 obtained by the method of the present invention has the same pattern as the core pattern 31 and the chromogenic cladding pattern 11 is formed. By detecting the color development, the core pattern 31 can be visually recognized.

Hereinafter, each component of the optical waveguide and the photoelectric composite substrate will be described.
(Clad layer)
Hereinafter, the color-forming clad layer 10, the lower clad layer 20, and the upper clad layer 40 used in the present invention will be described. As the lower clad layer 10 and the upper clad layer 40, a clad layer forming resin composition or a clad layer forming resin film can be used. The color developability of the color developable clad layer 10 can be obtained by adding a color former to the composition of the lower clad layer 10 and the upper clad layer 40. The color former will be described later in the section (Color former for color-forming clad layer).
The resin composition for forming a cladding layer used in the present invention is not particularly limited as long as it is a resin composition having a lower refractive index than that of the core layer 30 to be used and curable by light, and a photosensitive resin composition is preferably used. Can be used. More preferably, the resin composition for forming a clad layer is preferably composed of a resin composition containing (a) a carrier polymer, (b) a photopolymerizable compound, and (c) a photopolymerization initiator.

  The carrier polymer (a) 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 carrier polymers may be used alone or in combination of two or more. Of the carrier polymers exemplified above, the main chain preferably has an aromatic skeleton, and particularly preferably a phenoxy resin, from the viewpoint of high heat resistance. From the viewpoint of three-dimensional crosslinking and improving heat resistance, an epoxy resin, particularly a solid epoxy resin at room temperature (25 ° C.) is preferable. Furthermore, the compatibility with the photopolymerizable compound (b) described in detail later is important for ensuring the transparency of the resin composition for forming a cladding layer. From this point, the phenoxy resin and (meth) Acrylic resin 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.

  As an epoxy resin solid at room temperature (25 ° C.), for example, “Epototo YD-7020, Epototo YD-7019, Epototo YD-7007” (all trade names) manufactured by Toto Chemical Co., Ltd., Japan Epoxy Resins Co., Ltd. Examples thereof include bisphenol A type epoxy resins such as “Epicoat 1010, Epicoat 1009, Epicoat 1008” (all trade names).

Next, (b) the photopolymerizable compound is not particularly limited as long as it is polymerized by light irradiation, and a compound having an ethylenically unsaturated group in the molecule or two or more epoxy groups in the molecule. And the like.
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 dimethylaminobenzoic acid. Of the above compounds, aromatic ketones and phosphine oxides are preferable from the viewpoint of improving the transparency of the cladding layer.
These (c) photopolymerization initiators can be used alone or in combination of two or more.

(A) It is preferable that the compounding quantity of a carrier polymer shall be 5-80 mass% in the total amount of (a) component and (b) component. Moreover, it is preferable that the compounding quantity of (b) photopolymerizable compound shall be 95-20 mass% in the total amount of (a) and (b) component.
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 (a) component is 80% by mass or less and the (b) component is 20% by mass or more, (a) the carrier polymer can be easily entangled and cured, and the optical waveguide 1 is formed. Furthermore, the pattern forming property is improved and the photocuring reaction proceeds sufficiently. From the above viewpoint, as the blending amount of the component (a) and the component (b), in the total amount of the components (a) and (b), the component (a) is 10 to 85% by mass, and the component (b) is 90 to 15% by mass. % Is more preferable, (a) 20-70 mass% of component, (b) 80-30 mass% of component is still more preferable.
(C) It is preferable that the compounding quantity of a photoinitiator shall be 0.1-10 mass parts with respect to 100 mass parts of total amounts of (a) component and (b) component. 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. Further, when used as the optical waveguide 1, 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, it is more preferable that the amount of the (c) photopolymerization initiator is 0.2 to 5 parts by mass.

Regarding the thickness of the lower cladding layer 20, the thickness after drying is preferably in the range of 5 to 500 μm. 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.
The thickness of the upper clad layer 40 may be the same as or different from the thickness of the lower clad layer 20, but in order to embed a substantially rectangular parallelepiped member, the thickness of the upper clad layer 40 is set to be a color developing clad. It is preferable that the thickness of the layer 10 and the thickness of the core layer 30 be larger than the total thickness.
Regarding the thickness of the color-forming clad layer 10, when the lower clad layer 10 and the adhesion-assisting clad layer 71 are used as the adhesive layer 70 or when the color-forming clad layer 10 is formed on the core layer 30, Although there is no restriction | limiting of thickness, it is the thickness after drying, and the range of 1-500 micrometers is preferable. When the thickness is 500 μm or less, it is easy to uniformly control the film thickness. Further, when the color-developing clad layer 10 is directly formed on the substrate 50 or the electric wiring board 60, a clad thickness necessary for light confinement can be secured when the thickness is 5 μm or more. Further, it is sufficient that the core layer 30 is exposed to a film thickness that allows the color-forming clad layer 10 to be cured. From this viewpoint, the color-forming clad layer 10 has a thickness of 5 to 50 μm. More preferably, it is the range.

(Coloring agent for coloring layer)
The color-forming clad layer 10 is obtained by adding a color former to the composition of the lower clad layer 20, the upper clad layer 40, and the adhesion auxiliary clad layer 71. The color former is roughly classified into a light emission type, a light absorption type, and a combination type. Hereinafter, a color former for imparting color developability to the color developable cladding layer 10 will be described.
(Light-emitting color former)
The type of light-emitting color former introduced into the color-forming clad is not particularly limited, and examples thereof include fluorescent agents, phosphorescent agents, phosphorescent agents, fluorescent or phosphorescent photopolymerization initiators. , Fluorescent or phosphorescent photosensitizers, and combinations of two or more thereof. In particular, when an ultraviolet lamp is used to color the exposure light source and the cladding, it is preferable to use a fluorescent agent, a phosphorescent agent, a phosphorescent agent, a fluorescent or phosphorescent photosensitizer, and a light conversion type to be introduced. The amount of the ultraviolet absorber may be in a range that does not affect the light propagation loss.

(Light absorbing color former)
The type of light-absorbing color former to be introduced into the color-forming clad is not particularly limited, but examples include thermal energy conversion type ultraviolet absorbers, colorants, and combinations of two or more of them. It is done. In the case of a heat energy conversion type ultraviolet absorber, if the adhesive layer, the lower cladding layer, the base material, and the electric wiring board have a light emitting property due to ultraviolet rays, it is possible to develop a black color. If it is a coloring agent, a position can be visually recognized by light emission and coloration of the clad in a visible light region. The amount of the light absorbing color former to be introduced may be in a range that does not affect the light propagation loss.
(Combined color former)
The light-emitting color former and the light-absorbing color former may be appropriately combined for the purpose of adjusting the visibility. The amount of the light-emitting and light-absorbing colorants to be introduced depends on the light propagation loss. It may be in a range without influence.

(Core layer forming resin composition and core layer forming resin film)
As the resin composition for forming the core layer 30, the core pattern 31 is designed to have a higher refractive index than the lower cladding layer 20, the adhesion assisting cladding layer 71, the coloring clad layer 10, and the upper cladding layer 40. Thus, a resin composition capable of forming the core pattern 31 can be used, and a photosensitive resin composition is preferable. Specifically, it is preferable to use the same resin composition as that used in the resin composition for forming a clad layer.
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 forming the core layer 30 used for lamination will be described in detail.
The resin film for forming the core layer 30 can be easily manufactured by dissolving the resin composition in a solvent, applying the resin composition to the lower clad layer 20 or the color-forming clad layer 10, 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 content concentration in the resin composition solution is usually preferably 30 to 80% by mass.

  The thickness of the resin film for forming the core layer 30 is not particularly limited, and the thickness of the core layer 30 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, and when the thickness is 100 μm or less, the light receiving / emitting after the optical waveguide is formed. In coupling with an element or an optical fiber, there is an advantage that coupling efficiency is improved. From the above viewpoint, the thickness of the film is preferably in the range of 30 to 70 μm.

(Carrier film)
The material of the carrier film 51 used in the manufacturing process of the clad layer forming resin film is not particularly limited, and various materials can be used. For example, an FR-4 substrate, a polyimide substrate, a semiconductor substrate, a silicon substrate, a glass substrate, or the like can be used, which may be a flexible material or a non-flexible hard material.
Moreover, a flexible photoelectric composite member can be obtained by using a flexible material for the carrier film 51. 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 μm to 10 mm, and preferably 5 to 250 μm when flexibility is required. If it is 5 μm or more, there is an advantage that toughness can be easily obtained, and if it is 250 μm or less, sufficient flexibility can be obtained.

  Of the carrier film 51, the carrier film 51 used in the manufacturing process of the core layer 30 or various clad layer forming resin composition coatings is also peeled off later from the core layer 30 or various clad layer forming resin composition coatings. Suitable examples include polyesters such as polyethylene terephthalate, polypropylene, and polyethylene, from the viewpoint of being easy to do and having heat resistance and solvent resistance. In this case, the thickness of the carrier film 51 is preferably 5 to 50 μm. If it is 5 μm or more, there is an advantage that the strength as the carrier film 51 is easily obtained, and if 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 carrier film 51 used in the coating film production process is more preferably in the range of 10 to 40 μm, and particularly preferably 15 to 30 μm.

(Electric wiring board)
The electric wiring board 60 used in the present invention is not particularly limited, and various electric wiring boards 60 used for the photoelectric composite substrate 2 can be used, for example, an insulating substrate for an electric wiring board, Alternatively, the wiring board may be an insulating substrate having electrical wiring formed thereon, or a multilayer wiring board. When there is no adhesive force between the electrical wiring board 60 and the color-forming clad layer 10, the lower clad layer 20, and the upper clad layer 40, a physical roughening treatment or a chemical bonding film is formed on the surface of the electrical wiring board. May be appropriately performed. Further, an adhesive layer 70, for example, an auxiliary adhesion cladding layer 71 may be provided on the electric wiring board 60.

(Adhesive layer)
The method for adhering the electric wiring board 2 or the base material 50 and the color-developing clad layer 10 having a weak adhesive force is not particularly limited. However, when laminating via the adhesive layer 70, an adhesive or An adhesive film material can be used, and preferred examples of the material include double-sided tape, hot melt adhesive, UV or thermosetting adhesive.
Preferable examples of the adhesive material include prepregs, build-up materials, thermosetting adhesives, photo-curing adhesives, and laminates obtained by combining two or more thereof. Adhesion when an optical signal passes through the adhesive layer 70 requires an adhesive layer 70 with a high transmittance. In this case, the material of the adhesive layer 70 is not particularly limited, but various cladding layers or resins for forming 30 It is more preferable to use the composition, the resin composition for forming the core layer 30 or the adhesive described later.
Further, an adhesive or adhesive film having a high transmittance is required for adhesion of a portion through which an optical signal is transmitted, and the material of the adhesive or adhesive film is not particularly limited, but is described in (PCT / JP2008 / 05465). It is more preferable to use an adhesive auxiliary clad layer 71 that can be distinguished from an adhesive film of FIG.
Although the thickness of the contact bonding layer 70 does not have limitation in particular, it is preferable that it is 0.1-100 micrometers, and it is more preferable that it is 0.1-50 micrometers.

(Adhesive for adhesive layer 70)
Examples of the adhesive for the adhesive layer 70 include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, polyfunctional epoxy resin, amine type epoxy resin, amine type epoxy resin and the like. One or more of the resins (p), polyfunctional phenols (particularly novolac-type or resol-type phenolic resins), amines, imidazole compounds, acid anhydrides, organophosphorus compounds and their halides, One or more curing agents (q) such as polyamide, polysulfide, boron trifluoride (q), acrylic copolymer, acrylic rubber, acrylonitrile butadiene rubber, silicone rubber, silicone resin, silicone modified polyamideimide Silicone modified resin such as One or more of polymer compounds such as polyurethane, polyimide, polyimide amide (r), aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide One or more fillers such as aluminum oxide, crystalline silica, amorphous silica, acrylonitrile butadiene rubber filler, silicone rubber filler (s), and tertiary amines, imidazoles, quaternary ammonium salts, etc. The adhesive containing 1 type (s) or 2 or more types (t) of this hardening accelerator is preferable.
The blending ratio of the component (p) and the component (q) is preferably 0.70 / 0.30 to 0.30 / 0.70 in terms of the equivalent ratio of epoxy equivalent and hydroxyl equivalent, [{(p) Component + (q) component} / (r) component] ratio (parts by mass) is preferably 0.24 to 1.0, and {part (p) component + (q) component} is 100 parts by mass. The component (s) is preferably 1 to 50 parts by mass and the component (t) is 5.0 parts by mass or less. Moreover, you may mix | blend a coupling agent, ion trapping agents, etc., such as a silane type, a titanium type, and aluminum type, as needed.

(Adhesive auxiliary cladding layer)
The material of the adhesion auxiliary clad layer 71 used as the adhesion layer 70 is not particularly limited, and various materials can be used. However, the lower clad layer 20, the upper clad layer 40, and the color forming lower clad layer 10 forming resin. Compositions are preferred.
The thickness of the adhesion auxiliary clad 71 is not particularly limited, but if it is 1 to 50 μm, sufficient adhesion to the lower clad layer 10 or the lower clad pattern 11 can be secured.

(Composite method of electrical wiring board and optical waveguide)
The method of combining the electrical wiring board 60 and the optical waveguide 1 to form the photoelectric wiring board 2 is not particularly limited, and various methods can be used. For example, a method in which the optical waveguide 1 and the electrical wiring board 60 manufactured in advance are bonded together via the adhesive layer 60, a build-up formation method in which the clad layer and the core layer 30 are stacked on the electrical wiring board 60 manufactured in advance, For example, a method of building up the electrical wiring 60 on the optical waveguide 1 manufactured in advance may be used.

(Exposure method for core pattern with lower clad pattern)
The exposure method of the core pattern 31 with the lower clad pattern 11 that is a substantially rectangular parallelepiped member is not particularly limited, and may be either a negative type in which an exposed part remains as a pattern or a positive type in which an unexposed part remains as a pattern. You may decide by the property of the resin composition for clad layer formation and the resin composition for core layer formation to be used. However, from the viewpoint of simultaneously exposing the color-forming clad pattern 11 and the core pattern 31, the lower clad layer 10 and the core layer 30 need to be unified to a negative type or a positive type.

(Exposure method of upper clad layer or upper clad pattern)
The exposure method of the upper cladding layer 40 or the upper cladding pattern 41 is not particularly limited, and may be the entire surface exposure of the upper cladding layer 40 or the pattern exposure for forming the upper cladding pattern 41. When the adhesion between the color-forming clad pattern 11 and the core pattern 31 is weak, the upper clad pattern 41 is formed so as to partially remove the upper clad layer 40 in the gap between the core pattern 31 and the core pattern 31, thereby forming the upper clad layer 40. It is possible to suppress the peeling between the color-forming clad pattern 11 and the core pattern 31 due to thermal contraction.

EXAMPLES The present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
[Production of resin film for clad layer formation]
(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) As a photopolymerization initiator, triphenylsulfonium hexafluoroantimonate salt (trade name: SP-170, Asahi Denka Kogyo Co., Ltd.) 2 parts by mass, 40 parts by mass 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. Degassing under reduced pressure for 15 minutes under the condition of 50 mmHg gave a resin varnish A for forming a cladding layer.
Next, with respect to 100 parts by mass of (A) + (B) + (C), (D) color former (luminescent photosensitizer) (trade name: SP-100, manufactured by Asahi Denka Kogyo Co., Ltd.) 0.4 parts by mass was prepared, and a resin varnish B for forming a clad layer was obtained in the same manner as described above.
Next, (D) color former (light absorber) (trade name: LA-36, manufactured by ADEKA Corporation) 1.0 part by mass with respect to 100 parts by mass of (A) + (B) + (C) A clad layer forming resin varnish C was obtained by the same method as described above.
The coating varnish A, B, C for clad layer formation obtained above is applied to a release PET film (trade name: PUREX A31, Teijin DuPont Films, Inc., thickness: 25 μm) as the carrier film 51. (Multicoater TM-MC, manufactured by Hirano Techseed Co., Ltd.), dried at 80 ° C. for 10 minutes, then at 100 ° C. for 10 minutes, and then released as a protective film (Purex A31, Teijin) DuPont Film Co., Ltd., thickness: 25 μm) was attached so that the release surface was on the resin side, and resin films A, B, and C for forming a clad layer were 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 film thickness after curing is 15 μm for the color-forming clad layer 10 and the lower clad layer. 20 was adjusted to 25 μm, the upper cladding layer 40 was adjusted to 70 μm, and the auxiliary adhesion cladding layer 71 was adjusted to 15 μm.
Hereinafter, the phrase “color-forming clad layer 10” used in Examples or Comparative Examples is used as a meaning of a clad layer used for a clad layer portion having a color-forming property in terms of structure.

[Production of resin film for core layer formation]
(A) As a base polymer, 26 parts by mass of 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: yl (Cure 2959, manufactured by Ciba Specialty Chemicals) 1 part by weight, except that 40 parts by weight of propylene glycol monomethyl ether acetate was used as the organic solvent, the resin varnish D for forming the core layer was formed 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 D 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.

Example 1
[Production of optical waveguide]
UV exposure is performed on the clad resin surface of the carrier film 51 with the adhesion auxiliary clad layer 71 using the resin varnish A for clad layer formation obtained above in which the adhesive layer 70 is formed on the PET film substrate 50. An ultraviolet ray (wavelength 365 nm) was irradiated at 1.5 J / cm ² using a machine (manufactured by Oak Manufacturing Co., Ltd., EXM-1172), and then dried at 80 ° C. for 12 minutes (see FIG. 1A).
Next, the resin surface of the color-forming clad layer 10 forming resin film using the clad layer forming resin varnish B obtained above is placed on the adhesion auxiliary clad layer 71 with a roll laminator (HLM, manufactured by Hitachi Chemical Technoplant Co., Ltd.). -1500) under the conditions of a pressure of 0.4 MPa, a temperature of 50 ° C., and a laminating speed of 0.2 m / min (see FIG. 1B). Next, the PET film which is the carrier film 51 of the color forming clad layer 10 forming resin film is peeled off, and the resin surface of the core layer 30 forming resin film is placed on the color forming clad layer 10 with a roll laminator (Hitachi Chemical Technoplant). HLM-1500) was used for lamination under the conditions of a pressure of 0.4 MPa, a temperature of 50 ° C., and a lamination speed of 0.2 m / min (see FIG. 1C). Next, through a negative photomask having a width of 50 μm, ultraviolet rays (wavelength 365 nm) are irradiated with 0.8 J / cm ² with the above-described ultraviolet exposure machine, and the color-forming clad pattern 11 and core pattern 31 are photocured, and then 80 Heating was performed after exposure for 5 minutes at ° C. Thereafter, the PET film which is the carrier film 51 of the resin film for forming the core layer 30 is peeled off, and the color developability using a developer (propylene glycol monomethyl ether acetate / N, N-dimethylacetamide = 7/3, mass ratio). The clad layer 10 and the core layer 30 were developed to obtain a color-forming clad pattern 11 and a core pattern 31. Then, it wash | cleaned using the washing | cleaning liquid (isopropanol), and heat-dried at 100 degreeC for 10 minute (refer FIG.1 (d)). Next, the visibility of the core pattern 31 with the color-forming clad pattern 11 was confirmed with a fluorescence microscope (magnification 200) using 365 nm ultraviolet light from the core pattern 31 side. The results are shown in Table 1.
Next, the resin film for forming the upper clad layer 40 using the resin varnish A for forming the clad layer is vacuum pressure laminator (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd.), pressure 0.4 MPa, temperature 50 Lamination was performed under the conditions of a temperature of 30 ° C. and a pressurization time of 30 seconds (see FIG. 1E). Next, a part of 50 μm around the core pattern 31 and the color-forming clad pattern 11 is exposed through the negative photomask for the upper clad pattern with the same pattern as the negative photomask for forming the core pattern and having only the line width of 150 μm. In this way, ultraviolet rays (wavelength 365 nm) were irradiated with 3.0 J / cm ² , and then after exposure for 12 minutes at 80 ° C., heating was performed. Thereafter, the PET film which is the carrier film 51 of the resin film for forming the upper clad layer 40 was peeled off, and the upper clad layer 40 was developed using a developer (isopropanol) to obtain an upper clad pattern 41. Then, it wash | cleaned using the washing | cleaning liquid (isopropanol), and heat-dried at 100 degreeC for 10 minute (s). Next, the upper clad pattern 41 was cured by heat treatment at 160 ° C. for 1 hour, and the optical waveguide 1 was manufactured (see FIG. 1F).

(Formation of optical path conversion mirror)
A 45 ° mirror portion was formed from the upper clad pattern 41 side of the obtained optical waveguide 1 using a dicing saw (DAC552, manufactured by DISCO Corporation).
Next, the visibility of the core pattern 31 with the color-forming clad pattern 11 was confirmed with a fluorescence microscope (magnification 200) using 365 nm ultraviolet light from the upper clad pattern 41 side. The results are shown in Table 1.

Examples 2-8
In Example 1, the optical waveguide 1 was produced in the same manner except that the varnish shown in Table 1 was used as the varnish used for the adhesion auxiliary clad layer 71, the coloring clad layer 10 and the upper clad layer 40. Table 1 shows the results of confirming the visibility of the core pattern 31 after development and the visibility after forming the upper clad, as in Example 1.
In Examples 7 and 8, the core pattern was black.

Example 9
In Example 1, before laminating the color-forming clad layer 10 using the clad layer-forming resin varnish B on the adhesion auxiliary clad layer 71, the color-forming clad layer using the clad layer-forming resin varnish A was further added. The optical waveguide 1 was produced in the same manner except that the laminate was changed to a two-color coloring clad layer 10. Table 1 shows the results of confirming the visibility of the core pattern 31 after development and the visibility after forming the upper clad, as in Example 1.

Comparative Examples 1-6
In Example 1, the optical waveguide 1 was produced in the same manner except that the varnish shown in Table 1 was used as the varnish used for the adhesion auxiliary clad layer 71, the coloring clad layer 10 and the upper clad layer 40. Table 1 shows the results of confirming the visibility of the core pattern 31 after development and the visibility after forming the upper clad, as in Example 1.
In Comparative Example 6, the color-forming clad layer 10 was not formed.

Example 10
(Production of adhesive layer described in PCT / JP2008 / 05465)
The adhesive layer 70 described in PCT / JP2008 / 05465 was produced. That is, (a) YDCN-703 (trade name, manufactured by Toto Kasei Co., Ltd., cresol novolac 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 reduction 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 weight of γ-mercaptopropyltrimethoxysilane) and 3.2 parts by weight of NUC A-1160 (trade name, γ-ureidopropyltriethoxysilane manufactured by Nihon 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, weight average molecular weight of 800,000 manufactured by Nagase ChemteX Corporation) 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 and mixed, and vacuum degassed. This adhesive varnish was applied as a carrier film onto a 75 μm-thick polyethylene terephthalate (PET) film (Purex A31) subjected to a release treatment, dried by heating at 140 ° C. for 5 minutes, and then as a protective film, a 25 μm release mold. The treated polyethylene terephthalate (PET) film (Purex A31) was attached so that the release surface was on the resin side, and an adhesive layer 70 was obtained.
Hereinafter, description will be made on the assumption that the adhesive layer 70 is in a state immediately after the protective film is peeled off immediately before use.

(Production of electrical wiring board)
A photosensitive dry film on a copper foil of 150 mm square polyimide with a single-sided copper foil (trade name: Upicel N, manufactured by Ube Nitto Kasei Kogyo Co., Ltd., copper foil thickness: 9 μm, polyimide thickness 12.5 μm) as the base material 50 Using a roll laminator (HLM-1500, manufactured by Hitachi Chemical Technoplant Co., Ltd.), a resist (trade name: Photec, manufactured by Hitachi Chemical Co., Ltd., thickness: 25 μm), pressure 0.4 MPa, temperature 110 ° C., laminating speed 0. The film was applied under the condition of 4 m / min, and then UV (wavelength 365 nm) was applied to 120 mJ / mm via a negative photomask having 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.). Irradiate cm ² and unexposed photosensitive dry film resist was diluted with 0.1-5 wt% sodium carbonate at 35 ° C. Removed with thin solution. Thereafter, using a ferric chloride solution, the exposed copper foil of the photosensitive dry film resist was removed by etching, and exposure was performed using a 1-10 wt% sodium hydroxide aqueous solution at 35 ° C. A portion of the photosensitive dry film resist was removed (see FIG. 2A).

(Formation of insulation coating)
Next, a cover lay film (trade name: Nikaflex CISG, manufactured by Nikkan Kogyo Co., Ltd., polyimide thickness: 12.5 μm, adhesive thickness: 15 μm) is exposed so that both end portions (5.0 mm) of the electrical wiring 61 are exposed. And then vacuum-pressed under conditions of a pressure of 4.0 MPa, a temperature of 160 ° C., and a pressurization time of 90 minutes to provide an insulating coating for protecting the electrical wiring.

(Formation of Ni / Au plating)
Thereafter, degreasing, soft etching, acid cleaning, immersion in a sensitizer for electroless Ni plating (trade name: SA-100, manufactured by Hitachi Chemical Co., Ltd.) at 25 ° C. for 5 minutes, water washing, and 83 ° C. electroless It was immersed in a Ni plating solution (Okuno Pharmaceutical Co., Ltd., ICP Nicolon GM-SD solution, pH 4.6) for 8 minutes to form a 3 μm Ni film, and then washed with pure water.
Next, a substitution gold plating solution (100 mL; HGS-500 and 1.5 g; a bath with potassium gold cyanide / L) (trade name: HGS-500, manufactured by Hitachi Chemical Co., Ltd.) at 85 ° C. for 8 minutes. Immersion was performed to form a 0.06 μm displacement gold film on the Ni film. As a result, an electric wiring board 60 in which the electric wiring portion without the cover lay film was covered with the Ni and Au plating 62 was obtained (see FIG. 2B).
Next, the adhesive surface of the adhesive layer 70 described in PCT / JP2008 / 05465 previously adjusted is applied to the polyimide surface of the base material 50 using a roll laminator (HLM-1500, manufactured by Hitachi Chemical Technoplant Co., Ltd.), and the pressure is 0.4 MPa. Lamination was performed under the conditions of a temperature of 50 ° C. and a laminating speed of 0.2 m / min.
Thereafter, the adhesive layer 70 is irradiated with 1 J / cm ² of ultraviolet light (wavelength 365 nm) with an ultraviolet exposure machine (EXM-1172, manufactured by Oak Manufacturing Co., Ltd.), and the PET film which is the carrier film 51 of the adhesive layer 70 (Purex A31) was peeled off to obtain a flexible wiring board (see FIG. 2C).

Next, the release PET film (Purex A31), which is a protective film for the resin film for forming the lower clad layer 20 produced using the resin varnish A for forming the clad layer obtained above, is peeled off and obtained above. Affixed to the surface of the adhesive layer 70 on the flexible wiring board under the same laminating conditions as described above, ultraviolet rays (wavelength 365 nm) were applied from the resin side with an ultraviolet exposure machine (EXM-1172, manufactured by Oak Manufacturing Co., Ltd.) to 1.5 J. / Cm ^{2 is} irradiated, and then the release PET film (trade name: PUREX A31, Teijin DuPont Films Co., Ltd., thickness: 25 μm) which is the carrier film 51 is peeled off and subjected to heat treatment at 80 ° C. for 10 minutes. A clad layer 20 was formed (see FIG. 2D).
Next, the core layer 30 was formed on the lower clad layer 20 by laminating the above resin film for forming the core layer 30 under the same laminating conditions as described above (see FIG. 2E). Next, the PET film which is the carrier film 51 of the core layer 30 is peeled off, and the color-forming clad layer 10 forming resin film produced using the clad layer forming resin varnish B obtained above is laminated in the same manner as above. Under the conditions, it was laminated on the core layer 30 (see FIG. 2 (f)).

Next, ultraviolet rays (wavelength 365 nm) were irradiated with 0.8 J / cm ² with a UV photomask through a negative photomask having a width of 50 μm, and then after exposure at 80 ° C. for 5 minutes, heating was performed. Thereafter, the PET film as the carrier film is peeled off, and the color-developing clad pattern 11 and the core pattern 31 are developed using a developer (propylene glycol monomethyl ether acetate / N, N-dimethylacetamide = 7/3, mass ratio). did. Then, it wash | cleaned using the washing | cleaning liquid (isopropanol), and heat-dried at 100 degreeC for 10 minute (refer FIG.2 (g)). Next, the visibility of the core pattern 31 with the color-forming clad pattern 11 was confirmed with a fluorescence microscope (magnification 200) using ultraviolet light of 365 nm. The results are shown in Table 2.

Next, the clad layer forming resin film prepared using a vacuum pressure laminator (manufactured by Meiki Seisakusho Co., Ltd., MVLP-500) as the flat plate type laminator and using the clad layer forming resin varnish A as the upper clad layer 40, After evacuating to 500 Pa or less, thermocompression bonding was performed under the conditions of a pressure of 0.4 MPa, a temperature of 50 ° C., and a pressurization time of 30 seconds (see FIG. 2H).
Further, a 50 μm portion around the core pattern 31 and the color-forming clad pattern 11 is exposed through a negative photomask for the upper clad pattern having the same pattern as that of the negative photomask for forming the core pattern and having only a line width of 150 μm. In this way, ultraviolet rays (wavelength 365 nm) were irradiated with 3.0 J / cm ² , and then after exposure for 12 minutes at 80 ° C., heating was performed. Thereafter, the PET film which is the carrier film 51 of the resin film for forming the upper clad layer 40 was peeled off, and the upper clad layer 40 was developed using a developer (isopropanol) to obtain an upper clad pattern 41. Then, it wash | cleaned using the washing | cleaning liquid (isopropanol), and heat-dried at 100 degreeC for 10 minute (s). Next, the upper clad pattern 41 was cured by heat treatment at 160 ° C. for 1 hour, thereby producing the photoelectric composite substrate 2 (see FIG. 2 (i)).

(Formation of optical path conversion mirror)
A 45 ° mirror portion was formed from the upper clad pattern 41 side of the obtained photoelectric composite substrate 2 using a dicing saw (DAC552, manufactured by Disco Corporation).
The visibility of the core pattern 31 with the color-forming clad pattern 11 was confirmed by a fluorescence microscope (magnification 200) using 365 nm ultraviolet light from the upper clad pattern 41 side. The results are shown in Table 2.

Examples 11-17
In Example 10, an optoelectric composite substrate 2 was produced in the same manner except that the varnish shown in Table 2 was used as the varnish used for the lower clad layer 20, the chromogenic clad layer 10, and the upper clad layer 40. As in Example 10, Table 2 shows the results of confirming the visibility of the core pattern 31 after development and the visibility after forming the upper clad.
In Examples 16 and 17, the core pattern was black.

Example 18
In Example 10, before the color developing clad layer 10 using the clad layer forming resin varnish B was laminated on the lower clad layer 20, the color forming clad layer using the clad layer forming resin varnish A was further laminated. Then, an optoelectric composite substrate 2 was produced in the same manner except that the two color-forming clad layers 10 were used. As in Example 10, Table 2 shows the results of confirming the visibility of the core pattern 31 after development and the visibility after forming the upper clad.

Comparative Examples 7-12
In Example 10, an optoelectric composite substrate 2 was produced in the same manner except that the varnish shown in Table 2 was used as the varnish used for the lower clad layer 20, the chromogenic clad layer 10, and the upper clad layer 40. As in Example 10, Table 2 shows the results of confirming the visibility of the core pattern 31 after development and the visibility after forming the upper clad.
In Comparative Example 12, the color-forming clad layer 10 was not formed.

Example 19
[Production of optical waveguide]
The color-forming clad layer 10 using the resin varnish B for forming a clad layer obtained above is placed on a roll laminator (Hitachi Chemical Techno Plant) on a polyimide film (trade name; Kapton EN, thickness 25 μm) as a base material 50. Lamination was carried out under the conditions of a pressure of 0.4 MPa, a temperature of 50 ° C., and a laminating speed of 0.2 m / min (see FIG. 3A). Next, the PET film as the carrier film 51 is peeled off, and the resin surface of the resin film for forming the core layer 30 is pressed on the color-forming clad layer 10 using a roll laminator (HLM-1500, manufactured by Hitachi Chemical Technoplant Co., Ltd.). Lamination was performed under the conditions of 0.4 MPa, a temperature of 50 ° C., and a laminating speed of 0.2 m / min (see FIG. 3B). Next, through a negative photomask having a width of 50 μm, ultraviolet rays (wavelength 365 nm) are irradiated with 0.8 J / cm ² with the above-described ultraviolet exposure machine, and the color-forming clad pattern 11 and core pattern 31 are photocured, and then 80 Heating was performed after exposure for 5 minutes at ° C. Thereafter, the PET film which is the carrier film 51 of the resin film for forming the core layer 30 is peeled off, and the color developability using a developer (propylene glycol monomethyl ether acetate / N, N-dimethylacetamide = 7/3, mass ratio). The clad layer 10 and the core layer 30 were developed to obtain a color-forming clad pattern 11 and a core pattern 31.
Then, it wash | cleaned using the washing | cleaning liquid (isopropanol), and heat-dried at 100 degreeC for 10 minute (refer FIG.3 (c)). Next, the visibility of the core pattern 31 with the color-forming clad pattern 11 was confirmed with a fluorescence microscope (magnification 200) using 365 nm ultraviolet light from the core pattern 31 side. The results are shown in Table 3.
Next, the resin film for forming the upper clad layer 40 using the resin varnish A for forming the clad layer is vacuum pressure laminator (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd.), pressure 0.4 MPa, temperature 50 Lamination was performed at a temperature of 30 ° C. for 30 seconds (see FIG. 3D). Next, ultraviolet rays (wavelength 365 nm) were irradiated with 3.0 J / cm ² and the PET film as the carrier film 51 was peeled off, followed by heat curing at 160 ° C. for 1 hour to produce the optical waveguide 1. (See FIG. 3 (e)).

(Formation of optical path conversion mirror)
A 45 ° mirror part was formed from the upper clad layer 40 side of the obtained optical waveguide 1 using a dicing saw (DAC552, manufactured by Disco Corporation).
Next, the visibility of the core pattern 31 with the color-forming clad pattern 11 was confirmed with a fluorescence microscope (magnification 200) using 365 nm ultraviolet light from the upper clad layer 40 side. The results are shown in Table 3.

Comparative Example 13
In Example 19, the optical waveguide 1 was produced in the same manner except that the varnish shown in Table 3 was used as the varnish used for the color-forming clad layer 10. As in Example 19, Table 3 shows the results of confirming the visibility of the core pattern 31 after development and the visibility after forming the upper clad.

  The optical waveguide and the optoelectric composite member obtained by the production method of the present invention can be applied to various fields such as various optical devices and optical interconnections.

DESCRIPTION OF SYMBOLS 1 Optical waveguide 2 Photoelectric composite board 10 Color-forming clad layer 11 Patterned color-forming clad layer (color-forming clad pattern)
20 Lower clad layer 30 Core layer 31 Patterned core layer (core pattern)
40 Upper clad layer 41 Patterned upper clad layer (upper clad pattern)
50 Substrate 51 Carrier Film 60 Electric Wiring Board 61 Electric Wiring 62 Plating 70 Adhesive Layer 71 Adhesive Auxiliary Cladding Layer

Claims (20)

  A first step of forming a substantially rectangular parallelepiped-shaped member comprising a substantially rectangular parallelepiped color-forming clad layer and a substantially rectangular solid-shaped core layer mounted on an upper surface or a lower surface of the color-forming clad layer; A method of manufacturing an optical waveguide, comprising: a second step of forming an upper clad layer covering an upper surface and side surfaces of a member.   2. The method of manufacturing an optical waveguide according to claim 1, wherein the color-developing clad layer is one or more multilayer films, and at least one of the multilayer films has color developability.   The first step includes a step (A) of laminating the photosensitive color-forming clad layer and the photosensitive core layer on a substrate, and the color-forming clad layer after the step (A). And pattern-exposing the core layer, and then developing and removing the uncured portion of the color-forming clad layer and the uncured portion of the core layer. The method for manufacturing an optical waveguide according to claim 1, further comprising a step (B) of forming the substantially rectangular parallelepiped member including a layer and the patterned core layer.   4. The method of manufacturing an optical waveguide according to claim 3, wherein the color-developing clad layer is laminated on the base material via an adhesive layer.   (C) in which the first step forms a lower clad layer on a substrate, and the photosensitive core layer and the photosensitive color-forming clad layer are laminated on the lower clad layer; After the step (C), the color-forming clad layer and the core layer are simultaneously subjected to pattern exposure, and then the uncured portion of the color-forming clad layer and the uncured portion of the core layer are developed. 3. A step (D) of forming the substantially rectangular parallelepiped member comprising the patterned color-forming clad layer and the patterned core layer by removing the step (D). The manufacturing method of the optical waveguide as described in any one of.   The second step includes a step (E) of laminating the upper clad layer from the patterned substantially rectangular parallelepiped member side after the step (B) or (D). 6. A method for producing an optical waveguide according to 3 or 5.   The said 2nd process includes the process (F) which forms the said upper clad layer patterned by exposing the said upper clad layer after the said process (E), The said 6th process is characterized by the above-mentioned. Manufacturing method of the optical waveguide.   An optical waveguide manufactured by the method according to claim 1.   The optical waveguide according to claim 8, wherein the optical waveguide has an optical path conversion mirror.   A first step of forming a substantially rectangular parallelepiped-shaped member comprising a substantially rectangular parallelepiped color-forming clad layer and a substantially rectangular solid-shaped core layer mounted on an upper surface or a lower surface of the color-forming clad layer on an electrical wiring board; And a second step of forming an upper clad layer covering the upper surface and side surfaces of the rectangular parallelepiped member.   11. The method for producing an optoelectric composite substrate according to claim 10, wherein the color-developing clad layer is a multilayer film having one or more layers, and at least one layer of the multilayer film has color-developing properties. The first step includes a step (A ^* ) of laminating the photosensitive color-forming clad layer and the photosensitive core layer on the electrical wiring board, and the color development after the step (A ^* ). The patterned clad layer and the core layer are subjected to pattern exposure at the same time, and then the uncured portion of the color-forming clad layer and the uncured portion of the core layer are developed and removed to develop the patterned layer. The method for producing an optoelectric composite substrate according to claim 10, further comprising a step (B ^* ) of forming the substantially rectangular parallelepiped member comprising a color-forming clad layer and the patterned core layer.   13. The method of manufacturing an optoelectric composite substrate according to claim 12, wherein the color-developing clad layer is laminated on the electric wiring board via an adhesive layer. In the first step, a lower clad layer is formed on the electric wiring board, and the photosensitive core layer and the photosensitive color-forming clad layer are laminated on the lower clad layer (C ^* ) And after the step (C ^* ), the color-forming clad layer and the core layer are simultaneously subjected to pattern exposure, and then the uncured portion of the color-forming clad layer and the core layer are cured. A step (D ^* ) of forming the substantially rectangular parallelepiped member composed of the patterned color-forming clad layer and the patterned core layer by developing and removing a non-existing portion. The method for producing an optoelectric composite substrate according to claim 10. The second step includes a step (E ^* ) of laminating the upper cladding layer from the patterned core layer side after the step (B ^* ) or (D ^* ). Item 15. A method for producing an optoelectric composite substrate according to Item 12 or 14. The second step includes a step (E ^* ) of laminating the upper clad layer from the patterned substantially rectangular parallelepiped member side after the step (B ^* ) or (D ^* ). The method for producing an optoelectric composite substrate according to claim 12 or 14. 16. The second step includes a step (F ^* ) of patterning the upper clad layer to form the patterned upper clad layer after the step (E ^* ). Or the manufacturing method of the optical waveguide of 16.   An optical / electrical composite substrate obtained by combining the optical waveguide according to claim 8 and an electrical wiring board.   An optoelectric composite substrate manufactured by the method according to claim 12.   The photoelectric composite substrate according to claim 19, wherein the photoelectric composite substrate has an optical path conversion mirror.

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