JP4293161B2 - Optical waveguide structure - Google Patents

Description

  The present invention relates to an optical waveguide structure.

  As optical components in the field of optical communication that have been attracting attention in recent years, there are optical branching couplers (optical couplers), optical multiplexers / demultiplexers, and the like, and optical waveguide devices used for these are promising.

  As this optical waveguide type element, there is a polymer optical waveguide that is easy to manufacture (patterning) and is versatile, in addition to the conventional quartz optical waveguide, and the latter has been actively developed in recent years.

  As a substrate (optical waveguide structure) on which such an optical waveguide type element can be formed, an optical waveguide composed of a core part and a clad part and a metal wiring provided on the optical waveguide are disclosed (for example, , See Patent Document 1).

  However, the optical waveguide structure described in Patent Document 1 has the following problems.

1. The process of forming the optical waveguide is complicated, and the degree of freedom in designing and selecting the pattern shape of the core part constituting the optical path of the transmitted light is narrow.
2. The core pattern shape accuracy and dimensional accuracy are poor.
3. When combined with a wiring pattern, the degree of freedom in designing the wiring pattern is narrow.

JP 2004-12635 A

  An object of the present invention is to provide an optical waveguide structure including an optical waveguide that can form a core portion (optical path) with a wide degree of freedom in designing a pattern shape and high dimensional accuracy by a simple method. .

Such an object is achieved by the present inventions (1) to (16) below.
(1) An optical waveguide structure having an optical waveguide having a core layer including a core portion, a cladding portion having a refractive index lower than that of the core portion, and a conductor layer provided on at least one surface side of the optical waveguide. Because
The core layer includes a substance that is activated by irradiation with actinic radiation, a main chain and a branch that is branched from the main chain, and at least a part of the molecular structure can be detached from the main chain by the activated substance. Forming a layer containing a polymer having a functional group,
Thereafter, by selectively irradiating the layer with the actinic radiation, the substance is activated in the irradiation region irradiated with the actinic radiation, and the leaving group of the polymer is released, By producing a refractive index difference between the irradiation region and the non-irradiation region of the active radiation, either the irradiation region or the non-irradiation region was obtained as the core portion, and the other was obtained as the cladding portion. Is,
The substance includes a compound that generates a cation and a weakly coordinating anion upon irradiation with the active radiation,
The leaving group causes a decrease in the refractive index of the polymer due to the leaving, and has a -O-Si-diphenyl structure,
The optical waveguide structure, wherein the polymer is mainly a norbornene-based polymer.

(2) The optical waveguide structure according to (1), wherein the core layer is obtained by performing a heat treatment on the layer after the irradiation with the active radiation.

(3) The optical waveguide structure according to (1) or (2) , wherein the active radiation has a peak wavelength in a range of 200 to 450 nm.

(4) The optical waveguide structure according to any one of (1) to (3) , wherein an irradiation amount of the active radiation is 0.1 to 9 J / cm ² .

(5) The optical waveguide structure according to any one of (1) to (4) , wherein the active radiation is applied to the layer through a mask.

(6) The optical waveguide structure according to any one of (1) to (5) , wherein the layer further includes an antioxidant.

(7) The optical waveguide structure according to any one of (1) to (6) , wherein the layer further includes a sensitizer.

(8) The optical waveguide structure according to any one of (1) to (7) , wherein the leaving group is an acid leaving group that is released by the action of the cation.

( 9 ) Any of the above (1) to ( 8 ), wherein the core part and the clad part are different in refractive index due to a difference in the number of the leaving groups bonded to the main chain. An optical waveguide structure according to claim 1.

( 10 ) The optical waveguide structure according to any one of (1) to ( 9 ), wherein the norbornene-based polymer is an addition polymer.

( 11 ) The optical waveguide structure according to any one of (1) to ( 10 ), wherein the norbornene-based polymer includes a repeating unit of diphenylmethylnorbornenemethoxysilane.

( 12 ) The optical waveguide structure according to any one of (1) to ( 11 ), wherein the norbornene-based polymer includes an alkylnorbornene repeating unit.

( 13 ) The optical waveguide structure according to any one of (1) to ( 12 ), wherein the norbornene-based polymer includes a repeating unit of hexylnorbornene.

( 14 ) The optical waveguide according to any one of (1) to ( 13 ), wherein the optical waveguide is provided in contact with at least one surface of the core layer and has a cladding layer having a refractive index lower than that of the core portion. Waveguide structure.

( 15 ) The optical waveguide structure according to any one of (1) to ( 14 ), wherein an average thickness of the conductor layer is 10 to 90% of an average thickness of the optical waveguide.

( 16 ) In any one of the above (1) to ( 15 ), the conductor layer is formed by at least one of a dry plating method, a wet plating method, and joining of conductive sheet materials. The optical waveguide structure described.

  According to the present invention, since the conductor layer is formed in advance, wiring to the element (formation of an electric circuit) is easy, and wiring suitable for the element can be provided regardless of the type of element (terminal installation location). This is possible, and the degree of freedom of the configuration of the wiring circuit (for example, the degree of freedom of selection of the terminal installation location) is wide and versatile.

  According to the present invention, the core portion can be patterned by a simple method of irradiation with actinic radiation, the core portion (optical circuit) has a wide degree of freedom in designing the pattern shape, and the core has high dimensional accuracy. Part is obtained.

  In addition, according to the present invention, since both the wiring (electric circuit) and the core part (optical circuit) can be formed with high arrangement density, efficient circuit design is possible in a hybrid optical and electrical circuit. In addition, further circuit integration is possible.

Further, according to the present invention, such an optical waveguide structure can be easily manufactured.
Further, by configuring the core layer with a material containing a norbornene-based polymer, high optical transmission performance can be imparted to the core portion.

  In this case, even when the optical waveguide structure is bent and deformed, defects such as microcracks are not easily generated in the core portion, so that durability can be improved.

  Furthermore, in this case, the difference in refractive index between the core portion and the clad portion can be further increased, and the heat resistance is excellent. As a result, a high-performance optical waveguide is obtained.

  Such an optical waveguide structure of the present invention has a wide range of optical circuit (optical waveguide pattern) and electrical circuit design, good yield, high optical transmission performance, excellent reliability and durability, Rich in versatility. Therefore, the present invention can be used for various electronic components, electronic devices, and the like.

  Hereinafter, the optical waveguide structure of the present invention will be described in detail based on preferred embodiments shown in the accompanying drawings.

  FIG. 1 is a perspective view (partially cut away) showing an embodiment of an optical waveguide structure of the present invention.

  In the following description, the upper side in FIG. 1 is “upper” or “upper”, and the lower side is “lower” or “lower” (the same applies to the following drawings).

Each figure is exaggerated in the thickness direction of the layer (the vertical direction in each figure).
The optical waveguide structure 9 shown in FIG. 1 has an optical waveguide 90 and conductor layers 901 and 902 provided on the upper surface and the lower surface, respectively, and these layers are bonded.

  The constituent materials of the conductor layers 901 and 902 are, for example, various metal materials such as copper, copper-based alloy, aluminum, and aluminum-based alloy, indium tin oxide (ITO), and fluorine-containing indium tin oxide (FTO). And various oxide materials.

  The average thicknesses of the conductor layers 901 and 902 are each preferably about 10 to 90% of the average thickness of the optical waveguide 90, and more preferably about 20 to 80%. Specifically, the average thickness of the conductor layers 901 and 902 is not particularly limited, but is usually preferably about 3 to 100 μm and more preferably about 5 to 70 μm. Thereby, it is possible to make the conductor layers 901 and 902 excellent in conductivity while preventing the flexibility of the optical waveguide structure 9 from being lowered.

  Moreover, in the structure shown in FIG. 1, both the conductor layers 901 and 902 have comprised flat form (sheet form). In this case, after processing into a predetermined pattern of the conductor layers 901 and 902, an optical element (light emitting element, light receiving element, etc.) is mounted at a desired location, thereby manufacturing a composite device including an optical circuit and an electric circuit. can do.

  The conductor layers 901 and 902 may be previously patterned (wiring). Moreover, you may abbreviate | omit either one of the conductor layers 901 and 902 as needed.

  Further, between the conductor layers 901 and 902 and the optical waveguide 90, one layer or two or more layers for any purpose (for example, the purpose of improving adhesion) may be provided.

  The optical waveguide 90 is formed by laminating a clad layer (lower clad layer) 91, a core layer 93, and a clad layer (upper clad layer) 92 in this order from the lower side in FIG. A pattern core portion 94 and a clad portion 95 adjacent to the core portion (waveguide channel) 94 are formed.

  The difference in refractive index between the core portion 94 and the clad portion 95 is not particularly limited, but is preferably about 0.3 to 5.5%, and particularly preferably about 0.8 to 2.2%. If the difference in refractive index is less than the lower limit, the effect of transmitting light may be reduced, and even if the upper limit is exceeded, no further increase in light transmission efficiency can be expected.

The refractive index difference is expressed by the following equation, where A is the refractive index of the core portion 94 and B is the refractive index of the cladding portion 95.
Refractive index difference (%) = | A / B-1 | × 100

  In the configuration shown in FIG. 1, the core portion 94 is formed in a straight line shape in a plan view, but may be curved or branched in the middle, and the shape is arbitrary. In addition, if the manufacturing method of the optical waveguide structure 9 which is mentioned later is used, the core part 94 of a complicated and arbitrary shape can be formed easily and with a sufficient dimensional accuracy.

  The core section 94 has a quadrangular shape such as a square shape or a rectangular shape (rectangular shape).

  The width and height of the core portion 94 are not particularly limited, but are preferably about 1 to 200 μm, more preferably about 5 to 100 μm, and still more preferably about 10 to 60 μm.

  The core portion 94 is made of a material having a higher refractive index than that of the cladding portion 95, and is also made of a material having a higher refractive index than the cladding layers 91 and 92.

  The clad layers 91 and 92 constitute the clad portions located at the lower part and the upper part of the core part 94, respectively. With such a configuration, the core portion 94 functions as a light guide path whose outer periphery is surrounded by the cladding portion.

  The average thickness of the cladding layers 91 and 92 is not particularly limited, but is preferably about 1 to 200 μm, more preferably about 5 to 100 μm, and still more preferably about 10 to 60 μm.

  The constituent materials of the clad layer 91, the clad portion 95, and the clad layer 92 may be the same (same type) or different from each other, but they have the same or similar refractive index. Is preferred. Details of the constituent materials of the cladding layers 91 and 92 and the core layer 93 will be described later.

  The optical waveguide structure 9 of the present invention is slightly different depending on the optical characteristics of the material of the core portion 94 and is not particularly limited. For example, the optical waveguide structure 9 is preferably used in data communication using light in the wavelength region of about 600 to 1550 nm. The

Next, an example of a method for manufacturing the optical waveguide structure 9 will be described.
<First manufacturing method>
First, the 1st manufacturing method of the optical waveguide structure 9 is demonstrated.

  2-7 is sectional drawing which shows typically the process example of the 1st manufacturing method of the optical waveguide structure of this invention, respectively.

[1A] First, a layer 910 is formed over a supporting substrate 951 (see FIG. 2).
The layer 910 is formed by a method in which a core layer forming material (varnish) 900 is applied and cured (solidified).

  Specifically, the layer 910 is formed by applying the core layer forming material 900 on the support substrate 951 to form a liquid film, and then placing the support substrate 951 on a ventilated level table so that the surface of the liquid film is not coated. It is formed by leveling the uniform part and evaporating (desolving) the solvent.

  When the layer 910 is formed by a coating method, examples thereof include a doctor blade method, a spin coating method, a dipping method, a table coating method, a spray method, an applicator method, a curtain coating method, a die coating method, and the like. It is not done.

  As the support substrate 951, for example, a silicon substrate, a silicon dioxide substrate, a glass substrate, a quartz substrate, a polyethylene terephthalate (PET) film, or the like is used.

  The core layer forming material 900 contains a light-induced heat-developable material (PITDM) composed of a polymer 915 and an additive 920 (in this embodiment, including at least a monomer, a promoter, and a catalyst precursor). It is a material in which a monomer reaction occurs in the polymer 915 by irradiation with actinic radiation and heating.

  In the resulting layer 910, any polymer (matrix) 915 is distributed substantially uniformly and randomly, and the additive 920 is substantially uniformly and randomly dispersed within the polymer 915. ing. Thereby, the additive 920 is substantially uniformly and arbitrarily dispersed in the layer 910.

  The average thickness of the layer 910 is appropriately set according to the thickness of the core layer 93 to be formed, and is not particularly limited, but is preferably about 5 to 200 μm, and preferably about 10 to 100 μm. More preferably, it is about 15 to 65 μm.

  The polymer 915 has sufficiently high transparency (colorless and transparent) and is compatible with the monomer described later, and the monomer can react (polymerization reaction or crosslinking reaction) as described later. Even after the monomers are polymerized, those having sufficient transparency are preferably used.

  Here, “having compatibility” means that the monomer is at least mixed and does not cause phase separation with the polymer 915 in the core layer forming material 900 or the layer 910.

  Examples of such a polymer 915 include cyclic olefin resins such as norbornene resins and benzocyclobutene resins, acrylic resins, methacrylic resins, polycarbonates, polystyrenes, epoxy resins, polyamides, polyimides, polybenzoxazoles, and the like. Among them, one or a combination of two or more thereof (polymer alloy, polymer blend (mixture), copolymer, etc.) can be used.

  Among these, those mainly composed of norbornene resins (norbornene polymers) are preferable. By using a norbornene-based polymer as the polymer 915, the core layer 93 having excellent optical transmission performance and heat resistance can be obtained.

  Moreover, since norbornene-type polymer has high hydrophobicity, the core layer 93 which cannot produce the dimensional change by water absorption etc. easily can be obtained.

  The norbornene polymer may be either one having a single repeating unit (homopolymer) or one having two or more norbornene repeating units (copolymer).

  Examples of such norbornene-based polymers include (1) addition (co) polymers of norbornene monomers obtained by addition (co) polymerization of norbornene monomers, and (2) norbornene monomers and ethylene or α-olefins. (3) addition polymers such as addition copolymers with norbornene-type monomers and non-conjugated dienes, and other monomers as required, (4) ring opening of norbornene-type monomers ( A (co) polymer, and a resin obtained by hydrogenating the (co) polymer if necessary, (5) a ring-opening copolymer of a norbornene-type monomer and ethylene or α-olefins, and ( (Co) polymer hydrogenated resin, (6) ring-opening copolymer of norbornene type monomer and non-conjugated diene or other monomer, and (co) polymerization if necessary And a ring-opening polymer such as a polymer obtained by hydrogenating the body. Examples of these polymers include random copolymers, block copolymers, and alternating copolymers.

  These norbornene-based polymers include, for example, ring-opening metathesis polymerization (ROMP), combination of ROMP and hydrogenation reaction, polymerization by radical or cation, polymerization using a cationic palladium polymerization initiator, and other polymerization initiators ( For example, it can be obtained by any known polymerization method such as polymerization using a polymerization initiator of nickel or another transition metal).

  Among these, as the norbornene-based polymer, those having at least one repeating unit represented by the following chemical formula 1 (Structural Formula B), that is, an addition (co) polymer is preferable. This is preferable because it is rich in transparency, heat resistance and flexibility.

  Such a norbornene polymer is suitably synthesized by using, for example, a norbornene monomer described later (a norbornene monomer represented by Chemical Formula 3 described below or a crosslinkable norbornene monomer).

  In order to obtain a polymer 915 having a relatively high refractive index, a monomer having an aromatic ring (aromatic group), a nitrogen atom, a bromine atom or a chlorine atom in the molecular structure is generally selected, A polymer 915 is synthesized (polymerized). On the other hand, in order to obtain a polymer 915 having a relatively low refractive index, a monomer having an alkyl group, a fluorine atom or an ether structure (ether group) is generally selected in the molecular structure, and the polymer 915 is synthesized ( Polymerization).

  As the norbornene-based polymer having a relatively high refractive index, those containing a repeating unit of aralkylnorbornene are preferable. Such norbornene-based polymers have a particularly high refractive index.

  Examples of the aralkyl group (arylalkyl group) of the aralkylnorbornene repeating unit include benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, naphthylethyl group, naphthylpropyl group, fluorenylethyl group, fluorene group, and the like. Examples thereof include a nylpropyl group, and a benzyl group and a phenylethyl group are particularly preferable.

  A norbornene-based polymer having such a repeating unit is preferable because it has a very high refractive index.

  Further, the norbornene-based polymer preferably contains an alkylnorbornene repeating unit. Since the norbornene-based polymer containing the alkylnorbornene repeating unit has high flexibility, high flexibility (flexibility) can be imparted to the optical waveguide 90 by using such norbornene-based polymer.

  Examples of the alkyl group that the alkylnorbornene repeating unit has include a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group, and a hexyl group is particularly preferable. These alkyl groups may be either linear or branched.

  By including the repeating unit of hexyl norbornene, it is possible to prevent the refractive index of the entire norbornene-based polymer from being lowered and to maintain high flexibility. Such a norbornene-based polymer is preferable because of its excellent transmittance with respect to light in the wavelength region as described above (particularly in the wavelength region near 850 nm).

  Preferred examples of such norbornene polymers include hexyl norbornene homopolymer, phenylethyl norbornene homopolymer, benzyl norbornene homopolymer, hexyl norbornene and phenylethyl norbornene copolymer, and hexyl norbornene and benzyl norbornene copolymer. However, it is not limited to these.

  The core layer forming material 900 of this embodiment includes a monomer, a promoter (first substance), and a catalyst precursor (second substance) as the additive 920.

  The monomer reacts in the active radiation irradiated region by irradiation with actinic radiation, which will be described later, and forms a reaction product. It is a compound that can cause a rate difference.

  Here, as this reaction product, a polymer (polymer) formed by polymerizing a monomer in a polymer (matrix) 915, a crosslinked structure that cross-links the polymers 915, and a polymer 915 that is polymerized from the polymer 915 Examples thereof include at least one of branched structures (branch polymer and side chain (pendant group)).

  Here, in the layer 910, when it is desired that the refractive index of the irradiated region is high, a polymer 915 having a relatively low refractive index and a monomer having a high refractive index with respect to the polymer 915 are combined. When used and it is desired that the refractive index of the irradiated region be low, a polymer 915 having a relatively high refractive index and a monomer having a low refractive index for this polymer 915 are used in combination.

  Note that “high” or “low” in the refractive index does not mean the absolute value of the refractive index but means a relative relationship between certain materials.

  When the refractive index of the irradiated region in the layer 910 decreases due to the monomer reaction (reactant generation), the portion becomes the cladding portion 95, and when the refractive index of the irradiated region increases, the portion becomes the core portion 94. It becomes.

  Such a monomer is not particularly limited as long as it is a compound having a polymerizable site, and examples thereof include norbornene monomers, acrylic acid (methacrylic acid) monomers, epoxy monomers, styrene monomers, and the like. These can be used alone or in combination of two or more.

  Among these, it is preferable to use a norbornene-based monomer as the monomer. By using the norbornene-based monomer, it is possible to obtain the core layer 93 (optical waveguide 90) having excellent optical transmission performance and excellent heat resistance and flexibility.

  Here, the norbornene-based monomer is a generic term for monomers containing at least one norbornene skeleton represented by the following chemical formula 2 (structural formula A), and examples thereof include compounds represented by the following chemical formula 3 (structural formula C). .

［式中、ａは、単結合または二重結合を表し、Ｒ^１〜Ｒ^４は、それぞれ独立して、水素原子、置換もしくは無置換の炭化水素基、または官能置換基を表し、ｍは、０〜５の整数を表す。ただし、ａが二重結合の場合、Ｒ^１およびＲ^２のいずれか一方、Ｒ^３およびＲ^４のいずれか一方は存在しない。］

[Wherein, a represents a single bond or a double bond, R ^{1 to} R ⁴ each independently represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or a functional substituent; Represents an integer of 0 to 5; However, when a is a double bond, either one of R ¹ and R ² or one of R ³ and R ⁴ does not exist. ]

Examples of the unsubstituted hydrocarbon group (hydrocarbyl group) include, for example, a linear or branched alkyl group having 1 to 10 carbon atoms (C _{1 to} C ₁₀ ), a linear or branched carbon number of 2 -10 (C ₂ -C ₁₀ alkenyl group, linear or branched alkynyl group having 2 to 10 carbon atoms (C ₂ -C ₁₀ ), cycloalkyl having 4 to 12 carbon atoms (C ₄ -C ₁₂ ) Group, C 4-12 (C ₄ -C ₁₂ ) cycloalkenyl group, C 6-12 (C ₆ -C ₁₂ ) aryl group, C 7-24 (C ₇ -C ₂₄ ) aralkyl group In addition, R ¹ and R ² , R ³ and R ⁴ may each be an alkylidenyl group having 1 to 10 carbon atoms (C _{1 to} C ₁₀ ).

  Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group. , Nonyl and decyl groups, but are not limited thereto.

  Specific examples of the alkenyl group include, but are not limited to, a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.

  Specific examples of the alkynyl group include, but are not limited to, ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group and 2-butynyl group.

  Specific examples of the cycloalkyl group include, but are not limited to, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

  Specific examples of the aryl group include, but are not limited to, a phenyl group, a naphthyl group, and an anthracenyl group.

  Specific examples of the aralkyl group include, but are not limited to, a benzyl group and a phenylethyl (phenethyl) group.

  Further, specific examples of the alkylidenyl group include, but are not limited to, a methylidenyl group and an ethylidenyl group.

  Examples of the substituted hydrocarbon group include those in which some or all of the hydrogen atoms of the hydrocarbon group are substituted with a halogen atom, that is, a halohydrocarbyl group, a perhalohydrocarbyl group. Or halogenated hydrocarbon groups such as perhalocarbyl groups.

  In these halogenated hydrocarbon groups, the halogen atom substituted with a hydrogen atom is preferably at least one selected from a chlorine atom, fluorine and bromine, more preferably a fluorine atom.

  Among these, specific examples of the perhalogenated hydrocarbon group (perhalohydrocarbyl group, perhalocarbyl group) include, for example, a perfluorophenyl group, a perfluoromethyl group (trifluoromethyl group), and a perfluoroethyl group. Perfluoropropyl group, perfluorobutyl group, perfluorohexyl group and the like.

As the halogenated alkyl group, those having 11 to 20 carbon atoms can be suitably used in addition to those having 1 to 10 carbon atoms. That is, as the halogenated alkyl group, a group that is partially or completely halogenated, linear or branched, and represented by the general formula: —C _Z X ″ _{2Z + 1} can be selected. Here, X '' represents a halogen atom or a hydrogen atom each independently, and Z represents the integer of 1-20.

In addition to the halogen atom, the substituted hydrocarbon group may be a linear or branched alkyl group having 1 to 5 carbon atoms (C _{1 to} C ₅ ), a haloalkyl group, an aryl group, and a cycloalkyl group. Examples thereof include a substituted cycloalkyl group, aryl group, and aralkyl group (aralkyl group).

Moreover, as a functional substituent, for example, — (CH ₂ ) _n —CH (CF ₂ ) ₂ —O—Si (Me) ₃ , — (CH ₂ ) _n —CH (CF ₃ ) ₂ —O—CH ₂ —O—CH ₃ , — (CH ₂ ) _n —CH (CF ₃ ) ₂ —O—C (O) —O—C (CH ₃ ) ₃ , — (CH ₂ ) _n —C (CF ₃ ) ₂ — OH, — (CH ₂ ) _n —C (O) —NH ₂ , — (CH ₂ ) _n —C (O) —Cl, — (CH ₂ ) _n —C (O) —O—R ⁵ , — ( ^{_{CH 2) n-O-R}} 5, - (CH 2) n -O-C (O) -R 5, - (CH 2) n -C (O) -R 5, - (CH 2) n -O —C (O) —OR ⁵ , — (CH ₂ ) _n —Si (R ⁵ ) ₃ , — (CH ₂ ) _n —Si (OR ⁵ ) ₃ , — (CH ₂ ) _n —O—Si (R ⁵⁾ ) ₃ and-(C _{H 2) n -C (O)} -OR 6 , and the like.

Here, in each of the formulas above, each, n is an integer of 0, ^{R 5} are each independently a hydrogen atom, a linear or branched C 1 to 20 _(C 1 -C ₂₀₎ alkyl group, a linear or branched halogenated or perhalogenated alkyl group having a carbon number 1 to 20 _(C 1 _{-C 20)} linear or branched C 2 to 10 _(C 2 ~ alkenyl group of C _10), a linear or branched alkynyl group having 2 to 10 carbon atoms _(C 2 _{~C 10),} a cycloalkyl group having 5 to 12 carbon atoms _(C 5 _{~C 12),} to 6 carbon atoms -14 (C ₆ -C ₁₄ ) aryl group, C 6-14 (C ₆ -C ₁₄ ) halogenated or perhalogenated aryl group or C 7-24 (C ₇ -C ₂₄ ) aralkyl group Represents.

Incidentally, the hydrocarbon group represented by R ⁵ represents the same hydrocarbon groups as those represented by R ¹ to R ^4. As represented by R ^{1 to} R ⁴ , the hydrocarbon group represented by R ⁵ may be halogenated or perhalogenated.

For example, when R ⁵ is a halogenated or perhalogenated alkyl group having 1 to 20 carbon atoms (C _{1 to} C ₂₀ ), R ⁵ is represented by the general formula: —C _Z X ″ _{2Z + 1} . Here, z and X ″ are the same as defined above, and at least one of X ″ is a halogen atom (for example, a bromine atom, a chlorine atom, or a fluorine atom).

Here, the perhalogenated alkyl group is a group in which all X ″ are halogen atoms in the above general formula, and specific examples thereof include a trifluoromethyl group, a trichloromethyl group, —C ₇ F _15. Although _-C 11 _{F 23} and the like, but are not limited to.

  Specific examples of the perhalogenated aryl group include, but are not limited to, a pentachlorophenyl group and a pentafluorophenyl group.

Examples of R ⁶ include —C (CH ₃ ) ₃ , —Si (CH ₃ ) ₃ , —CH (R ⁷ ) —O—CH ₂ CH ₃ , —CH (R ⁷ ) OC (CH ₃ ). ₃ and the cyclic group of the following chemical formula 4 and the like.

Here, R ⁷ represents a hydrogen atom or a linear or branched alkyl group having ₁ to ₅ carbon atoms (C _{1 to} C ₅ ).

  Examples of the alkyl group include methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl group, t-butyl, pentyl group, t-pentyl group, and neopentyl group.

  In the cyclic group represented by Chemical Formula 4, an ester bond is formed between the single bond extending from the ring structure and the acid substituent.

Specific examples of R ⁶ include, for example, a 1-methyl-1-cyclohexyl group, an isobornyl group, a 2-methyl-2-isobornyl group, a 2-methyl-2-adamantyl group, a tetrahydrofuranyl group, Examples thereof include a tetrahydropyranoyl group, a 3-oxocyclohexanoyl group, a mevalonic lactonyl group, a 1-ethoxyethyl group, and a 1-t-butoxyethyl group.

Other examples of R ⁶ include a dicyclopropylmethyl group (Dcpm) and a dimethylcyclopropylmethyl group (Dmcp) represented by the following chemical formula 5.

  Moreover, it can replace with said monomer for a monomer, or can also use a crosslinkable monomer (crosslinking agent) with said monomer. This crosslinkable monomer is a compound capable of causing a crosslinking reaction in the presence of a catalyst precursor described later.

  The use of the crosslinkable monomer has the following advantages. That is, since the crosslinkable monomer is polymerized faster, the time required for the formation (process) of the core layer 93 (optical waveguide 90) can be shortened. Moreover, since the crosslinkable monomer is difficult to evaporate even when heated, an increase in vapor pressure can be suppressed. Furthermore, since the crosslinkable monomer is excellent in heat resistance, the heat resistance of the core layer 93 can be improved.

  Among these, the crosslinkable norbornene-based monomer is a compound including a norbornene-based moiety (norbornene-based double bond) represented by Formula 2 (Structural Formula A).

  As the crosslinkable norbornene-based monomer, there are a compound of a continuous polycyclic ring system and a compound of a linked multicyclic ring system.

  Examples of the continuous polycyclic ring-based compound (continuous polycyclic ring-based crosslinkable norbornene-based monomer) include compounds represented by the following chemical formula (6).

［式中、Ｙは、メチレン（−ＣＨ_２−）基を表し、ｍは、０〜５の整数を表わす。ただし、ｍが０である場合、Ｙは、単結合である。］

[Wherein Y represents a methylene (—CH ₂ —) group, and m represents an integer of 0 to 5. However, when m is 0, Y is a single bond. ]

  For the sake of simplification, norbornadiene is included in the continuous polycyclic ring system and is considered to include a polymerizable norbornene double bond.

  Specific examples of this continuous polycyclic compound include, but are not limited to, compounds represented by the following chemical formula (7).

  On the other hand, examples of the linked polycyclic ring-based compound (linked polycyclic ring-based crosslinkable norbornene-based monomer) include compounds represented by the following chemical formula (8).

［式中、ａは、それぞれ独立して、単結合または二重結合を表し、ｍは、それぞれ独立して、０〜５の整数を表し、Ｒ^９は、それぞれ独立して二価の炭化水素基、二価のエーテル基または二価のシリル基を表す。また、ｎは、０または１である。］

[Wherein, a independently represents a single bond or a double bond; m independently represents an integer of 0 to 5; and R ⁹ independently represents a divalent hydrocarbon. Represents a group, a divalent ether group or a divalent silyl group. N is 0 or 1. ]

  Here, the divalent substituent refers to a group having two bonds that can be bonded to the norbornene structure at the end.

Specific examples of the divalent hydrocarbon group (hydrocarbyl group) include an alkylene group represented by the general formula:-(C _d H _2d )-(d is preferably an integer of 1 to 10). And a divalent aromatic group (aryl group).

The divalent alkylene group is preferably a linear or branched alkylene group having 1 to 10 carbon atoms (C _{1 to} C ₁₀ ), such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, Examples include a hexylene group, a heptylene group, an octylene group, a nonylene group, and a decylene group.

  The branched alkylene group is one in which a main chain hydrogen atom is substituted with a linear or branched alkyl group.

On the other hand, the divalent aromatic group is preferably a divalent phenyl group or a divalent naphthyl group.
The divalent ether group is a group represented by —R ¹⁰ —O—R ¹⁰ —.

Here, R ¹⁰ independently represents the same as R ⁹ .
Specific examples of the linked polycyclic ring compound include compounds represented by the following chemical formula 9, chemical formula 10, chemical formula 11 and chemical formula 12, as well as fluorine-containing compounds represented by chemical formula 13 and chemical formula 14 (fluorine-containing crosslinks). Norbornene-based monomers), but is not limited thereto.

  The compound represented by the chemical formula 10 is dimethylbis [bicyclo [2.2.1] hept-2-ene-5-methoxy] silane, and is named dimethylbis (norbornenemethoxy) silane (“ Abbreviated as “SiX”).

［式中、ｎは、０〜４の整数を表す。］

[Wherein, n represents an integer of 0 to 4. ]

［式中、ｍおよびｎは、それぞれ、１〜４の整数を表す。］

[Wherein, m and n each represent an integer of 1 to 4. ]

  Among various crosslinkable norbornene monomers, dimethylbis (norbornenemethoxy) silane (SiX) is particularly preferable. SiX has a sufficiently low refractive index with respect to a norbornene-based polymer containing a repeating unit of alkylnorbornene and / or a repeating unit of aralkylnorbornene. For this reason, the refractive index of the irradiation region irradiated with actinic radiation, which will be described later, can be reliably lowered to form the cladding portion 95. Moreover, the refractive index difference between the core part 94 and the clad part 95 can be increased, and the characteristics (optical transmission performance) of the core layer 93 (optical waveguide 90) can be improved.

  In addition, you may make it use the above monomers individually or in arbitrary combinations.

  The catalyst precursor (second substance) is a substance capable of initiating the above-described monomer reaction (polymerization reaction, crosslinking reaction, etc.), and is a promoter (first substance) activated by irradiation with actinic radiation described later. It is a substance whose activation temperature changes by the action of.

  As the catalyst precursor (procatalyst), any compound may be used as long as the activation temperature changes (increases or decreases) with irradiation of actinic radiation. Those whose activation temperature decreases with irradiation are preferred. As a result, the core layer 93 (optical waveguide 90) can be formed by heat treatment at a relatively low temperature, and unnecessary heat is applied to the other layers, which degrades the characteristics (optical transmission performance) of the optical waveguide 90. Can be prevented.

  As such a catalyst precursor, a catalyst precursor containing (mainly) at least one of the compounds represented by the following formulas (Ia) and (Ib) is preferably used.

［式Ｉａ、Ｉｂ中、それぞれ、Ｅ（Ｒ）_３は、第１５族の中性電子ドナー配位子を表し、Ｅは、周期律表の第１５族から選択される元素を表し、Ｒは、水素原子（またはその同位体の１つ）または炭化水素基を含む部位を表し、Ｑは、カルボキシレート、チオカルボキシレートおよびジチオカルボキシレートから選択されるアニオン配位子を表す。また、式Ｉｂ中、ＬＢは、ルイス塩基を表し、ＷＣＡは、弱配位アニオンを表し、ａは、１〜３の整数を表し、ｂは、０〜２の整数を表し、ａとｂとの合計は、１〜３であり、ｐおよびｒは、パラジウムカチオンと弱配位アニオンとの電荷のバランスをとる数を表す。］

[In the formulas Ia and Ib, E (R) ₃ represents a neutral electron donor ligand of group 15, respectively, E represents an element selected from group 15 of the periodic table, and R represents Represents a hydrogen atom (or one of its isotopes) or a moiety containing a hydrocarbon group, Q represents an anionic ligand selected from carboxylate, thiocarboxylate and dithiocarboxylate. In Formula Ib, LB represents a Lewis base, WCA represents a weakly coordinating anion, a represents an integer of 1 to 3, b represents an integer of 0 to 2, and a and b , P and r represent numbers that balance the charge of the palladium cation and the weakly coordinated anion. ]

Typical catalyst precursors according to Formula Ia include Pd (OAc) ₂ (P (i-Pr) ₃ ) ₂ , Pd (OAc) ₂ (P (Cy) ₃ ) ₂ , Pd (O ₂ CCMe ₃ ) ₂ (P (Cy) ₃ ) ₂ , Pd (OAc) ₂ (P (Cp) ₃ ) ₂ , Pd (O ₂ CCF ₃ ) ₂ (P (Cy) ₃ ) ₂ , Pd (O ₂ CC ₆ H ₅ ) ₃ (P (Cy) ₃ ) ₂ may be mentioned, but is not limited thereto. Here, Cp represents a cyclopentyl group, and Cy represents a cyclohexyl group.

  The catalyst precursor represented by the formula Ib is preferably a compound in which p and r are each selected from integers of 1 and 2.

Typical catalyst precursors according to such formula Ib include Pd (OAc) ₂ (P (Cy) ₃ ) ₂ . Here, Cy represents a cyclohexyl group, and Ac represents an acetyl group.

  These catalyst precursors can efficiently react with a monomer (in the case of a norbornene-based monomer, an efficient polymerization reaction, a crosslinking reaction, etc. by an addition polymerization reaction).

  In the state where the activation temperature is lowered (active latent state), the catalyst precursor has an activation temperature lower by about 10 to 80 ° C. (preferably about 10 to 50 ° C.) than the original activation temperature. Is preferred. Thereby, the refractive index difference between the core part 94 and the clad part 95 can be produced reliably.

Such a catalyst precursor includes (mainly) one containing at least one of Pd (OAc) ₂ (P (i-Pr) ₃ ) ₂ and Pd (OAc) ₂ (P (Cy) ₃ ) _2. Is preferred.

Hereinafter, Pd (OAc) ₂ (P (i-Pr) ₃ ) ₂ may be abbreviated as “Pd545”, and Pd (OAc) ₂ (P (Cy) ₃ ) ₂ may be abbreviated as “Pd785”. .

  The cocatalyst (first substance) is a substance that can be activated by irradiation with actinic radiation to change the activation temperature of the catalyst precursor (procatalyst) (the temperature at which the monomer reacts).

  As the cocatalyst (cocatalyst), any compound can be used as long as it has a molecular structure that changes (reacts or decomposes) when activated by irradiation with actinic radiation. A compound (photoinitiator) that decomposes upon irradiation with actinic radiation and generates a cation such as a proton or other cation and a weakly coordinated anion (WCA) that can be substituted with a leaving group of the catalyst precursor ( (Mainly) is preferably used.

Examples of the weak coordination anion include tetrakis (pentafluorophenyl) borate ion (FABA ⁻ ), hexafluoroantimonate ion (SbF ₆ ⁻ ), and the like.

  Examples of the cocatalyst (photoacid generator or photobase generator) include tetrakis (pentafluorophenyl) borate and hexafluoroantimonate represented by the following chemical formula 17, tetrakis (pentafluorophenyl) Examples include gallates, aluminates, antimonates, other borates, gallates, carboranes, halocarboranes, and the like.

An example of such a cocatalyst commercially available is “RHODORSIL (registered trademark, the same applies hereinafter) available from Rhodia USA, Cranberry, NJ.
“PHOTOINITIATOR 2074 (CAS No. 178233-72-2)”, “TAG-372R ((dimethyl (2- (2-naphthyl) -2-oxoethyl) sulfo) available from Toyo Ink Manufacturing Co., Ltd., Tokyo, Japan” Nitrotetrakis (pentafluorophenyl) borate: CAS number 193957-54-9)), “MPI-103 (CAS number 87709-41-9)” available from Midori Chemical Co., Tokyo, Japan, “TAG-371 (CAS No. 193957-53-8)” available from Toyo Ink Manufacturing Co., Ltd., Tokyo, Japan, “TTBPS-TPFPB” (Tris (available from Toyo Gosei Kogyo Co., Ltd., Tokyo, Japan) 4-tert-butylphenyl) sulfonium tetrakis (pentapentafluoro) Rophenyl) borate) ”,“ NAI-105 (CAS No. 85342-62-7) ”available from Midori Chemical Industries, Tokyo, Japan, and the like.

  When RHODORSIL PHOTOINITIATOR 2074 is used as the cocatalyst (first substance), ultraviolet rays (UV light) are preferably used as actinic radiation (chemical rays) described later, and mercury lamps ( A high-pressure mercury lamp) is preferably used. Thereby, ultraviolet rays (active radiation) having sufficient energy of less than 300 nm can be supplied to the layer 910, and RHODOLSIL PHOTOINITIATOR 2074 can be efficiently decomposed to generate the above-described cation and WCA.

  Moreover, you may make it add a sensitizer in the core layer forming material (varnish) 900 as needed.

  The sensitizer increases the sensitivity of the cocatalyst to actinic radiation, reduces the time and energy required for the activation (reaction or decomposition) of the cocatalyst, and the wavelength of the actinic radiation to a wavelength suitable for the activation of the cocatalyst. It has a function of changing the wavelength.

  Such a sensitizer is appropriately selected depending on the sensitivity of the promoter and the peak wavelength of absorption of the sensitizer, and is not particularly limited. For example, 9,10-dibutoxyanthracene (CAS No. 76275) is selected. 14-4) anthracenes, xanthones, anthraquinones, phenanthrenes, chrysenes, benzpyrenes, fluoranthenes, rubrenes, pyrenes, indanthrines, thioxanthen-9-ones (Thioxanthen-9-ones) and the like, and these are used alone or as a mixture.

  Specific examples of the sensitizer include 2-isopropyl-9H-thioxanthen-9-one, 4-isopropyl-9H-thioxanthen-9-one, 1-chloro-4-propoxythioxanthone, phenothiazine, and these Of the mixture.

  9,10-dibutoxyanthracene (DBA) can be obtained from Kawasaki Kasei Kogyo Co., Ltd., Kanagawa, Japan.

  The content of the sensitizer in the core layer forming material 900 is not particularly limited, but is preferably 0.01% by weight or more, more preferably 0.5% by weight or more, and 1% by weight or more. More preferably. In addition, it is preferable that an upper limit is 5 weight% or less.

  Furthermore, an antioxidant can be added to the core layer forming material 900. Thereby, generation | occurrence | production of an undesired free radical and the natural oxidation of the polymer 915 can be prevented. As a result, the characteristics of the obtained core layer 93 (optical waveguide 90) can be improved.

  Examples of the antioxidant include Ciba (registered trademark, the same applies hereinafter) IRGANOX (registered trademark, the same applies hereinafter) 1076 and Ciba IRGAFOS (registered trademark, available) from Ciba Specialty Chemicals of Tarrytown, New York. The same applies hereinafter.) 168 is preferably used.

  Other antioxidants include, for example, Ciba Irganox (registered trademark, hereinafter the same) 129, Ciba Irganox 1330, Ciba Irganox 1010, Ciba Cyanox (registered trademark, the same applies below) 1790, Ciba Irg. (Registered trademark) 3114, Ciba Irganox 3125, etc. can also be used.

  Note that such an antioxidant can be omitted, for example, when the layer 910 is not exposed to oxidation conditions or when the exposure period is extremely short.

  Examples of the solvent used for preparing the core layer forming material (varnish) 900 include diethyl ether, diisopropyl ether, 1,2-dimethoxyethane (DME), 1,4-dioxane, tetrahydrofuran (THF), tetrahydropyran (THP). ), Ether solvents such as anisole, diethylene glycol dimethyl ether (diglyme), diethylene glycol ethyl ether (carbitol), cellosolv solvents such as methyl cellosolve, ethyl cellosolve, phenyl cellosolve, aliphatic hydrocarbons such as hexane, pentane, heptane, cyclohexane Solvent, aromatic hydrocarbon solvent such as toluene, xylene, benzene, mesitylene, aromatic heterocyclic compound solvent such as pyridine, pyrazine, furan, pyrrole, thiophene, methylpyrrolidone, Amide solvents such as N, N-dimethylformamide (DMF) and N, N-dimethylacetamide (DMA), halogen compound solvents such as dichloromethane, chloroform and 1,2-dichloroethane, ethyl acetate, methyl acetate, ethyl formate, etc. Examples thereof include various organic solvents such as ester solvents, sulfur compound solvents such as dimethyl sulfoxide (DMSO) and sulfolane, and mixed solvents containing these.

  As a method for removing (desolving) the solvent from the liquid film formed on the support substrate 951, for example, natural drying, heating, leaving under reduced pressure, or blowing of an inert gas (blow) or the like is performed. Examples include forced drying.

  As described above, the layer 910 that is a film-like solidified product (or cured product) of the core layer forming material 900 is formed on the support substrate 951.

  At this time, the layer (dry film of PITDM) 910 has a first refractive index (RI). This first refractive index is due to the action of the polymer 915 and monomers that are uniformly dispersed (distributed) in the layer 910.

  [2A] Next, a mask (masking) 935 in which an opening (window) 9351 is formed is prepared, and the layer 910 is irradiated with active radiation (active energy light) 930 through the mask 935 (FIG. 3). reference).

  Hereinafter, a case where a monomer having a refractive index lower than that of the polymer 915 is used as a monomer, and a catalyst precursor whose activation temperature decreases with irradiation of the active radiation 930 will be described as an example.

  That is, in the example shown here, the irradiation region 925 of the active radiation 930 becomes the clad portion 95.

  Therefore, in the example shown here, an opening (window) 9351 equivalent to the pattern of the clad portion 95 to be formed is formed in the mask 935. This opening 9351 forms a transmission part through which the active radiation 930 to be irradiated passes.

  The mask 935 may be formed in advance (separately formed) (for example, plate-shaped) or may be formed on the layer 910 by, for example, a vapor deposition method or a coating method.

  Preferred examples of the mask 935 include a photomask made of quartz glass or a PET base material, a stencil mask, a metal thin film formed by a vapor deposition method (evaporation, sputtering, etc.), etc. Among these, it is particularly preferable to use a photomask or a stencil mask. This is because a fine pattern can be formed with high accuracy, and handling is easy, which is advantageous in improving productivity.

  In FIG. 3, an opening (window) 9351 equivalent to the pattern of the clad portion 95 to be formed is shown by partially removing the mask along the pattern of the unirradiated region 940 of the active radiation 930. In the case of using a photomask made of quartz glass, PET base material, or the like, it is also possible to use a photomask provided with a shielding portion of active radiation 930 made of a shielding material made of metal such as chromium. it can. In this mask, the part other than the shielding part is the window (transmission part).

  The actinic radiation 930 to be used is not particularly limited as long as it can cause a photochemical reaction (change) to the promoter. For example, in addition to visible light, ultraviolet light, infrared light, and laser light, an electron beam or X Lines or the like can also be used.

  Among these, the actinic radiation 930 is appropriately selected depending on the type of co-catalyst and the type of sensitizer when it contains a sensitizer, and is not particularly limited, but has a peak wavelength in the range of 200 to 450 nm. It is preferable to have it. Thereby, a cocatalyst can be activated comparatively easily.

The irradiation dose of the actinic radiation 930 is preferably in the range of about 0.1~9J / cm ^2, more preferably about ^{0.2~6J / cm 2, 0.2~3J / cm} 2 of about More preferably. Thereby, a promoter can be activated reliably.

  When the layer 910 is irradiated with the active radiation 930 through the mask 935, the cocatalyst (first substance: cocatalyst) present in the irradiation region 925 irradiated with the active radiation 930 reacts by the action of the active radiation 930. (Binding) or decomposition to release (generate) cations (protons or other cations) and weakly coordinating anions (WCA).

  These cations and weakly coordinating anions cause a change (decomposition) in the molecular structure of the catalyst precursor (second substance: procatalyst) present in the irradiation region 925, and this changes the active latent state (latent potential). Active state).

  Here, the catalyst precursor in the active latent state (or the latent active state) has an activation temperature lower than the original activation temperature, but there is no temperature increase, that is, at about room temperature, the irradiation region. It refers to a catalyst precursor that is in a state where a monomer reaction cannot occur within 925.

  Therefore, even after irradiation with the active radiation 930, if the layer 910 is stored at, for example, about −40 ° C., the state can be maintained without causing a monomer reaction. For this reason, the core layer 93 can be obtained by preparing a plurality of layers 910 after irradiation with the active radiation 930 and subjecting them to heat treatment at once, which is highly convenient.

  Note that in the case where light having high directivity such as laser light is used as the active radiation 930, the use of the mask 935 may be omitted.

[3A] Next, the layer 910 is subjected to heat treatment (first heat treatment).
Thereby, in the irradiation region 925, the catalyst precursor in the active latent state is activated (becomes active), and monomer reaction (polymerization reaction or cross-linking reaction) occurs.

  As the monomer reaction proceeds, the monomer concentration in the irradiation region 925 gradually decreases. As a result, a difference in monomer concentration occurs between the irradiated region 925 and the unirradiated region 940, and in order to eliminate this, the monomer diffuses from the unirradiated region 940 (monomer diffusion) and collects in the irradiated region 925. come.

  As a result, in the irradiated region 925, the monomer and its reaction product (polymer, cross-linked structure or branched structure) increase, and the structure derived from the monomer greatly affects the refractive index of the region, so that the first refraction The second refractive index lower than the refractive index. As the monomer polymer, an addition (co) polymer is mainly produced.

  On the other hand, in the unirradiated region 940, the amount of monomer decreases due to the diffusion of the monomer from the region to the irradiated region 925, so that the influence of the polymer 915 greatly appears on the refractive index of the region, and the first refraction The third refractive index rises higher than the refractive index.

  In this way, a refractive index difference (second refractive index <third refractive index) occurs between the irradiated region 925 and the non-irradiated region 940, and the core portion 94 (non-irradiated region 940) and the cladding portion 95. (Irradiation region 925) is formed (see FIG. 4).

  Although the heating temperature in this heat processing is not specifically limited, It is preferable that it is about 30-80 degreeC, and it is more preferable that it is about 40-60 degreeC.

  The heating time is preferably set so that the reaction of the monomer in the irradiation region 925 is almost completed. Specifically, the heating time is preferably about 0.1 to 2 hours, and 0.1 to 1 hour. More preferred is the degree.

[4A] Next, the layer 910 is subjected to a second heat treatment.
As a result, the catalyst precursor remaining in the unirradiated region 940 and / or the irradiated region 925 is activated (activated) directly or with activation of the cocatalyst, thereby causing the regions 925 and 940 to be activated. The remaining monomer is reacted.

  In this way, by reacting the monomers remaining in the regions 925 and 940, the core portion 94 and the clad portion 95 obtained can be stabilized.

  The heating temperature in the second heat treatment is not particularly limited as long as it can activate the catalyst precursor or the cocatalyst, but is preferably about 70 to 100 ° C, and is about 80 to 90 ° C. Is more preferable.

  The heating time is preferably about 0.5 to 2 hours, more preferably about 0.5 to 1 hour.

[5A] Next, the layer 910 is subjected to a third heat treatment.
Thereby, the internal stress generated in the obtained core layer 93 can be reduced, and the core portion 94 and the cladding portion 95 can be further stabilized.

  The heating temperature in the third heat treatment is preferably set to 20 ° C. or more higher than the heating temperature in the second heat treatment, specifically, preferably about 90 to 180 ° C., 120 to 160 ° C. More preferred is the degree.

  The heating time is preferably about 0.5 to 2 hours, more preferably about 0.5 to 1 hour.

The core layer 93 is obtained through the above steps.
For example, when a sufficient refractive index difference is obtained between the core portion 94 and the clad portion 95 in a state before the second heat treatment or the third heat treatment is performed, this step is performed. [5A] and the step [4A] may be omitted.

  [6A] Next, the cladding layer 91 (92) is formed on the support substrate 952 (see FIG. 5).

  As a method for forming the clad layer 91 (92), a method in which a varnish containing a clad material (clad layer forming material) is applied and cured (solidified), and a method in which a curable monomer composition is applied and cured (solidified). Any method may be used.

When the clad layer 91 (92) is formed by a coating method, examples thereof include a spin coating method, a dipping method, a table coating method, a spray method, an applicator method, a curtain coating method, and a die coating method.
As the support substrate 952, a substrate similar to the support substrate 951 can be used.

  Examples of the constituent material of the clad layer 91 (92) include acrylic resins, methacrylic resins, polycarbonate, polystyrene, epoxy resins, polyamides, polyimides, polybenzoxazoles, benzocyclobutene resins, and norbornene resins. These resins can be used, and one or more of these can be used in combination (polymer alloy, polymer blend (mixture), copolymer, composite (laminate), etc.).

  Of these, epoxy resins, polyimides, polybenzoxazoles, cyclic olefin resins such as benzocyclobutene resins and norbornene resins, and those containing them (mainly) in terms of particularly excellent heat resistance It is preferable to use it.

  When a (main) resin material containing a cyclic olefin resin, particularly a norbornene resin (norbornene polymer) is used as the material of the clad layer 91 (92), it is preferably used as a constituent material of the core layer 93. Since it is the same kind of material, the adhesion to the core layer 93 is further increased, and delamination between the clad layer 91 (92) and the core layer 93 can be prevented. For this reason, the optical waveguide 90 having excellent durability can be obtained.

  Examples of such norbornene-based polymers include (1) addition (co) polymers of norbornene monomers obtained by addition (co) polymerization of norbornene monomers, and (2) norbornene monomers and ethylene or α-olefins. (3) addition polymers such as addition copolymers with norbornene-type monomers and non-conjugated dienes, and other monomers as required, (4) ring opening of norbornene-type monomers ( A (co) polymer, and a resin obtained by hydrogenating the (co) polymer if necessary, (5) a ring-opening copolymer of a norbornene-type monomer and ethylene or α-olefins, and ( (Co) polymer hydrogenated resin, (6) ring-opening copolymer of norbornene type monomer and non-conjugated diene or other monomer, and (co) polymerization if necessary And a ring-opening polymer such as a polymer obtained by hydrogenating the body. Examples of these polymers include random copolymers, block copolymers, and alternating copolymers.

  These norbornene-based polymers include, for example, ring-opening metathesis polymerization (ROMP), combination of ROMP and hydrogenation reaction, polymerization by radical or cation, polymerization using a cationic palladium polymerization initiator, and other polymerization initiators ( For example, it can be obtained by any known polymerization method such as polymerization using a polymerization initiator of nickel or another transition metal).

  Among these, as the norbornene-based polymer, an addition (co) polymer is preferable. This is preferable because it is rich in transparency, heat resistance and flexibility.

  The norbornene-based polymer used for the cladding layers 91 and 92 is preferably one having a relatively low refractive index.

  As the norbornene-based polymer having a relatively low refractive index, those containing a norbornene repeating unit having a substituent containing an epoxy structure at the terminal are preferable. Such norbornene-based polymers have a particularly low refractive index.

  Further, the norbornene-based polymer preferably contains an alkylnorbornene repeating unit. Since the norbornene-based polymer containing the alkylnorbornene repeating unit has high flexibility, high flexibility (flexibility) can be imparted to the optical waveguide 90 by using such norbornene-based polymer.

  Examples of the alkyl group that the alkylnorbornene repeating unit has include a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group, and a hexyl group is particularly preferable. These alkyl groups may be either linear or branched.

By including the repeating unit of hexyl norbornene, it is possible to prevent the refractive index of the entire norbornene-based polymer from increasing. A norbornene-based polymer having a repeating unit of hexyl norbornene is preferable because it has excellent transmittance with respect to light in the wavelength region as described above (particularly in the wavelength region near 850 nm).
The clad layer 91 (92) may be any material as long as it has a refractive index lower than that of the core portion 94 of the core layer 93, and the core layer forming material as described above may be used.
As described above, the clad layer 91 (92) is formed on the support substrate 952.

  [7A] Next, the core layer 93 is peeled from the support substrate 951, and the core layer 93 is sandwiched between the support substrate 952 on which the cladding layer 91 is formed and the support substrate 952 on which the cladding layer 92 is formed ( (See FIG. 6).

Then, as indicated by the arrows in FIG. 6, pressure is applied from the upper surface side of the support substrate 952 on which the cladding layer 92 is formed, and the cladding layers 91 and 92 and the core layer 93 are pressure bonded.
Thereby, the clad layers 91 and 92 and the core layer 93 are joined and integrated.

  Further, this crimping operation is preferably performed under heating. The heating temperature is appropriately determined depending on the constituent materials of the clad layers 91 and 92 and the core layer 93, and is usually preferably about 80 to 200 ° C, more preferably about 120 to 180 ° C.

  Next, the support substrate 952 is peeled off and removed from the cladding layers 91 and 92, respectively. Thereby, the optical waveguide 90 is obtained.

  [8A] Next, conductor layers 901 and 902 are formed on the upper and lower surfaces of the optical waveguide 90, respectively (see FIG. 7).

As a method for forming each of the conductor layers 901 and 902, for example, a chemical vapor deposition method (CVD method) such as a plasma CVD method, a thermal CVD method, or a laser CVD method, a vacuum deposition method, a sputtering method, or an ion is used. Among the bonding of conductive sheet materials by dry plating methods such as physical vapor deposition methods (PVD methods) such as plating methods, wet plating methods such as electrolytic plating, immersion plating and electroless plating, and laminating methods At least one of the following can be used. Thereby, high adhesiveness between each of the conductor layers 901 and 902 and the optical waveguide 90 is obtained.
As described above, the optical waveguide structure 9 of the present invention is completed.

  In a preferred example of such an optical waveguide structure 9, in the core layer 93, the core portion 94 is configured with the first norbornene-based material as a main material, and the cladding portion 95 has a lower refractive index than that of the first norbornene-based material. The second norbornene-based material is used as a main material, and the cladding layers 91 and 92 each have a lower refractive index than the first norbornene-based material, and the third norbornene-based material containing the norbornene-based polymer is used as the main material. Configured as

  The first norbornene-based material and the second norbornene-based material both contain the same norbornene-based polymer, but contain a reaction product of a norbornene-based monomer having a refractive index different from that of the norbornene-based polymer. Due to the different amounts, the refractive indices are different from each other.

  Since the norbornene-based polymer has high transparency, the optical waveguide structure 9 having such a configuration can provide high optical transmission performance of the optical waveguide 90.

  Further, with such a configuration, not only high adhesion between the core portion 94 and the clad portion 95 but also high adhesion between the core layer 93, the clad layer 91, and the clad layer 92 can be obtained. Even when deformation such as bending occurs in the structure 9, peeling between the core portion 94 and the clad portion 95 and delamination between the core layer 93 and the clad layers 91 and 92 do not easily occur. It is also possible to prevent micro cracks from occurring in 95. As a result, the optical transmission performance of the optical waveguide 90 is maintained.

  Further, since the norbornene-based polymer has high heat resistance and high hydrophobicity, the optical waveguide 90 (optical waveguide structure 9) having such a configuration has excellent durability.

  In addition, since high heat resistance and high hydrophobicity can be imparted to the optical waveguide 90, the conductor layers 901 and 902 can be formed by adopting various methods as described above while preventing deterioration (deterioration) of the characteristics. It can be reliably formed. In particular, even when the conductor layers 901 and 902 are formed so as to overlap with the core portion 94 important for light transmission, the core portion 94 can be prevented from being deteriorated or deteriorated.

  Further, according to the manufacturing method as described above, the optical waveguide structure 9 having the core portion 94 having a desired shape and high dimensional accuracy can be obtained by a simple process and in a short time. .

<Second production method>
Next, a second manufacturing method of the optical waveguide structure 9 will be described.

  Hereinafter, the second manufacturing method will be described, but the description will focus on differences from the first manufacturing method, and description of similar matters will be omitted.

  In the second manufacturing method, the composition of the core layer forming material 900 is different, and the rest is the same as the first manufacturing method.

That is, the core layer forming material 900 used in the second production method is a release agent (substance) that is activated by irradiation with actinic radiation and the action of the release agent activated by branching from the main chain and the main chain. Thus, at least a part of the molecular structure contains a polymer 915 having a leaving group (leaving pendant group) that can leave from the main chain.
As the releasing agent, the same promoter as that mentioned in the first production method can be used.

  Examples of the polymer 915 used in the second production method include those obtained by substituting the substituents of the polymer 915 exemplified in the first production method with a leaving group, and polymers 915 exemplified in the first production method. The thing which introduce | transduced the leaving group is mentioned.

  The refractive index of the polymer 915 changes (increases or decreases) due to the leaving (cleavage) of the leaving group.

  The leaving group may be any of those leaving by the action of a cation, anion or free radical, that is, any of an acid (cation) leaving group, a base (anion) leaving group, and a free radical leaving group. Although it is good, it is preferably a group capable of leaving by the action of a cation (proton) (acid group leaving group).

  As the acid leaving group, those having at least one of an —O— structure, an —Si—aryl structure and an —O—Si— structure in its molecular structure are preferable. Such an acid leaving group is released relatively easily by the action of a cation.

  Among these, as the acid leaving group that causes a decrease in the refractive index of the polymer 915 by leaving, at least one of a -Si-diphenyl structure and a -O-Si-diphenyl structure is preferable.

  In addition, as a free radical leaving group which leaves | separates by the effect | action of a free radical, the substituent etc. which have an acetophenone structure at the terminal are mentioned, for example.

  The polymer 915 is preferably a norbornene polymer for the same reason as described in the first production method, and more preferably a norbornene polymer containing a repeating unit of alkyl (particularly hexyl) norbornene. preferable.

  In consideration of the above, as the polymer 915 whose refractive index decreases due to the leaving group leaving, a homopolymer of diphenylmethylnorbornenemethoxysilane or a copolymer of hexylnorbornene and diphenylmethylnorbornenemethoxysilane is preferably used. .

  Hereinafter, as an example, a case where the polymer 915 has a refractive index that decreases due to the removal of a leaving group (particularly, an acid leaving group) will be described.

  That is, in the example shown here, the irradiation region 925 of the active radiation 930 becomes the clad portion 95.

[1B] A step similar to the step [1A] is performed.
At this time, the layer (dry film of PITDM) 10 has a first refractive index (RI). This first refractive index is due to the action of the polymer 915 that is uniformly dispersed (distributed) in the layer 910.

[2B] A step similar to the step [2A] is performed.
When the layer 910 is irradiated with the actinic radiation 930 through the mask 935, the release agent present in the irradiation region 925 irradiated with the actinic radiation 930 reacts (bonds) or decomposes by the action of the actinic radiation 930, and becomes a cation. Liberate (generate) protons (or other cations) and weakly coordinating anions (WCA).

  Then, the cation causes the leaving group itself to leave the main chain, or cleaves from the middle of the molecular structure of the leaving group (photo bleach).

  As a result, in the irradiated region 925, the number of leaving groups in a complete state is decreased as compared with the unirradiated region 940, and the second refractive index is lower than the first refractive index. At this time, the refractive index of the unirradiated region 940 is maintained at the first refractive index.

  In this way, a refractive index difference (second refractive index <first refractive index) occurs between the irradiated region 925 and the non-irradiated region 940, and the core portion 94 (non-irradiated region 940) and the cladding portion 95. (Irradiation region 925) is formed.

In this case, the irradiation dose of the actinic radiation 930 is preferably in the range of about 0.1~9J / cm ^2, more preferably about 0.3~6J / cm ^2, 0.6~6J / More preferably, it is about cm ² . Thereby, a release agent can be activated reliably.

[3B] Next, the layer 910 is subjected to heat treatment.
As a result, the leaving group detached (cut) from the polymer 915 is removed from the irradiated region 925 or rearranged or cross-linked in the polymer 915.

  Further, at this time, it is considered that a part of the leaving group remaining in the cladding part 95 (irradiation region 925) is further detached (cut).

  Therefore, the refractive index difference between the core portion 94 and the cladding portion 95 can be further increased by performing such heat treatment.

  Although the heating temperature in this heat processing is not specifically limited, It is preferable that it is about 70-195 degreeC, and it is more preferable that it is about 85-150 degreeC.

  Further, the heating time is set so as to sufficiently remove the leaving group detached (cut) from the irradiation region 925, and is not particularly limited, but is preferably about 0.5 to 3 hours, More preferably, it is about 2 hours.

  For example, when a sufficient refractive index difference is obtained between the core portion 94 and the cladding portion 95 in a state before the heat treatment, this step [3B] may be omitted. .

Moreover, the process of 1 time or several times of heat processing (for example, about 150-200 degreeC x about 1 to 8 hours) can also be added as needed.
The core layer 93 is obtained through the above steps.

[4B] A step similar to the step [6A] is performed.
[5B] A step similar to the step [7A] is performed.

[6B] A step similar to the step [8A] is performed.
As described above, the optical waveguide structure 9 of the present invention is completed.

  In a preferred example of such an optical waveguide structure 9, the core layer 93 is composed of a norbornene-based material as a main material, and the cladding layers 91 and 92 each have a lower refractive index than the core portion 94 of the core layer 93, and norbornene The main material is a norbornene-based material containing a polymer.

  The core portion 94 and the clad portion 95 are mainly composed of a norbornene-based polymer having a main chain and a main chain branched from the main chain and having a leaving group capable of leaving at least a part of the molecular structure from the main chain. The core part 94 and the clad part 95 have different refractive indexes due to the difference in the number of leaving groups bonded to the main chain.

  Since the norbornene-based polymer has high transparency, the optical waveguide structure 9 having such a configuration can provide high optical transmission performance of the optical waveguide 90.

  Further, with such a configuration, not only high adhesion between the core portion 94 and the clad portion 95 but also high adhesion between the core layer 93, the clad layer 91, and the clad layer 92 can be obtained. Even when deformation such as bending occurs in the structure 9, peeling between the core portion 94 and the clad portion 95 and delamination between the core layer 93 and the clad layers 91 and 92 do not easily occur. It is also possible to prevent micro cracks from occurring in 95. As a result, the optical transmission performance of the optical waveguide 90 is maintained.

  Further, since the norbornene-based polymer has high heat resistance and high hydrophobicity, the optical waveguide 90 (optical waveguide structure 9) having such a configuration has excellent durability.

  In addition, since high heat resistance and high hydrophobicity can be imparted to the optical waveguide 90, the conductor layers 901 and 902 can be formed by adopting various methods as described above while preventing deterioration (deterioration) of the characteristics. It can be reliably formed. In particular, even when the conductor layers 901 and 902 are formed so as to overlap with the core portion 94 important for light transmission, the core portion 94 can be prevented from being deteriorated or deteriorated.

  Further, according to the manufacturing method as described above, the optical waveguide structure 9 having the core portion 94 having a desired shape and high dimensional accuracy can be obtained by a simple process and in a short time. .

  In particular, according to the second manufacturing method, at least actinic radiation may be used, and the core layer 93 can be formed by an extremely simple process.

<Third production method>
Next, the 3rd manufacturing method of the optical waveguide structure 9 is demonstrated.

  Hereinafter, the third manufacturing method will be described, but the description will focus on differences from the first and second manufacturing methods, and the description of the same matters will be omitted.

  In the third manufacturing method, a combination of the core layer forming materials used in the first and second manufacturing methods is used as the core layer forming material 900. Otherwise, the first or second manufacturing method is used. It is the same as the method.

  That is, the core layer forming material 900 used in the third manufacturing method includes a polymer 915 having a leaving group as described above, a monomer, a promoter (first substance), and a catalyst precursor (second Substance). The cocatalyst is the same as the release agent in the second production method, and has a function of releasing the release agent.

  In such a core layer forming material 900, the refractive index difference between the core portion 94 and the clad portion 95 is more increased in the obtained core layer 93 due to the combination of the selected leaving group and the selected monomer. It becomes possible to adjust in stages.

  As described above, a monomer having a refractive index lower than that of the polymer 915 is used as a monomer, and a catalyst precursor whose activation temperature is reduced with irradiation of the active radiation 930 is used as a polymer 915. If a material whose refractive index is lowered by the removal of the leaving group is used, the irradiation region 925 can be used as the cladding portion 95, and the core layer 93 having a very large refractive index difference from the core portion 94 can be obtained.

  Hereinafter, a case where such a combination of the polymer 915, the monomer, and the catalyst precursor is used will be described as an example.

  That is, in the example shown here, the irradiation region 925 of the active radiation 930 becomes the clad portion 95.

[1C] A step similar to the step [1A] is performed.
At this time, the layer (dry film of PITDM) 910 has a first refractive index (RI). This first refractive index is due to the action of the polymer 915 and monomers that are uniformly dispersed (distributed) in the layer 910.

[2C] A step similar to the step [2A] is performed.
When the layer 910 is irradiated with the active radiation 930 through the mask 935, the cocatalyst (first substance: cocatalyst) present in the irradiation region 925 irradiated with the active radiation 930 reacts by the action of the active radiation 930. Alternatively, it decomposes to liberate (generate) cations (protons or other cations) and weakly coordinating anions (WCA).

  These cations and weakly coordinating anions cause a change (decomposition) in the molecular structure of the catalyst precursor (second substance: procatalyst) present in the irradiation region 925, and this changes the active latent state (latent potential). Active state).

  In addition, the cation causes the leaving group itself to leave the main chain, or cleaves from the middle of the molecular structure of the leaving group.

  As a result, in the irradiated region 925, the number of leaving groups in a complete state is reduced as compared with the non-irradiated region 940, and the refractive index is lowered to be lower than the first refractive index. At this time, the refractive index of the unirradiated region 940 is maintained at the first refractive index.

In this case, the irradiation dose of the actinic radiation 930 is preferably in the range of about 0.1~9J / cm ^2, more preferably about 0.2~5J / cm ^2, 0.2~4J / More preferably, it is about cm ² . Thereby, a promoter can be activated reliably.

[3C] The same step as the above step [3A] is performed.
Thereby, in the irradiation region 925, the catalyst precursor in the active latent state is activated (becomes active), and monomer reaction (polymerization reaction or cross-linking reaction) occurs.

  As the monomer reaction proceeds, the monomer concentration in the irradiation region 925 gradually decreases. As a result, there is a difference in monomer concentration between the irradiated region 925 and the unirradiated region 940, and the monomer diffuses from the unirradiated region 940 and collects in the irradiated region 925 in order to eliminate this.

  In addition, by this heat treatment, the leaving group detached (cut) from the polymer 915 is removed from, for example, the irradiation region 925, or rearranged or crosslinked in the polymer 915.

  As a result, in the irradiated region 925, the monomer and its reactant (polymer, cross-linked structure and branched structure) increase, and the structure derived from the monomer greatly affects the refractive index of the region. The refractive index is further lowered to the second refractive index due to a decrease in the leaving (cleaved) leaving group.

  On the other hand, in the unirradiated region 940, the amount of monomer decreases due to the diffusion of the monomer from the region to the irradiated region 925, so that the influence of the polymer 915 greatly appears on the refractive index of the region, and the first refraction The third refractive index rises higher than the refractive index.

  In this way, a refractive index difference (second refractive index <third refractive index) occurs between the irradiated region 925 and the non-irradiated region 940, and the core portion 94 (non-irradiated region 940) and the cladding portion 95. (Irradiation region 925) is formed.

[4C] A step similar to the step [4A] is performed.
[5C] A step similar to the step [5A] is performed.

[6C] The same step as the above step [6A] is performed.
[7C] The same step as the above step [7A] is performed.

[8C] The same step as the above step [8A] is performed.
As described above, the optical waveguide structure 9 of the present invention is completed.

  In a preferred example of such an optical waveguide structure 9, the core layer 93 is a norbornene polymer having a main chain and a leaving group that is branched from the main chain and at least a part of the molecular structure can be detached from the main chain. The core portion 94 and the clad portion 95 are different in the number of leaving groups bonded to the main chain and the reaction product of a norbornene monomer having a refractive index different from that of the norbornene polymer. Due to the different contents, their refractive indexes are different, and the cladding layers 91 and 92 are each composed mainly of a norbornene-based material containing a norbornene-based polymer.

  Since the norbornene-based polymer has high transparency, the optical waveguide structure 9 having such a configuration can provide high optical transmission performance of the optical waveguide 90.

  Further, with such a configuration, not only high adhesion between the core portion 94 and the clad portion 95 but also high adhesion between the core layer 93, the clad layer 91, and the clad layer 92 can be obtained. Even when deformation such as bending occurs in the structure 9, peeling between the core portion 94 and the clad portion 95 and delamination between the core layer 93 and the clad layers 91 and 92 do not easily occur. It is also possible to prevent micro cracks from occurring in 95. As a result, the optical transmission performance of the optical waveguide 90 is maintained.

  Further, since the norbornene-based polymer has high heat resistance and high hydrophobicity, the optical waveguide 90 (optical waveguide structure 9) having such a configuration has excellent durability.

  In addition, since high heat resistance and high hydrophobicity can be imparted to the optical waveguide 90, the conductor layers 901 and 902 can be formed by adopting various methods as described above while preventing deterioration (deterioration) of the characteristics. It can be reliably formed. In particular, even when the conductor layers 901 and 902 are formed so as to overlap with the core portion 94 important for light transmission, the core portion 94 can be prevented from being deteriorated or deteriorated.

  Further, according to the manufacturing method as described above, the optical waveguide structure 9 having the core portion 94 having a desired shape and high dimensional accuracy can be obtained by a simple process and in a short time. .

  In particular, according to the third manufacturing method, the refractive index difference between the core portion 94 and the cladding portion 95 can be set in multiple stages.

<Fourth manufacturing method>
Next, the 4th manufacturing method of the optical waveguide structure 9 is demonstrated.

  8 to 13 are cross-sectional views schematically showing process examples of the fourth manufacturing method of the optical waveguide structure of the present invention.

  Hereinafter, although the 4th manufacturing method is explained, it explains centering on difference with the 1st-3rd manufacturing methods, and omits the explanation about the same matter.

  In the fourth manufacturing method, the formation process of the optical waveguide 90 is different, and the other processes are the same as those in the first to third manufacturing methods.

  That is, as the core layer forming material 900 and the clad layer forming material, the same materials as described in the first to third manufacturing methods can be used.

  In the following description, the case where the materials described in the first manufacturing method are used as the core layer forming material will be described as a representative.

  [1D] First, a clad layer forming material (first varnish) is applied onto the support substrate 1000 using the same method as described above to form the first layer 1110 (see FIG. 8). .

As the support substrate 1000, a substrate similar to the support substrate 951 can be used.
The average thickness of the first layer 1110 is not particularly limited, but is preferably about 5 to 200 μm, more preferably about 10 to 100 μm, and still more preferably about 15 to 65 μm.

  [2D] Next, a core layer forming material (second varnish) is applied onto the first layer 1110 using the same method as described above to form the second layer 1120 (FIG. 9).

  The core layer forming material may be applied after the first layer 1110 is almost completely dried, or may be applied before the first layer 1110 is dried.

  In the latter case, the first layer 1110 and the second layer 1120 are mixed with each other at the interface between them. In this case, in the obtained optical waveguide 90, the adhesion between the clad layer 91 and the core layer 93 can be improved.

  In this case, each of the first varnish and the second varnish is prepared so that the viscosity (normal temperature) is preferably about 100 to 10000 cP, more preferably about 150 to 5000 cP, and further preferably about 200 to 3500 cP. Thus, the first layer 1110 and the second layer 1120 can be prevented from being mixed more than necessary at the interface between them, and the thicknesses of the first layer 1110 and the second layer 1120 can be reduced. Nonuniformity can be prevented.

  The viscosity of the second varnish is preferably higher than that of the first varnish. Accordingly, it is possible to reliably prevent the first layer 1110 and the second layer 1120 from being mixed more than necessary at the interface between them.

  The average thickness of the second layer 1120 is not particularly limited, but is preferably about 5 to 200 μm, more preferably about 15 to 125 μm, and still more preferably about 25 to 100 μm.

  [3D] Next, a clad layer forming material (third varnish) is applied onto the second layer 1120 using the same method as described above to form the third layer 1130 (FIG. 10).

The third layer 1130 can be formed in the same manner as the second layer 1120.
The average thickness of the third layer 1130 is not particularly limited, but is preferably about 5 to 200 μm, more preferably about 10 to 100 μm, and still more preferably about 15 to 65 μm.
Thereby, the laminated body 2000 is obtained.

[4D] Next, the solvent in the laminate 2000 is removed (desolvent).
Examples of the method for removing the solvent include methods such as heating, leaving under atmospheric pressure or reduced pressure, and spraying (blowing) an inert gas, etc., but a method using heating is preferred. Thereby, it is possible to remove the solvent relatively easily and in a short time.

  The heating temperature is preferably about 25 to 60 ° C, and more preferably about 30 to 45 ° C.

  The heating time is preferably about 15 to 60 minutes, and more preferably about 15 to 30 minutes.

  [5D] Next, a mask (masking) 935 in which an opening (window) 9351 is formed is prepared, and active radiation (active energy ray) 930 is irradiated to the stacked body 2000 through the mask 935 (FIG. 11).

  When the stacked body 2000 is irradiated with the active radiation 930 through the mask 935, the promoter (first substance: cocatalyst) present in the irradiation region 925 irradiated with the active radiation 930 of the second layer 1120 is: It reacts or decomposes by the action of actinic radiation 930 to liberate (generate) cations (protons or other cations) and weakly coordinating anions (WCA).

  These cations and weakly coordinating anions cause a change (decomposition) in the molecular structure of the catalyst precursor (second substance: procatalyst) present in the irradiation region 925, and this changes the active latent state (latent potential). Active state).

[6D] Next, heat treatment (first heat treatment) is performed on the stacked body 2000.
Thereby, in the irradiation region 925, the catalyst precursor in the active latent state is activated (becomes active), and monomer reaction (polymerization reaction or cross-linking reaction) occurs.

  As the monomer reaction proceeds, the monomer concentration in the irradiation region 925 gradually decreases. As a result, there is a difference in monomer concentration between the irradiated region 925 and the unirradiated region 940, and the monomer diffuses from the unirradiated region 940 and collects in the irradiated region 925 in order to eliminate this.

  As a result, in the irradiated region 925, the monomer and its reaction product (polymer, cross-linked structure or branched structure) increase, and the structure derived from the monomer greatly affects the refractive index of the region, so that the first refraction The second refractive index lower than the refractive index.

  On the other hand, in the unirradiated region 940, the amount of monomer decreases due to the diffusion of the monomer from the region to the irradiated region 925, so that the influence of the polymer 915 greatly appears on the refractive index of the region, and the first refraction The third refractive index rises higher than the refractive index.

  In this way, a refractive index difference (second refractive index <third refractive index) occurs between the irradiated region 925 and the non-irradiated region 940, and the core portion 94 (non-irradiated region 940) and the cladding portion 95. (Irradiation region 925) is formed (see FIG. 12).

[7D] Next, the stacked body 2000 is subjected to a second heat treatment.
As a result, the catalyst precursor remaining in the unirradiated region 940 and / or the irradiated region 925 is activated (activated) directly or with activation of the cocatalyst, thereby causing the regions 925 and 940 to be activated. The remaining monomer is reacted.

  In this way, by reacting the monomers remaining in the regions 925 and 940, the core portion 94 and the clad portion 95 obtained can be stabilized.

[8D] Next, the stacked body 2000 is subjected to a third heat treatment.
Thereby, the internal stress generated in the obtained core layer 93 can be reduced, and the core portion 94 and the cladding portion 95 can be further stabilized.
The optical waveguide 90 is obtained through the above steps.

[9D] Next, conductor layers 901 and 902 are formed on the upper and lower surfaces of the optical waveguide 90, respectively (see FIG. 13).
This can be performed in the same manner as in the step [8A].

As described above, the optical waveguide structure 9 of the present invention is completed.
In such a method, the core portion 94 can be visually confirmed in the stacked body 2000 after the first heat treatment.

  Further, as the first varnish and the third varnish, the same composition as that of the second varnish, that is, one containing a polymer 915, a monomer, a promoter and a catalyst precursor may be used. Accordingly, the monomer reaction causes the interface between the first layer 1110 and the third layer 1130 and the second layer 1120, and / or beyond the interface, in the first layer 1110 and the third layer 1130. And the peeling between the clad layers 91 and 92 and the core layer 93 can be prevented more reliably.

  Further, in this case, for example, I: As the polymer 915 of the first layer 1110 and the third layer 1130, one having a refractive index (RI) relatively lower than the refractive index of the polymer 915 of the second layer 1120 is selected. II: The same monomer as the second layer 1120 is used as the monomer of the first layer 1110 and the third layer 1130, but the catalyst precursor in the first layer 1110 and the third layer 1130 and The monomer ratio may be adjusted to be lower than that of the second layer 1120.

  Accordingly, even when the active radiation 930 is irradiated, it is possible to prevent the formation of a region having a refractive index higher than that of the core portion 94 of the core layer 93 in the cladding layers 91 and 92.

  When a material containing a polymer 915 having a leaving group is used as the core layer forming material (second varnish), the cladding layer forming material (first varnish, third varnish) A polymer prepared using a polymer 915 having no releasing group is used, or a polymer 915 having a releasing group is used, but a polymer containing no releasing agent may be used.

Thereby, in the first layer 1110 and the third layer 1130, it is possible to prevent the leaving group from leaving (decomposing) from the polymer 915.
In the fourth production method, it is preferable to use the first varnish and the third varnish containing a norbornene-based polymer having a substituent containing an epoxy structure at the terminal and a promoter. Thereby, when forming the core part 94 and the clad part 95, an epoxy structure is cleaved and a reaction (polymerization) with the polymer 915 of the core layer 93 comes to occur. As a result, the adhesion of the cladding layers 91 and 92 to the core layer 93 can be improved.

  Examples of such norbornene-based polymers include copolymers of hexyl norbornene (HxNB) and norbornene methyl glycidyl ether (AGENB).

  In this case, a promoter that is not activated when the core layer 93 is formed may be selected. For example, a cocatalyst that does not absorb actinic radiation suitable for activating the cocatalyst contained in the second varnish or is activated by the action of heat in place of the actinic radiation may be selected.

  Examples of such a co-catalyst include a non-absorbing photobase generator (PBG) and a thermal base generator (TBG).

  In the first to fourth manufacturing methods, the support substrates 951, 952, and 1000 have been described as being removed. However, these are made of a conductive material, and the conductor layer 901 is left as it is without being removed. , 902 may be used.

  Moreover, you may abbreviate | omit either one or both of the clad layers 91 and 92 as needed.

  Further, the optical waveguide 90 is not limited to the configuration shown in the figure. For example, the optical waveguide 90 may have a configuration in which a plurality of core layers are provided between two cladding layers. May be laminated in order, or a laminated body in which a single core layer is provided between two clad layers may be laminated.

  In addition, an inclined surface (reflecting surface) inclined by approximately 45 ° with respect to the optical path, that is, the longitudinal direction of the core portion 94 may be formed in the middle of the core portion 94. Thereby, the light (transmission light) propagating through the core portion 94 can be bent by approximately 90 ° on this inclined surface.

  Then, by appropriately setting the direction of the inclined surface, the optical path of the transmitted light is changed not only in the core layer 90 (two-dimensional direction) but also in a three-dimensional direction including the thickness direction of the optical waveguide 90. Is possible.

  This inclined surface can be formed by, for example, cutting or removing (deleting) the core portion 94. A reflective film such as a multilayer optical thin film or a metal thin film (for example, an aluminum vapor deposition film) or a reflection increasing film may be formed on the inclined surface.

  As described above, the waveguide structure of the present invention has been described based on the illustrated embodiments. However, the present invention is not limited to these, and the configuration of each part may be any configuration that can exhibit the same function. It can be substituted, and an arbitrary configuration may be added.

Hereinafter, specific examples of the present invention will be described.
1. Synthesis of Catalyst Precursor << Catalyst Precursor C1: Synthesis of Pd (OAc) ₂ (P (i-Pr) ₃ ) ₂ >>
A nitrogen-filled flask equipped with a funnel was charged with a solution of P (i-Pr) ₃ (8.51 mL (44.6 mmol)) in CH ₂ Cl ₂ (20 mL) and Pd (OAc) ₂ (5.00 g, 22.3 mmol). ) And CH ₂ Cl ₂ (30 mL) was added dropwise to a stirred red-brown suspension at −78 ° C.

  The suspension gradually passed through a yellowish green solution, then warmed to room temperature and stirred for 2 hours. Then, it filtered with the 0.45 micrometer filter.

The filtrate was concentrated to 10 mL and hexane (20 mL) was added to give a yellow solid.
This was filtered (in air), washed with hexane (5 × 5 mL) and vacuum dried.

The yield was 10.937 g (89%). The NMR data was as follows. ¹ H-NMR (δ, CD ₂ Cl ₂ ): 1.37 (dd, 36H, CHCH ₃ ), 1.77 (s, 6H, CCH ₃ ), 2.12 (m, 6H, CH), ³¹ P _{-NMR (δ, CD 2 Cl 2} ): 32.9 (s).

<< Catalyst Precursor C2: Synthesis of Pd (OAc) ₂ (P (Cy) ₃ ) ₂ >>
In a 2-neck round bottom flask equipped with a funnel, a reddish brown suspension consisting of Pd (OAc) ₂ (5.00 g, 22.3 mmol) and CH ₂ Cl ₂ (30 mL) was stirred at −78 ° C.

A funnel was charged with a CH ₂ Cl ₂ solution (30 mL) of P (Cy) ₃ (13.12 mL (44.6 mmol)) and added dropwise to the stirred suspension over 15 minutes. As a result, the color gradually changed from reddish brown to yellow.

  After stirring at −78 ° C. for 1 hour, the suspension was warmed to room temperature, stirred for an additional 2 hours, and diluted with hexane (20 mL).

  The yellow solid was then filtered in air, washed with pentane (5 × 10 mL) and dried in vacuo.

The secondary collection was separated by cooling the filtrate to 0 ° C., washed and dried as above.
The yield was 15.42 g (88%). The NMR data was as follows. ¹ H-NMR (δ, CD ₂ Cl ₂ ): 1.18-1.32 (br m, 18 H, Cy), 1.69 (br m, 18 H, Cy), 1.80 (br m, 18 H, Cy), 1.84 (s, 6H, CH ₃ ), 2.00 (br d, 12H, Cy), ³¹ P-NMR (δ, CD ₂ Cl ₂ ): 21.2 (s).

<< catalyst precursor _{C3: trans-Pd (O 2} C-t-Bu) 2 (P (Cy) 3) 2 Synthesis >>
Pd (O ₂ Ct-Bu) ₂ (1.3088 g, 4.2404 mmol) was dispersed in CH ₂ Cl ₂ (10 mL) in a Schlenker flask and the flask contents were cooled to −78 ° C. and allowed to stir. It was.

To this solution was added a solution of P (Cy) ₃ (2.6749 g, 9.5382 mmol) in CH ₂ Cl ₂ (15 mL) and stirred at −78 ° C. for 1 hour and at room temperature for 2 hours.

  Hexane (20 mL) was added to the reaction mixture to give the title yellow solid complex (1.391 g).

The solid was filtered, washed with hexane (10 mL) and dried under reduced pressure.
Solvent was removed from the filtrate to give an orange solid, which was then dissolved in a CHCl ₃ / hexane mixture (1/1: v / v) and the resulting solution was evaporated in a fume hood. The indicated complex was further obtained (648 mg).

The overall yield was 2.039 g (2.345 mmol, 55.3%).
Calculated as C ₄₆ H ₈₄ O ₄ P ₂ Pd, C is 63.54% and H is 9.74%.

<< Catalyst Precursor C4: Synthesis of Pd (OAc) ₂ (P (Cp) ₃ ) ₂ >>
A red-brown suspension of Pd (OAc) ₂ (2.00 g, 8.91 mmol) in CH ₂ Cl ₂ (˜25 mL) was stirred at −78 ° C. in a nitrogen-filled flask.

With a cannula, P (Cp) ₃ (4.25 g, 17.83 mmol) was dissolved in CH ₂ Cl ₂ (˜20 mL) and added dropwise to the suspension over 10 min. As a result, the color gradually changed from reddish brown to yellow.

  The suspension was warmed to room temperature and stirred for an additional hour. The solvent was concentrated (˜5 mL) and hexane (˜15 mL) was added to give a yellow solid.

  It was filtered in air, washed with hexane (5 × 10 mL) and dried in vacuo. The secondary collection was separated by cooling the filtrate to 0 ° C., filtered, washed and dried in the same manner as catalyst precursor C3.

The yield was 4.88 g (85%). The NMR data was as follows. _{^{1 H-NMR (δ, CD}} 2 Cl 2): 1.52-1.56 (br m, 12H, Cp 3), 1.67-1.72 (br m, 12H, Cp 3), 1.74 _{(s, 6H, CH 3)} , 1.85-1.89 (br m, 12H, Cp 3), 1.96-1.99 (br d, 6H, Cp 3), 2.03-2.09 _{(br m, 12H, Cp 3} ). ³¹ P-NMR (δ, CD ₂ Cl ₂ ): 22.4 (s).

2. Synthesis of Polymer (Polymer Matrix) As shown below, each of the polymers P1 to P6, P8, P9 and P11 to P34 was synthesized.

  In the following, hexyl norbornene (CAS number 22094-83-3) is “HxNB”, diphenylmethylnorbornene methoxysilane (CAS number 376634-34-3) is “diPhNB”, phenylethyl norbornene ( CAS number 29415-09-6) is “PENB”, butylnorbornene (CAS number 22094-81-1) is “BuNB”, and decylnorbornene (CAS number 22094-85-5) is “ DeNB ", benzylnorbornene (CAS number 2665989-73-9)" BzNB ", methylglycidyl ether norbornene (CAS number 3188-75-8)" AGENB ", norbornenylethyltrimethoxy Silane (CAS No. 68245-19- No.) "TMSENB", triethoxysilyl norbornene (CAS number 18401-43-9) "TESNB", trimethoxysilyl norbornene (CAS number 7538-46-7) "TMSNB", Each may be abbreviated.

<< Polymer P1: Synthesis of hexylnorbornene (HxNB) / diphenylmethylnorbornenemethoxysilane (diPhNB) copolymer >>
HxNB (8.94 g, 0.05 mol), diPhNB (16.1 g, 0.05 mol), 1-hexene (4.2 g, 0.05 mol) and toluene (142.0 g) were mixed in a 250 mL sealam bottle. And heated to 120 ° C. in an oil bath to form a solution.

To this solution, [Pd (PCy ₃ ) ₂ (O ₂ CCH ₃ ) (NCCH ₃ )] tetrakis (pentafluorophenyl) borate (hereinafter abbreviated as “Pd1446”) (5.8 × 10 ⁻³ g, 4 0.0 × 10 ⁻⁶ mol) and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (hereinafter abbreviated as “DANFABA”) (3.2 × 10 ⁻³ g, 4.0 × 10 ^{− 6} mol) was added in the form of a concentrated dichloromethane solution, respectively.

  After the addition, the resulting solution was maintained at 120 ° C. for 6 hours. When methanol was added dropwise to the vigorously stirred mixture, the copolymer precipitated.

  The precipitated copolymer was collected by filtration and dried in an oven at 80 ° C. under vacuum. The weight after drying was 12.0 g (yield: 48%).

  When the molecular weight of the copolymer was measured by GPC method (gel permeation chromatography method) using THF as a solvent (polystyrene conversion), it was Mw = 16,196 and Mn = 8,448.

When the composition of the copolymer was measured by ¹ H-NMR, it was ¹ H-NMR: 54/46 = HxNB / diPhNB copolymer.

  When the refractive index of the copolymer was measured by the prism coupling method, it was 1.5569 in the TE mode and 1.5555 in the TM mode at a wavelength of 633 nm.

<< Polymer P2: Synthesis of Hexylnorbornene (HxNB) / Phenylethylnorbornene (PENB) Copolymer >>
HxNB (2.78 g, 0.0156 mol), PENB (7.22 g, 0.036 mol), 1-hexene (2.18 g, 0.026 mol) and toluene (57.0 g) were mixed in a 250 mL sealam bottle. And heated to 120 ° C. in an oil bath to form a solution.

To this solution, Pd1446 (3.0 × 10 ⁻³ g, 2.1 × 10 ⁻⁶ mol) and DANFABA (6.7 × 10 ⁻³ g, 8.4 × 10 ⁻⁶ mol) were each concentrated dichloromethane solution. Added in the form of

  After the addition, the resulting solution was maintained at 120 ° C. for 1 hour. After cooling to room temperature, methanol was added dropwise to the reaction mixture to precipitate a copolymer.

  The precipitated copolymer was collected by filtration and dried in an oven at 80 ° C. under vacuum. The weight after drying was 8.0 g (yield: 80%).

  When the molecular weight of the copolymer was measured by GPC method using THF as a solvent (polystyrene conversion), it was Mw = 127,332 and Mn = 39,206.

When the composition of the copolymer was measured by ¹ H-NMR, it was ¹ H-NMR: 22/78 = HxNB / PENB copolymer.

  When the refractive index of the copolymer was measured by the prism coupling method, it was 1.5601 in the TE mode and 1.5585 in the TM mode at a wavelength of 633 nm.

<< Polymer P3: Synthesis of hexylnorbornene (HxNB) / diphenylmethylnorbornenemethoxysilane (diPhNB) copolymer >>
HxNB (8.94 g, 0.050 mol), diPhNB (16.1 g, 0.050 mol), 1-hexene (2.95 g, 0.035 mol) and toluene (142 g) are weighed and placed in a 250 mL sealam bottle. And heated to 80 ° C. in an oil bath.

To this solution was added Pd1446 (5.8 × 10 ⁻³ g, 4.0 × 10 ⁻⁶ mol) and DANFABA (3.2 × 10 ⁻³ g, 4.0 × 10 ⁻⁶ mol). The ratio of norbornene monomer / Pd1446 / DANFABA was 25K / 1/1.

  The mixture was maintained at 80 ° C. for 7 hours, after which 20 mL of acetonitrile was added to quench the activity of the Pd catalyst. Thereafter, when methanol was added dropwise to the reaction mixture, the copolymer was precipitated.

  The precipitated copolymer was collected by filtration and dried in an oven at 65 ° C. under vacuum. The weight after drying was 19.8 g (yield: 79%).

  When the molecular weight of the copolymer was measured by GPC method using THF as a solvent (polystyrene conversion), it was Mw = 86,186 and Mn = 21,602.

When the composition of the copolymer was measured by ¹ H-NMR, it was ¹ H-NMR: 46/54 = HxNB / diPhNB copolymer.

When the refractive index of the copolymer was measured by the prism coupling method, it was 1.5569 in the TE mode and 1.5556 in the TM mode at a wavelength of 633 nm.
Tg based on the thermomechanical analysis (TMA) of the copolymer was 203 ° C.

<< Polymer P4: Synthesis of hexylnorbornene (HxNB) / diphenylmethylnorbornenemethoxysilane (diPhNB) copolymer >>
HxNB (8.94 g, 0.050 mol), diPhNB (16.1 g, 0.050 mol), 1-hexene (20.0 g, 0.239 mol) and toluene (142 g) were mixed in a 250 mL sealam bottle and oil A solution was formed by heating to 80 ° C. in a bath.

To this solution was added Pd1446 (5.80 × 10 ⁻³ g, 4.0 × 10 ⁻⁶ mol) and DANFABA (3.21 × 10 ⁻³ g, 4.01 × 10 ⁻⁶ mol).

After the addition, the resulting solution was maintained at 80 ° C. for 6 hours. Thereafter, 20 mL of acetonitrile was added to extinguish the activity of the Pd catalyst. Thereafter, when methanol was added dropwise to the reaction mixture, the copolymer was precipitated.
The precipitated copolymer was collected by filtration and dried in an oven at 65 ° C. under vacuum.

  When the molecular weight of the copolymer was measured by GPC method using THF as a solvent (in terms of polystyrene), it was Mw = 20,586 and Mn = 11,613.

When the composition of the copolymer was measured by ¹ H-NMR, it was ¹ H-NMR: 60/40 = HxNB / diPhNB copolymer.

  When the refractive index of the copolymer was measured by the prism coupling method, it was 1.5547 in the TE mode and 1.5540 in the TM mode at a wavelength of 633 nm.

<< Polymer P5: Synthesis of hexylnorbornene (HxNB) / diphenylmethylnorbornene methoxysilane copolymer (diPhNB) >>
HxNB (8.94 g, 0.050 mol), diPhNB (16.06 g, 0.050 mol), 1-hexene (5.0 g, 0.060 mol) and toluene (142 g) were mixed in a 500 mL sealam bottle and oil A solution was formed by heating to 80 ° C. in a bath.

To this solution, Pd1446 (2.90 × 10 ⁻³ g, 2.00 × 10 ⁻⁶ mol) and DANFABA (3.2 × 10 ⁻³ g, 4.01 × 10 ⁻⁶ mol) were concentrated in dichloromethane. Added in the form of a solution.

  After the addition, the resulting solution was maintained at 80 ° C. for 6 hours. When methanol was added dropwise to the vigorously stirred mixture, the copolymer precipitated.

  The precipitated copolymer was collected by filtration and dried in an oven at 60 ° C. under vacuum. The weight after drying was 19.3 g (yield: 77%).

  When the molecular weight of the copolymer was measured by GPC method using THF as a solvent (polystyrene standard), it was Mw = 58,749 and Mn = 18,177.

When the composition of the copolymer was measured by ¹ H-NMR, it was ¹ H-NMR: 53/47 = HxNB / diPhNB copolymer.

  When the refractive index of this copolymer was measured by the prism coupling method, it was 1.5572 in the TE mode and 1.5558 in the TM mode at a wavelength of 633 nm.

<< Polymer P6: Synthesis of Butylnorbornene (BuNB) / Diphenylmethylnorbornenemethoxysilane (diPhNB) Copolymer >>
BuNB (2.62 g, 0.017 mol), diPhNB (22.38 g, 0.07 mol), 1-hexene (8.83 g, 0.011 mol) and toluene (141.4 g) were mixed in a 500 mL sealam bottle. And heated to 80 ° C. in an oil bath to form a solution.

To this solution, Pd1446 (5.05 × 10 ⁻³ g, 3.49 × 10 ⁻⁶ mol) and DANFABA (1.12 × 10 ⁻² g, 1.40 × 10 ⁻⁵ mol) were concentrated in dichloromethane. Added in the form of a solution.

  After the addition, the resulting solution was maintained at 80 ° C. for 2 hours. When methanol was added dropwise to the vigorously stirred mixture, the copolymer precipitated.

  The precipitated copolymer was collected by filtration and dried in an oven at 60 ° C. under vacuum. The weight after drying was 7.5 g (yield: 30%).

  When the molecular weight of the copolymer was measured by GPC method using THF as a solvent (polystyrene standard), it was Mw = 32,665 and Mn = 19,705.

When the composition of the copolymer was measured by ¹ H-NMR, it was ¹ H-NMR: 28/72 = BuNB / diPhNB copolymer.

  When the refractive index of this copolymer was measured by the prism coupling method, it was 1.5785 in the TE mode and 1.5771 in the TM mode at a wavelength of 633 nm.

<< Polymer P8: Synthesis of Hexylnorbornene (HxNB) Homopolymer >>
HxNB (10.0 g, 0.056 mol), 1-hexene (4.71 g, 0.056 mol) and toluene (56.7 g) were mixed in a 250 mL sealam bottle and heated to 80 ° C. in an oil bath. A solution was formed.

To this solution, Pd1446 (4.10 × 10 ⁻⁴ g, 2.80 × 10 ⁻⁷ mol) and DANFABA (2.20 × 10 ⁻⁴ g, 2.80 × 10 ⁻⁷ mol) were concentrated in dichloromethane. Added in the form of a solution.

  After the addition, the resulting solution was maintained at 80 ° C. for 40 minutes. When methanol was added dropwise to the vigorously stirred mixture, the polymer precipitated.

  The precipitated polymer was collected by filtration and dried in an oven at 60 ° C. under vacuum. The weight after drying was 5.8 g (yield: 58%).

  When the molecular weight of the polymer was measured by GPC method using THF as a solvent (polystyrene standard), it was Mw = 121,541 and Mn = 59,213.

When the refractive index of this polymer was measured by the prism coupling method, it was 1.5146 in the TE mode and 1.5129 in the TM mode at a wavelength of 633 nm.
Tg based on thermomechanical analysis (TMA) of the polymer was 208 ° C.

<< Polymer P9: Synthesis of hexylnorbornene (HxNB) / diphenylmethylnorbornenemethoxysilane (diPhNB) copolymer >>
HxNB (9.63 g, 0.054 mol), diPhNB (40.37 g, 0.126 mol), 1-hexene (4.54 g, 0.054 mol) and toluene (333 g) were mixed in a 500 mL sealum bottle, A solution was formed by heating to 80 ° C. in an oil bath.

To this solution, Pd1446 (1.04 × 10 ⁻² g, 7.20 × 10 ⁻⁶ mol) and DANFABA (2.30 × 10 ⁻² g, 2.88 × 10 ⁻⁵ mol) were concentrated in dichloromethane. Added in the form of a solution.

  After the addition, the resulting solution was maintained at 80 ° C. for 2 hours. When methanol was added dropwise to the vigorously stirred mixture, the copolymer precipitated.

  The precipitated copolymer was collected by filtration and dried in an oven at 60 ° C. under vacuum. The weight after drying was 19.0 g (yield: 38%).

  When the molecular weight of the copolymer was measured by GPC method using THF as a solvent (polystyrene conversion), it was Mw = 118,000 and Mn = 60,000.

When the composition of the copolymer was measured by ¹ H-NMR, it was ¹ H-NMR: 32/68 = HxNB / diPhNB copolymer.

  When the refractive index of this copolymer was measured by the prism coupling method, it was 1.5695 in TE mode and 1.5681 in TM mode at a wavelength of 633 nm.

<< Polymer P11: Synthesis of diphenylmethylnorbornenemethoxysilane (diPhNB) homopolymer >>
DiPhNB (30 g, 0.094 mol), 1-hexene (1.57 g, 0.019 mol) and toluene (170.0 g) were mixed in a 250 mL sealam bottle and heated to 80 ° C. in an oil bath to obtain a solution. Formed.

To this solution, Pd1446 (1.4 × 10 ⁻² g, 9.4 × 10 ⁻⁶ mol) and DANFABA (3.0 × 10 ⁻² g, 3.7 × 10 ⁻⁵ mol) were concentrated in dichloromethane. Added in the form of a solution.

  After the addition, the resulting solution was maintained at 80 ° C. for 4 hours. When methanol was added dropwise to the vigorously stirred mixture, the polymer precipitated.

  The precipitated polymer was collected by filtration and dried in an oven at 60 ° C. under vacuum. The weight after drying was 15.0 g (yield: 50%).

  When the molecular weight of the polymer was measured by GPC method using THF as a solvent (in terms of polystyrene), it was Mw = 91,000 and Mn = 44,000.

<< Polymer P12: Synthesis of hexylnorbornene (HxNB) / diphenylmethylnorbornenemethoxysilane (diPhNB) copolymer >>
HxNB (10.72 g, 0.06 mol), diPhNB (19.28 g, 0.06 mol), 1-hexene (3.5 g, 0.04 mol) and toluene (170.0 g) were mixed in a 250 mL sealam bottle. And heated to 80 ° C. in an oil bath to form a solution.

To this solution, Pd1446 (7.0 × 10 ⁻³ g, 4.8 × 10 ⁻⁶ mol) and DANFABA (3.9 × 10 ⁻³ g, 4.8 × 10 ⁻⁶ mol) were concentrated in dichloromethane. Added in the form of a solution.

  After the addition, the resulting solution was maintained at 80 ° C. for 3.5 hours. When methanol was added dropwise to the vigorously stirred mixture, the copolymer precipitated.

  The precipitated copolymer was collected by filtration and dried in an oven at 60 ° C. under vacuum. The weight after drying was 18.6 g (yield: 62%).

  When the molecular weight of the copolymer was measured by GPC method using THF as a solvent (polystyrene conversion), it was Mw = 102,000 and Mn = 38,000.

When the composition of the copolymer was measured by ¹ H-NMR, it was ¹ H-NMR: 54/46 = HxNB / diPhNB copolymer.

<< Polymer P13: Synthesis of Butylnorbornene (BuNB) / Diphenylmethylnorbornenemethoxysilane (diPhNB) Copolymer >>
BuNB (2.62 g, 0.038 mol), diPhNB (22.38 g, 0.057 mol), 1-hexene (8.83 g, 0.011 mol) and toluene (141.4 g) were mixed in a 500 mL sealum bottle. And heated to 80 ° C. in an oil bath to form a solution.

To this solution, Pd1446 (5.05 × 10 ⁻³ g, 3.49 × 10 ⁻⁶ mol) and DANFABA (1.12 × 10 ⁻² g, 1.40 × 10 ⁻⁵ mol) were concentrated in dichloromethane. Added in the form of a solution.

  After the addition, the resulting solution was maintained at 80 ° C. for 2 hours. When methanol was added dropwise to the vigorously stirred mixture, the copolymer precipitated.

  The precipitated copolymer was collected by filtration and vacuum dried in an oven at 60 ° C. The weight after drying was 7.5 g (yield: 30%).

  When the molecular weight of the copolymer was measured by GPC method using THF as a solvent (polystyrene conversion), it was Mw = 32,665 and Mn = 19,705.

When the composition of the copolymer was measured by ¹ H-NMR, it was ¹ H-NMR: 28/72 = BuNB / diPhNB copolymer.

  When the refractive index of this copolymer was measured by the prism coupling method, it was 1.5785 in the TE mode and 1.5771 in the TM mode at a wavelength of 633 nm.

<< Polymer 14: Synthesis of hexylnorbornene (HxNB) / diphenylmethylnorbornenemethoxysilane (diPhNB) copolymer >>
HxNB (9.63 g, 0.054 mol), diPhNB (1.92 g, 0.006 mol), 1-hexene (5.04 g, 0.060 mol) and toluene (56.7 g) were mixed in a 250 mL sealam bottle. And heated to 80 ° C. in an oil bath to form a solution.

To this solution, Pd1446 (4.30 × 10 ⁻⁴ g, 3.00 × 10 ⁻⁷ mol) and DANFABA (2.40 × 10 ⁻⁴ g, 3.00 × 10 ⁻⁷ mol) were concentrated in dichloromethane. Added in the form of a solution.

  After the addition, the resulting solution was maintained at 80 ° C. for 2 hours. When methanol was added dropwise to the vigorously stirred mixture, the copolymer precipitated.

  The precipitated copolymer was collected by filtration and vacuum dried in an oven at 60 ° C. The weight after drying was 7.7 g (yield: 67%).

  When the molecular weight of the copolymer was measured by GPC method using THF as a solvent (in terms of polystyrene), it was Mw = 82,000 and Mn = 40,000.

When the composition of the copolymer was measured by ¹ H-NMR, it was ¹ H-NMR: 89/11 = HxNB / diPhNB copolymer.

  When the refractive index of this copolymer was measured by the prism coupling method, it was 1.5238 in the TE mode and 1.5225 in the TM mode at a wavelength of 633 nm.

<< Polymer P15: Synthesis of diphenylmethylnorbornenemethoxysilane (diPhNB) homopolymer >>
DiPhNB (30 g, 0.094 mol), 1-hexene (2.36 g, 0.028 mol) and toluene (170.0 g) were mixed in a 500 mL sealum bottle and heated to 80 ° C. in an oil bath to obtain a solution. Formed.

To this solution, Pd1446 (0.0135 g, 9.36 × 10 ⁻⁶ mol) and DANFABA (0.030 g, 3,74 × 10 ⁻⁵ mol) were each added in the form of a concentrated dichloromethane solution.

  After the addition, the resulting solution was maintained at 80 ° C. for 4 hours. When methanol was added dropwise to the vigorously stirred mixture, the polymer precipitated.

  The precipitated polymer was collected by filtration and dried in an oven at 60 ° C. under vacuum. The weight after drying was 25.18 g (yield: 21%).

  When the molecular weight of the polymer was measured by GPC method using THF as a solvent (polystyrene conversion), it was Mw = 54,000 and Mn = 29,000.

When the composition of the polymer was measured by ¹ H-NMR, it was a diPhNB homopolymer.
When the refractive index of this polymer was measured by the prism coupling method, it was 1.5926 in the TE mode and 1.5910 in the TM mode at a wavelength of 633 nm.

<< Polymer P16: Synthesis of Butylnorbornene (BuNB) / Phenylethylnorbornene (PENB) Copolymer >>
BuNB (4.78 g, 0.032 mol), PENB (25.22 g, 0.127 mol), 1-hexene (13.36 g, 0.16 mol) and toluene (170.0 g) were mixed in a 500 mL sealam bottle. And heated to 80 ° C. in an oil bath to form a solution.

To this solution, Pd1446 (0.0092 g, 6.36 × 10 ⁻⁶ mol) and DANFABA (0.020 g, 2.54 × 10 ⁻⁵ mol) were each added in the form of a concentrated dichloromethane solution.

  After the addition, the resulting solution was maintained at 80 ° C. for 50 minutes. When methanol was added dropwise to the vigorously stirred mixture, the copolymer precipitated.

  The precipitated copolymer was collected by filtration and dried in an oven at 60 ° C. under vacuum. The weight after drying was 23.60 g (yield: 79%).

  When the molecular weight of the copolymer was measured by GPC method using THF as a solvent (polystyrene conversion), it was Mw = 73,000 and Mn = 28,000.

When the composition of the copolymer was measured by ¹ H-NMR, it was ¹ H-NMR: 15/85 = BuNB / PENB copolymer.

  When the refractive index of this copolymer was measured by the prism coupling method, it was 1.5684 in TE mode and 1.5657 in TM mode at a wavelength of 633 nm.

<< Polymer P17: Synthesis of Hexylnorbornene (HxNB) / Phenylethylnorbornene (PENB) Copolymer >>
HxNB (6.00 g, 0.034 mol), PENB (26.69 g, 0.135 mol), 1-hexene (11.31 g, 0.135 mol) and toluene (185.35 g) were mixed in a 500 mL sealum bottle. And heated to 80 ° C. in an oil bath to form a solution.

To this solution, Pd1446 (0.0097 g, 6.73 × 10 ⁻⁶ mol) and DANFABA (0.022 g, 2.69 × 10 ⁻⁵ mol) were each added in the form of a concentrated dichloromethane solution.

  After the addition, the resulting solution was maintained at 80 ° C. for 50 minutes. When methanol was added dropwise to the vigorously stirred reaction mixture, the copolymer precipitated.

  The precipitated copolymer was collected by filtration and dried in an oven at 60 ° C. under vacuum. The weight after drying was 22.21 g (yield: 68%).

  When the molecular weight of the copolymer was measured by GPC method using THF as a solvent (polystyrene conversion), it was Mw = 95,000 and Mn = 26,000.

When the composition of the copolymer was measured by ¹ H-NMR, it was ¹ H-NMR: 17/83 = HxNB / PENB copolymer.

  When the refractive index of the copolymer was measured by the prism coupling method, it was 1.5477 in the TE mode and 1.5454 in the TM mode at a wavelength of 633 nm.

<< Polymer P18: Synthesis of Decylnorbornene (DeNB) / Phenylethylnorbornene (PENB) Copolymer >>
DeNB (6.84 g, 0.029 mol), PENB (23.16 g, 0.117 mol), 1-hexene (12.26 g, 0.146 mol) and toluene (170.0 g) were mixed in a 500 mL sealam bottle. And heated to 80 ° C. in an oil bath to form a solution.

To this solution, Pd1446 (0.0084 g, 5.84 × 10 ⁻⁶ mol) and DANFABA (0.019 g, 2.33 × 10 ⁻⁵ mol) were each added in the form of a concentrated dichloromethane solution.

  After the addition, the resulting solution was maintained at 80 ° C. for 50 minutes. When methanol was added dropwise to the vigorously stirred reaction mixture, the copolymer precipitated.

  The precipitated copolymer was collected by filtration and dried in an oven at 60 ° C. under vacuum. The weight after drying was 19.74 g (yield: 66%).

  When the molecular weight of the copolymer was measured by GPC method using THF as a solvent (polystyrene conversion), it was Mw = 78,000 and Mn = 36,000.

When the composition of the copolymer was measured by ¹ H-NMR, it was ¹ H-NMR: 19/81 = DeNB / PENB copolymer.

  When the refractive index of the copolymer was measured by the prism coupling method, it was 1.5640 in the TE mode and 1.5622 in the TM mode at a wavelength of 633 nm.

<< Polymer P19: Synthesis of benzylnorbornene (BzNB) homopolymer >>
BzNB (30.00 g, 0.163 mol), triethylsilane (0.227 g, 1.95 × 10 ⁻³ mol), ethanol (0.360 g, 7.81 × 10 ⁻³ mol) and toluene (170.0 g) Were mixed in a 500 mL sealum bottle and heated to 80 ° C. in an oil bath to form a solution.

To this solution, Pd1446 (0.0188 g, 1.30 × 10 ⁻⁵ mol) and DANFABA (0.042 g, 5.21 × 10 ⁻⁵ mol) were each added in the form of a concentrated dichloromethane solution.

  After the addition, the resulting solution was maintained at 80 ° C. for 1.5 hours. When methanol was added dropwise to the vigorously stirred reaction mixture, the polymer precipitated.

  The precipitated polymer was collected by filtration and dried in an oven at 60 ° C. under vacuum. The weight after drying was 15.07 g (yield: 50%).

  When the molecular weight of the polymer was measured by GPC method using THF as a solvent (polystyrene conversion), it was Mw = 46,000 and Mn = 28,000.

When the composition of the polymer was measured by ¹ H-NMR, it was a BzNB homopolymer.
When the refractive index of the polymer was measured by the prism coupling method, it was 1.5778 in the TE mode and 1.5757 in the TM mode at a wavelength of 633 nm.

<< Polymer P20: Synthesis of Hexylnorbornene (HxNB) / Benzylnorbornene (BzNB) Copolymer >>
HxNB (8.79 g, 0.049 mol), BzNB (21.21 g, 0.115 mol), triethylsilane (0.23 g, 1.97 × 10 ⁻³ mol), ethanol (0.36 g, 7.89 × 10 9) ⁻³ mol) and toluene (170.0 g) were mixed in a 500 mL sealum bottle and heated to 80 ° C. in an oil bath to form a solution.

To this solution, Pd1446 (0.019 g, 1.32 × 10 ⁻⁵ mol) and DANFABA (0.042 g, 5.26 × 10 ⁻⁵ mol) were each added in the form of a concentrated dichloromethane solution.

  After the addition, the resulting solution was maintained at 80 ° C. for 1.5 hours. When methanol was added dropwise to the vigorously stirred reaction mixture, the copolymer precipitated.

  The precipitated copolymer was collected by filtration and dried in an oven at 60 ° C. under vacuum. The weight after drying was 18.59 g (yield: 62%).

  When the molecular weight of the copolymer was measured by GPC using THF as a solvent (polystyrene conversion), it was Mw = 52,000 and Mn = 30,000.

When the composition of the copolymer was measured by ¹ H-NMR, it was ¹ H-NMR: 35/65 = HxNB / BzNB copolymer.

  When the refractive index of the copolymer was measured by the prism coupling method, it was 1.5597 in the TE mode and 1.5579 in the TM mode at a wavelength of 633 nm.

<< Polymer P21: Synthesis of Decylnorbornene (DeNB) / Benzylnorbornene (BzNB) Copolymer >>
DeNB (6.84 g, 0.029 mol), BzNB (21.56 g, 0.117 mol), 1-hexene (12.26 g, 0.146 mol) and toluene (170.0 g) were mixed in a 500 mL sealam bottle. And heated to 80 ° C. in an oil bath to form a solution.

To this solution, Pd1446 (0.0084 g, 5.84 × 10 ⁻⁶ mol) and DANFABA (0.019 g, 2.33 × 10 ⁻⁵ mol) were each added in the form of a concentrated dichloromethane solution.

  After the addition, the resulting solution was maintained at 80 ° C. for 1.5 hours. When methanol was added dropwise to the vigorously stirred reaction mixture, the copolymer precipitated.

  The precipitated copolymer was collected by filtration and dried in an oven at 60 ° C. under vacuum. The weight after drying was 20.73 g (yield: 73%).

  When the molecular weight of the copolymer was measured by GPC method using THF as a solvent (in terms of polystyrene), it was Mw = 64,000 and Mn = 31,000.

When the composition of the copolymer was measured by ¹ H-NMR, it was ¹ H-NMR: 27/73 = DeNB / BzNB copolymer.

  When the refractive index of the copolymer was measured by the prism coupling method, it was 1.5680 in TE mode and 1.5662 in TM mode at a wavelength of 633 nm.

<< Polymer P22: Synthesis of Butyl Norbornene (BuNB) / Methyl Glycidyl Ether Norbornene (AGENB) Copolymer >>
BuNB (10.52 g, 0.07 mol), AGENB (5.41 g, 0.03 mol) and toluene (58.0 g) were mixed in a sealum bottle and heated to 80 ° C. in an oil bath to form a solution. .

To this solution was added a toluene solution (5 g) of (η ⁶ -toluene) Ni (C ₆ F ₅ ) ₂ (0.69 g, 0.0014 mol).

  After the addition, the resulting solution was maintained at room temperature for 4 hours. Toluene solution (87.0 g) was added to the reaction solution. When methanol was added dropwise to the vigorously stirred reaction mixture, the copolymer precipitated.

  The precipitated copolymer was collected by filtration and dried in an oven at 60 ° C. under vacuum. The weight after drying was 12.74 g (yield: 80%).

  When the molecular weight of the copolymer was measured by GPC method using THF as a solvent (polystyrene conversion), it was Mw = 75,000 and Mn = 30,000.

When the composition of the copolymer was measured by ¹ H-NMR, it was ¹ H-NMR: 78/22 = BuNB / AGENB copolymer.

  When the refractive index of the copolymer was measured by the prism coupling method, it was 1.5162 in the TE mode and 1.5157 in the TM mode at a wavelength of 633 nm.

<< Polymer P23: Synthesis of Hexyl Norbornene (HxNB) / Methyl Glycidyl Ether Norbornene (AGENB) Copolymer >>
HxNB (12.48 g, 0.07 mol), AGENB (5.41 g, 0.03 mol), and toluene (58.0 g) were added to the sealum bottle in the dry box. This solution was stirred in an oil bath at 80 ° C.

To this solution was added a toluene solution (5 g) of (η ⁶ -toluene) Ni (C ₆ F ₅ ) ₂ (0.69 g, 0.0014 mol).

  After the addition, the resulting mixture was maintained at room temperature for 4 hours. Toluene solution (87.0 g) was added to the reaction solution. When methanol was added dropwise to the vigorously stirred reaction mixture, the copolymer precipitated.

  The precipitated copolymer was collected by filtration and dried in an oven at 60 ° C. under vacuum. The weight after drying was 13.78 g (yield: 77%).

  When the molecular weight of the copolymer was measured by GPC method using THF as a solvent (polystyrene conversion), it was Mw = 78,000 and Mn = 33,000.

When the composition of the copolymer was measured by ¹ H-NMR, it was ¹ H-NMR: 79/21 = HxNB / AGENB copolymer.

  When the refractive index of the copolymer was measured by the prism coupling method, it was 1.5159 in the TE mode and 1.5153 in the TM mode at a wavelength of 633 nm.

<< Polymer P24: Synthesis of Decyl Norbornene (DeNB) / Methyl Glycidyl Ether Norbornene (AGENB) Copolymer >>
DeNB (16.4 g, 0.07 mol), AGENB (5.41 g, 0.03 mol) and toluene (58.0 g) were added to the sealum bottle in the dry box. This solution was stirred in an oil bath at 80 ° C.

To this solution was added a toluene solution (5 g) of (η ⁶ -toluene) Ni (C ₆ F ₅ ) ₂ (0.69 g, 0.0014 mol).

  After the addition, the resulting mixture was maintained at room temperature for 4 hours. Toluene solution (87.0 g) was added to the reaction solution. When methanol was added dropwise to the vigorously stirred reaction mixture, the copolymer precipitated.

  The precipitated copolymer was collected by filtration and dried in an oven at 60 ° C. under vacuum. The weight after drying was 17.00 g (yield: 87%).

  When the molecular weight of the copolymer was measured by GPC method using THF as a solvent (polystyrene conversion), it was Mw = 75,000 and Mn = 30,000.

When the composition of the copolymer was measured by ¹ H-NMR, it was ¹ H-NMR: 77/23 = DeNB / AGENB copolymer.

  When the refractive index of the copolymer was measured by the prism coupling method, it was 1.5153 in the TE mode and 1.5151 in the TM mode at a wavelength of 633 nm.

<< Polymer P25: Synthesis of Butylnorbornene (BuNB) / Norbornenylethyltrimethoxysilane (TMSENB) Copolymer >>
BuNB (25.44 g, 0.169 mol), TMSENB (4.56 g, 0.019 mol), triethylsilane (0.11 g, 9.41 × 10 ⁻⁴ mol), ethanol (0.10 g, 2.26 × 10) ⁻³ mol) and toluene (170.0 g) were mixed in a 300 mL sealam bottle and heated at 80 ° C. in an oil bath to form a solution.

To this solution, Pd1446 (0.022 g, 1.50 × 10 ⁻⁵ mol) and DANFABA (0.036 g, 4.51 × 10 ⁻⁵ mol) were each added in the form of a concentrated dichloromethane solution.

  After the addition, the resulting mixture was maintained at 80 ° C. for 4 hours. When methanol was added dropwise to the vigorously stirred reaction mixture, the copolymer precipitated.

  The precipitated copolymer was collected by filtration and dried in an oven at 60 ° C. under vacuum. The weight after drying was 22.60 g (yield: 69%).

  When the molecular weight of the copolymer was measured by the GPC method using THF as a solvent (polystyrene conversion), it was Mw = 20,000 and Mn = 13,000.

When the composition of the copolymer was measured by ¹ H-NMR, it was ¹ H-NMR: 91/9 = BuNB / TMSENB copolymer.

  When the refractive index of the copolymer was measured by the prism coupling method, it was 1.5106 in the TE mode and 1.5105 in the TM mode at a wavelength of 633 nm.

<< Polymer P26: Synthesis of Hexylnorbornene (HxNB) / Norbornenylethyltrimethoxysilane (TMSENB) Copolymer >>
HxNB (13.03 g, 0.073 mol), TMSENB (1.97 g, 0.0081 mol), triethylsilane (0.019 g, 1.62 × 10 ⁻⁴ mol), ethanol (0.030 g, 6.50 × 10) ^-4 mol) and toluene (85.0 g) were mixed in a 300 mL sealam bottle and heated at 80 ° C. in an oil bath to form a solution.

[Pd (P (iPr) ₃ ) ₂ (OCOCH ₃ ) (NCCH ₃ )] tetrakis (pentafluorophenyl) borate (hereinafter abbreviated as “Pd1206”) (0.0078 g, 6.50 × 10) ⁻⁶ mol) was added in the form of a concentrated dichloromethane solution.

  After the addition, the resulting mixture was maintained at 80 ° C. for 4 hours. When methanol was added dropwise to the vigorously stirred reaction mixture, the copolymer precipitated.

  The precipitated copolymer was collected by filtration and dried in an oven at 60 ° C. under vacuum. The weight after drying was 3.30 g (yield: 22%).

  When the molecular weight of the copolymer was measured by GPC method using THF as a solvent (polystyrene conversion), it was Mw = 53,000 and Mn = 33,000.

When the composition of the copolymer was measured by ¹ H-NMR, it was ¹ H-NMR: 93/7 = HxNB / TMSENB copolymer.

  When the refractive index of the copolymer was measured by the prism coupling method, it was 1.5126 in the TE mode and 1.5114 in the TM mode at a wavelength of 633 nm.

<< Polymer P27: Synthesis of Decylnorbornene (DeNB) / Norbornenylethyltrimethoxysilane (TMSENB) Copolymer >>
DeNB (22.31 g, 0.095 mol), TMSENB (7.69 g, 0.032 mol), triethylsilane (0.44 g, 3.81 × 10 ⁻⁴ mol), ethanol (0.70 g, 1.52 × 10) ⁻³ mol) and toluene (170.0 g) were mixed in a 500 mL sealam bottle and heated at 80 ° C. in an oil bath to form a solution.

To this solution, Pd1446 (0.015 g, 1.02 × 10 ⁻⁵ mol) and DANFABA (0.024 g, 3.05 × 10 ⁻⁵ mol) were each added in the form of a concentrated dichloromethane solution.

  After the addition, the resulting mixture was maintained at 80 ° C. for 4 hours. When methanol was added dropwise to the vigorously stirred reaction mixture, the copolymer precipitated.

  The precipitated copolymer was collected by filtration and dried in an oven at 60 ° C. under vacuum. The weight after drying was 12.2 g (yield: 40.7%).

  When the molecular weight of the copolymer was measured by GPC method using THF as a solvent (in terms of polystyrene), it was Mw = 34,000 and Mn = 24,000.

When the composition of the copolymer was measured by ¹ H-NMR, it was ¹ H-NMR: 77/23 = DeNB / TMSENB copolymer.

  When the refractive index of the copolymer was measured by the prism coupling method, it was 1.5063 in the TE mode and 1.5062 in the TM mode at a wavelength of 633 nm.

<< Polymer P28: Synthesis of Butylnorbornene (BuNB) / Triethoxysilylnorbornene (TESNB) Copolymer >>
BuNB (25.22 g, 0.168 mol), TENSB (4.78 g, 0.019 mol), triethylsilane (0.011 g, 9.32 × 10 ⁻⁵ mol), ethanol (0.10 g, 2.24 × 10) ⁻³ mol) and toluene (170.0 g) were mixed in a 500 mL sealam bottle and heated at 80 ° C. in an oil bath to form a solution.

To this solution, Pd1206 (0.018 g, 1.49 × 10 ⁻⁵ mol) was added in the form of a concentrated dichloromethane solution.

  After the addition, the resulting mixture was maintained at 80 ° C. for 9 hours. When methanol was added dropwise to the vigorously stirred reaction mixture, the copolymer precipitated.

  The precipitated copolymer was collected by filtration and dried in an oven at 60 ° C. under vacuum. The weight after drying was 20.58 g (yield: 69%).

  When the molecular weight of the copolymer was measured by GPC method using THF as a solvent (polystyrene conversion), it was Mw = 238,000 and Mn = 96,000.

When the composition of the copolymer was measured by ¹ H-NMR, it was ¹ H-NMR: 85/15 = BuNB / TESTNB copolymer.

When the refractive index of the copolymer was measured by the prism coupling method, it was 1.5061 in the TE mode and 1.5041 in the TM mode at a wavelength of 633 nm.
Tg based on the thermomechanical analysis (TMA) of the copolymer was 276 ° C.

<< Polymer P29: Synthesis of Hexyl Norbornene (HxNB) / Triethoxysilyl Norbornene (TESNB) Copolymer >>
HxNB (20.33 g, 0.114 mol), TESNB (3.26 g, 0.013 mol), triethylsilane (0.030 g, 2.54 × 10 ⁻³ mol), ethanol (0.07 g, 1.52 × 10) ⁻³ mol) and toluene (170.0 g) were mixed in a 500 mL sealam bottle and heated at 80 ° C. in an oil bath to form a solution.

To this solution, Pd1446 (0.015 g, 1.01 × 10 ⁻⁵ mol) was added in the form of a concentrated dichloromethane solution.

  After the addition, the resulting mixture was maintained at 80 ° C. for 9 hours. When methanol was added dropwise to the vigorously stirred reaction mixture, the copolymer precipitated.

  The precipitated copolymer was collected by filtration and dried in an oven at 60 ° C. under vacuum. The weight after drying was 7.31 g (yield: 31%).

  When the molecular weight of the copolymer was measured by GPC method using THF as a solvent (polystyrene conversion), it was Mw = 234,000 and Mn = 110,000.

When the composition of the copolymer was measured by ¹ H-NMR, it was ¹ H-NMR: 83/17 = HxNB / TENSB copolymer.

  When the refractive index of the copolymer was measured by the prism coupling method, it was 1.5053 in the TE mode and 1.5042 in the TM mode at a wavelength of 633 nm.

<< Polymer P30: Synthesis of Decylnorbornene (DeNB) / Triethoxysilylnorbornene (TESNB) Copolymer >>
DeNB (26.77 g, 0.114 mol), TESNB (3.26 g, 0.013 mol), triethylsilane (0.030 g, 2.54 × 10 ⁻³ mol), ethanol (0.07 g, 1.52 × 10) ⁻³ mol) and toluene (170.0 g) were mixed in a 500 mL sealam bottle and heated at 80 ° C. in an oil bath to form a solution.

To this solution, Pd1446 (0.015 g, 1.01 × 10 ⁻⁵ mol) was added in the form of a concentrated dichloromethane solution.

  After the addition, the resulting mixture was maintained at 80 ° C. for 9 hours. When methanol was added dropwise to the vigorously stirred reaction mixture, the copolymer precipitated.

  The precipitated copolymer was collected by filtration and dried in an oven at 60 ° C. under vacuum. The weight after drying was 18.01 g (yield: 60%).

  When the molecular weight of the copolymer was measured by GPC method using THF as a solvent (polystyrene conversion), it was Mw = 283,000 and Mn = 1118.

When the composition of the copolymer was measured by ¹ H-NMR, it was ¹ H-NMR: 84/16 = DeNB / TENSB copolymer.

  When the refractive index of the copolymer was measured by the prism coupling method, it was 1.5034 in the TE mode and 1.5018 in the TM mode at a wavelength of 633 nm.

<< Polymer P31: Synthesis of Butylnorbornene (BuNB) / Trimethoxysilyl Norbornene (TMSNB) Copolymer >>
BuNB (10.97 g, 0.073 mol), TMSNB (12.95 g, 0.073 mol), triethylsilane (0.34 g, 2.91 × 10 ⁻⁴ mol), ethanol (0.80 g, 1.75 × 10) ⁻³ mol) and toluene (170.0 g) were mixed in a 500 mL sealam bottle and heated at 80 ° C. in an oil bath to form a solution.

To this solution, Pd1446 (0.017 g, 1.16 × 10 ⁻⁵ mol) and DANFABA (0.028 g, 3.49 × 10 ⁻⁵ mol) were each added in the form of a concentrated dichloromethane solution.

  After the addition, the resulting mixture was maintained at 80 ° C. for 4 hours. When methanol was added dropwise to the vigorously stirred reaction mixture, the copolymer precipitated.

  The precipitated copolymer was collected by filtration and dried in an oven at 60 ° C. under vacuum. The weight after drying was 15.5 g (yield: 65%).

  When the molecular weight of the copolymer was measured by GPC method using THF as a solvent (polystyrene conversion), it was Mw = 48,000 and Mn = 27,000.

When the composition of the copolymer was measured by ¹ H-NMR, it was ¹ H-NMR: 47/53 = BuNB even TMSNB copolymer.

  When the refractive index of the copolymer was measured by the prism coupling method, it was 1.5093 in the TE mode and 1.5089 in the TM mode at a wavelength of 633 nm.

<< Polymer P32: Synthesis of Hexyl Norbornene (HxNB) / Trimethoxysilyl Norbornene (TMSNB) Copolymer >>
HxNB (13.02 g, 0.073 mol), TMSNB (12.95 g, 0.073 mol), triethylsilane (0.34 g, 2.91 × 10 ⁻⁴ mol), ethanol (0.80 g, 1.75 × 10) ⁻³ mol) and toluene (170.0 g) were mixed in a 500 mL sealam bottle and heated at 80 ° C. in an oil bath to form a solution.

To this solution, Pd1446 (0.017 g, 1.16 × 10 ⁻⁵ mol) and DANFABA (0.028 g, 3.49 × 10 ⁻⁵ mol) were each added in the form of a concentrated dichloromethane solution.

  After the addition, the resulting mixture was maintained at 80 ° C. for 4 hours. When methanol was added dropwise to the vigorously stirred reaction mixture, the copolymer precipitated.

  The precipitated copolymer was collected by filtration and dried in an oven at 60 ° C. under vacuum. The weight after drying was 17.7 g (yield: 68%).

  When the molecular weight of the copolymer was measured by GPC method using THF as a solvent (polystyrene conversion), it was Mw = 55,000 and Mn = 27,000.

When the composition of the copolymer was measured by ¹ H-NMR, it was ¹ H-NMR: 46/54 = HxNB / TMSNB copolymer.

  When the refractive index of the copolymer was measured by the prism coupling method, it was 1.5081 in the TE mode and 1.5078 in the TM mode at a wavelength of 633 nm.

<< Polymer P33: Synthesis of Decylnorbornene (DeNB) / Trimethoxysilylnorbornene (TMSNB) Copolymer >>
DeNB (17.05 g, 0.073 mol), TMSNB (12.95 g, 0.073 mol), triethylsilane (0.34 g, 2.91 × 10 ⁻⁴ mol), ethanol (0.80 g, 1.75 × 10) ⁻³ mol) and toluene (170.0 g) were mixed in a 500 mL sealam bottle and heated at 80 ° C. in an oil bath to form a solution.

To this solution, Pd1446 (0.017 g, 1.16 × 10 ⁻⁵ mol) and DANFABA (0.028 g, 3.49 × 10 ⁻⁵ mol) were each added in the form of a concentrated dichloromethane solution.

  After the addition, the resulting mixture was maintained at 80 ° C. for 4 hours. When methanol was added dropwise to the vigorously stirred reaction mixture, the copolymer precipitated.

  The precipitated copolymer was collected by filtration and dried in an oven at 60 ° C. under vacuum. The weight after drying was 21.0 g (yield: 70%).

  When the molecular weight of the copolymer was measured by the GPC method using THF as a solvent (polystyrene conversion), it was Mw = 82,000 and Mn = 31,000.

When the composition of the copolymer was measured by ¹ H-NMR, it was ¹ H-NMR: 46/54 = DeNB / TMSNB copolymer.

  When the refractive index of the copolymer was measured by the prism coupling method, it was 1.5029 in the TE mode and 1.5016 in the TM mode at a wavelength of 633 nm.

<< Polymer P34: Synthesis of hexylnorbornene (HxNB) / diphenylmethylnorbornenemethoxysilane (diPhNB) / norbornenylethyltrimethoxysilane (TMSENB) terpolymer >>
HxNB (5.94 g, 0.033 mol), diPhNB (21.36 g, 0.067 mol), TMSENB (2.69 g, 0.011 mol), 1-hexene (3.73 g, 0.044 mol) and toluene (170. 0 g) was mixed in a 500 mL sealum bottle and heated in an oil bath at 80 ° C. to form a solution.

To this solution, Pd1446 (0.0064 g, 4.44 × 10 ⁻⁶ mol) and DANFABA (0.0036 g, 4.44 × 10 ⁻⁶ mol) were each added in the form of a concentrated dichloromethane solution.

  After the addition, the resulting mixture was maintained at 80 ° C. for 3.5 hours. When methanol was added dropwise to the vigorously stirred reaction mixture, the copolymer precipitated.

  The precipitated copolymer was collected by filtration and dried in an oven at 60 ° C. under vacuum. The weight after drying was 10.26 g (yield: 34%).

  When the molecular weight of the copolymer was measured by GPC method using THF as a solvent (polystyrene conversion), it was Mw = 105,000 and Mn = 54,000.

When the composition of the copolymer was measured by ¹ H-NMR, it was ¹ H-NMR: 38/54/8 = HxNB / diPhNB / TMSENB copolymer.

When the refractive index of the copolymer was measured by the prism coupling method, it was 1.5586 in the TE mode and 1.5572 in the TM mode at a wavelength of 633 nm.
Each polymer synthesized above is summarized in Table 1 below.

3. Preparation of varnish Each varnish V1-V13, V38-V48 and V63-V66 was prepared as shown below. Each varnish was prepared under a yellow light because it contained a photosensitive material.

  Hereinafter, dimethylbis (norbornenemethoxy) silane (CAS No. 376609-87-9) may be abbreviated as “SiX”.

<< Preparation of Varnish V1 >>
HxNB (42.03 g, 0.24 mol) and SiX (7.97 g, 0.026 mol) were weighed and placed in a glass bottle.
Ciba IRGANOX 1076 (0.5 g) and Ciba IRGAFOS 168 (0.125 g) were added to the monomer solution as an antioxidant to obtain a monomer antioxidant solution.

A monomer antioxidant solution (3.0 g) and the catalyst precursor C2 (hereinafter abbreviated as “Pd785”) were added to a solution (30.0 g) of the polymer P1 dissolved in mesitylene so as to be 10 wt%. (4.94 × 10 ⁻⁴ g, 6.29 × 10 ⁻⁷ mol, in 0.1 mL of methylene chloride), as a photoacid generator (co-catalyst), RHODORSIL PHOTOINITIATOR 2074 (2.55 × 10 ⁻³ g, 2.51 × 10 ⁻⁶ mol in methylene chloride 0.1 mL) was added to prepare varnish V1.

This varnish V1 was used after being filtered with a 0.2 μm pore filter.
In the following description, Ciba IRGANOX 1076 is abbreviated as “IRGANOX 1076”, Ciba IRGAFOS 168 as “IRGAFOS 168”, and RHODORSIL PHOTOINITIATOR 2074 as “RHODORSIL 2074”.

<< Preparation of Varnish V2 >>
SiX (5 g, 0.0164 mol) was weighed and placed in a glass bottle.

  Irganox 1076 (0.05 g) and Irgafos 168 (0.013 g) were added to this SiX as an antioxidant to obtain a SiX solution (monomer antioxidant solution).

SiX solution (3 g), Pd785 (3.10 × 10 ⁻⁴ g, 3.94 × 10 ⁻⁷ mol, in 0.1 mL of methylene chloride) as a catalyst precursor, and RHODORSIL 2074 (1. 60 × 10 ⁻³ g, 1.58 × 10 ⁻⁶ mol in 0.1 mL of methylene chloride) and a solution (30 g) of the above polymer P2 dissolved in mesitylene so as to be 10 wt% were mixed to obtain varnish V2 Was prepared.

The weight ratio of polymer P2 (copolymer) / SiX (monomer) is 1/1, and the molar ratio of SiX (monomer) / Pd785 (Pd catalyst) / RHODORSIL 2074 (photoacid generator: PAG) is 25 K / 1. / 4.
This varnish V2 was used after being filtered with a 0.2 μm pore filter.

<< Preparation of Varnish V3 >>
HxNB (42.03 g, 0.24 mol) and SiX (7.97 g, 0.026 mol) were weighed and placed in a glass bottle.

  To this monomer solution, IRGANOX 1076 (0.5 g) and IRGAFOS 168 (0.125 g) were added as antioxidants to obtain a monomer antioxidant solution.

  Further, as a polymer solution, a solution (10 g) in which the above polymer P3 was dissolved in mesitylene so as to be 10 wt% and a solution (20 g) in which the above polymer P4 was dissolved in mesitylene so as to be 10 wt% were mixed. A mixture was prepared.

Then, to this polymer solution (30.0 g), as a monomer antioxidant solution (3.0 g), as a catalyst precursor, Pd785 (4.93 × 10 ⁻⁴ g, 6.28 × 10 ⁻⁷ mol, methylene chloride) In 0.1 mL), RHODORSIL 2074 (2.55 × 10 ⁻³ g, 2.51 × 10 ⁻⁶ mol, in 0.1 mL of methylene chloride) was added as a photoacid generator to prepare varnish V3.
This varnish V3 was used after being filtered with a 0.2 μm pore filter.

<< Preparation of Varnish V4 >>
As a polymer solution, a mixed solution obtained by mixing a solution (15 g) in which the above polymer P3 was dissolved in mesitylene so as to be 10 wt% and a solution (15 g) in which the above polymer P4 was dissolved in mesitylene so as to be 10 wt%. Varnish V4 was prepared in the same manner as Varnish V3 except that was used.
This varnish V4 was used after being filtered with a 0.2 μm pore filter.

<< Preparation of Varnish V5 >>
As a polymer solution, a mixed solution prepared by mixing a solution (20 g) in which the above polymer P3 was dissolved in mesitylene so as to be 10 wt% and a solution (10 g) in which the above polymer P4 was dissolved in mesitylene so as to be 10 wt%. Varnish V5 was prepared in the same manner as Varnish V3 except that was used.
This varnish V5 was used after being filtered with a filter having a pore size of 0.2 μm.

<< Preparation of Varnish V6 >>
Varnish V6 was prepared in the same manner as varnish V3 except that a solution (30 g) in which the above polymer P3 was dissolved in mesitylene so as to be 10 wt% was used as the polymer solution.
The varnish V6 was used after being filtered with a 0.2 μm pore filter.

<< Preparation of Varnish V7 >>
HxNB (40.33 g, 0.23 mol) and TMSENB (9.67 g, 0.039 mol) were weighed and placed in a glass bottle.

  To this monomer solution, IRGANOX 1076 (0.5 g) and IRGAFOS 168 (0.125 g) were added as antioxidants to obtain a monomer antioxidant solution.

  Further, as a polymer solution, a solution (15 g) in which the polymer P3 was dissolved in mesitylene so as to be 10 wt% and a solution (15 g) in which the polymer P4 was dissolved in mesitylene so as to be 10 wt% were mixed. A mixture was prepared.

Then, in this polymer solution (30.0 g), as a monomer antioxidant solution (3.0 g), Pd785 (5.02 × 10 ⁻⁴ g, 6.39 × 10 ⁻⁷ mol, methylene chloride) as a catalyst precursor. In 0.1 mL), RHODORSIL 2074 (2.59 × 10 ⁻³ g, 2.55 × 10 ⁻⁶ mol, in 0.1 mL of methylene chloride) was added as a photoacid generator to prepare varnish V7.
This varnish V7 was used after being filtered with a filter having a pore size of 0.2 μm.

<< Preparation of Varnish V8 >>
HxNB (42.03 g, 0.24 mol) and SiX (7.97 g, 0.026 mol) were weighed and placed in a glass bottle.

  To this monomer solution, IRGANOX 1076 (0.5 g) and IRGAFOS 168 (0.125 g) were added as antioxidants to obtain a monomer antioxidant solution.

In a solution (18.3 g) of the above polymer P5 dissolved in mesitylene so as to be 10 wt%, a monomer antioxidant solution (3.06 g), and Pd785 (3.85 × 10 ⁻⁴ g, 4.91 × 10 ⁻⁷ mol, in 0.1 mL of methylene chloride), RHODORSIL 2074 (1.99 × 10 ⁻³ g, 1.96 × 10 ⁻⁶ mol, in 0.1 mL of methylene chloride) as a photoacid generator ) And mesitylene (1.30 g) were added to prepare varnish V8.
This varnish V8 was used after being filtered with a 0.2 μm pore filter.

<< Preparation of Varnish V9 >>
HxNB (42.03 g, 0.24 mol) and SiX (7.97 g, 0.026 mol) were weighed and placed in a glass bottle.

  To this monomer solution, IRGANOX 1076 (0.5 g) and IRGAFOS 168 (0.125 g) were added as antioxidants to obtain a monomer antioxidant solution.

In a solution (9.15 g) of the above polymer P6 dissolved in mesitylene so as to be 10 wt%, a monomer antioxidant solution (1.53 g), and Pd785 (2.52 × 10 ⁻⁴ g, 3.21 × 10 ⁻⁷ mol, in 0.1 mL of methylene chloride), as a photoacid generator, RHODORSIL 2074 (1.30 × 10 ⁻³ g, 1.28 × 10 ⁻⁶ mol, in 0.1 mL of methylene chloride) ) And mesitylene (0.645 g) were added to prepare varnish V9.
This varnish V9 was used after being filtered with a 0.2 μm pore filter.

<< Preparation of Varnish V10 >>
HxNB (42.03 g, 0.24 mol) and SiX (7.97 g, 0.026 mol) were weighed and placed in a glass bottle.

  To this monomer solution, IRGANOX 1076 (0.5 g) and IRGAFOS 168 (0.125 g) were added as antioxidants to obtain a monomer antioxidant solution.

To a solution (20 g) of the above polymer P3 dissolved in mesitylene so as to be 10 wt%, a monomer antioxidant solution (2.4 g) and Pd785 (3.95 × 10 ⁻⁴ g, 5. 03 × 10 ⁻⁷ mol in 0.1 mL of methylene chloride), as a photoacid generator, RHODORSIL 2074 (2.55 × 10 ⁻³ g, 2.51 × 10 ⁻⁶ mol, in 0.1 mL of methylene chloride) and Toluene (2.5 g) was added to obtain varnish V10.
This varnish V10 was used after being filtered through a filter having a pore size of 0.2 μm.

<< Preparation of Varnish V11 >>
HxNB (42.03 g, 0.24 mol) and SiX (7.97 g, 0.026 mol) were weighed and placed in a glass bottle.

  To this monomer solution, IRGANOX 1076 (0.5 g) and IRGAFOS 168 (0.125 g) were added as antioxidants to obtain a monomer antioxidant solution.

To a solution (20 g) of the above polymer P8 dissolved in mesitylene so as to be 10 wt%, a monomer antioxidant solution (2.4 g) and Pd785 (3.95 × 10 ⁻⁴ g, 5. 03 × 10 ⁻⁷ mol in 0.1 mL of methylene chloride), as a photoacid generator, RHODORSIL 2074 (2.55 × 10 ⁻³ g, 2.51 × 10 ⁻⁶ mol, in 0.1 mL of methylene chloride) and Toluene (6.12 g) was added to prepare varnish V11.
This varnish V11 was used after being filtered with a filter having a pore size of 5 μm.

<< Preparation of Varnish V12 >>
HxNB (42.03 g, 0.24 mol) and SiX (7.97 g, 0.026 mol) were weighed and placed in a glass bottle.

  To this monomer solution, IRGANOX 1076 (0.5 g) and IRGAFOS 168 (0.125 g) were added as antioxidants to obtain a monomer antioxidant solution.

In a solution (30 g) of the above polymer P9 dissolved in mesitylene so as to be 10 wt%, a monomer antioxidant solution (1.0 g) and Pd785 (1.65 × 10 ⁻⁴ g, 2. 10 × 10 ⁻⁷ mol in methylene chloride 0.1 mL), RHODORSIL 2074 (8.51 × 10 ⁻⁴ g, 8.38 × 10 ⁻⁷ mol in methylene chloride 0.1 mL) and photoacid generator Toluene (5.0 g) was added to prepare varnish V12.
This varnish V12 was used after being filtered with a 0.2 μm pore filter.

<< Preparation of Varnish V13 >>
HxNB (42.03 g, 0.24 mol) and SiX (7.97 g, 0.026 mol) were weighed and placed in a glass bottle.

  To this monomer solution, IRGANOX 1076 (0.5 g) and IRGAFOS 168 (0.125 g) were added as antioxidants to obtain a monomer antioxidant solution.

In a solution (30 g) of the above polymer P14 dissolved in mesitylene so as to be 30 wt%, a monomer antioxidant solution (2.0 g) and Pd785 (3.29 × 10 ⁻⁴ g, 4. 19 × 10 ⁻⁷ mol, in 0.1 mL of methylene chloride), TAG-372R (7.63 × 10 ⁻⁴ g, 8.38 × 10 ⁻⁶ mol, in 0.1 mL of methylene chloride) as a photoacid generator And toluene (10.0 g) was added to prepare varnish V13.
This varnish V13 was used after being filtered with a 0.2 μm pore filter.

Incidentally, poured varnish V13 on SiO ₂ coating plate to form a dry film. This dry film had a Tg of 251 ° C. based on thermomechanical analysis (TMA) of the polymer.

<< Preparation of Varnish V38 >>
HxNB (16.64 g, 0.093 mol) and SiX (33.36 g, 0.110 mol) were weighed and placed in a glass bottle.

  To this monomer solution, IRGANOX 1076 (0.5 g) and IRGAFOS 168 (0.125 g) were added as antioxidants to obtain a monomer antioxidant solution.

In a solution (30.0 g) of the above polymer P3 dissolved in mesitylene so as to be 10 wt%, a monomer antioxidant solution (2.16 g) and a catalyst precursor, Pd785 (1.47 × 10 ⁻³ g, 1.88 × 10 ⁻⁶ mol in methylene chloride 0.1 mL), and RHODORSIL 2074 (7.67 × 10 ⁻³ g, 7.54 × 10 ⁻⁶ mol, methylene chloride 0. In 1 mL) was added to prepare varnish V38.
This varnish V38 was used after being filtered with a 0.2 μm pore filter.

<< Preparation of Varnish V39 >>
HxNB (16.64 g, 0.093 mol) and SiX (33.36 g, 0.110 mol) were weighed and placed in a glass bottle.

  To this monomer solution, IRGANOX 1076 (0.5 g) and IRGAFOS 168 (0.125 g) were added as antioxidants to obtain a monomer antioxidant solution.

In a solution (30.0 g) of the above polymer P34 dissolved in toluene so as to be 30 wt%, a monomer antioxidant solution (2.16 g), and Pd785 (1.47 × 10 ⁻³ g, 1.88 × 10 ⁻⁶ mol in methylene chloride 0.1 mL), and RHODORSIL 2074 (7.67 × 10 ⁻³ g, 7.54 × 10 ⁻⁶ mol, methylene chloride 0. In 1 mL) was added to prepare varnish V39.
This varnish V39 was used after being filtered with a 0.2 μm pore filter.

<< Preparation of Varnish V40 >>
HxNB (16.64 g, 0.093 mol) and SiX (33.36 g, 0.110 mol) were weighed and placed in a glass bottle.

  To this monomer solution, IRGANOX 1076 (0.5 g) and IRGAFOS 168 (0.125 g) were added as antioxidants to obtain a monomer antioxidant solution.

A monomer antioxidant solution (2.16 g) and Pd785 (1.47 × 10 ⁻³ g, 1.88 × 10) were added to a solution (30.0 g) of the above polymer P12 dissolved in mesitylene so as to be 30 wt%. ^-6 mol, in 0.1 mL of methylene chloride), 9,10-dibutoxyanthracene (4.86 × 10 ⁻² g, 1.51 × 10 ⁻⁴ mol, in 0.1 mL of methylene chloride) as a sensitizer And as a photoacid generator, RHODORSIL 2074 (7.67 × 10 ⁻³ g, 7.54 × 10 ⁻⁶ mol, in 0.1 mL of methylene chloride) was added to prepare varnish V40.
This varnish V40 was used after being filtered with a 0.2 μm pore filter.

<< Preparation of Varnish V41 >>
HxNB (16.64 g, 0.093 mol) and SiX (33.36 g, 0.110 mol) were weighed and placed in a glass bottle.

  To this monomer solution, IRGANOX 1076 (0.5 g) and IRGAFOS 168 (0.125 g) were added as antioxidants to obtain a monomer antioxidant solution.

In a solution (30.0 g) of the above polymer P16 dissolved in toluene so as to be 30 wt%, a monomer antioxidant solution (2.16 g), and Pd785 (1.47 × 10 ⁻³ g, 1.88 × 10 ⁻⁶ mol in methylene chloride 0.1 mL), and RHODORSIL 2074 (7.67 × 10 ⁻³ g, 7.54 × 10 ⁻⁶ mol, methylene chloride 0. In 1 mL) was added to prepare varnish V41.
This varnish V41 was used after being filtered with a 0.2 μm pore filter.

<< Preparation of Varnish V42 >>
HxNB (16.64 g, 0.093 mol) and SiX (33.36 g, 0.110 mol) were weighed and placed in a glass bottle.

  To this monomer solution, IRGANOX 1076 (0.5 g) and IRGAFOS 168 (0.125 g) were added as antioxidants to obtain a monomer antioxidant solution.

In a solution (30.0 g) of the above polymer P17 dissolved in toluene so as to be 30 wt%, a monomer antioxidant solution (2.16 g), and Pd785 (1.47 × 10 ⁻³ g, 1.88 × 10 ⁻⁶ mol in methylene chloride 0.1 mL), and RHODORSIL 2074 (7.67 × 10 ⁻³ g, 7.54 × 10 ⁻⁶ mol, methylene chloride 0. In 1 mL) was added to prepare varnish V42.
This varnish V42 was used after being filtered through a filter having a pore size of 0.2 μm.

<< Preparation of Varnish V43 >>
HxNB (16.64 g, 0.093 mol) and SiX (33.36 g, 0.110 mol) were weighed and placed in a glass bottle.

  To this monomer solution, IRGANOX 1076 (0.5 g) and IRGAFOS 168 (0.125 g) were added as antioxidants to obtain a monomer antioxidant solution.

In a solution (30.0 g) of the above polymer P18 dissolved in toluene so as to be 30 wt%, a monomer antioxidant solution (2.16 g) and Pd785 (1.47 × 10 ⁻³ g, 1.88 × 10 ⁻⁶ mol in methylene chloride 0.1 mL), and RHODORSIL 2074 (7.67 × 10 ⁻³ g, 7.54 × 10 ⁻⁶ mol, methylene chloride 0. In 1 mL) was added to obtain varnish V43.
This varnish V43 was used after being filtered with a 0.2 μm pore filter.

<< Preparation of Varnish V44 >>
SiX (50.0 g, 0.164 mol) was weighed and placed in a glass bottle.

  To this monomer solution, IRGANOX 1076 (0.5 g) and IRGAFOS 168 (0.125 g) were added as antioxidants to obtain a monomer antioxidant solution.

A monomer antioxidant solution (1.44 g) and the catalyst precursor C1 (hereinafter abbreviated as “Pd545”) were added to a solution (30.0 g) of the polymer P19 dissolved in toluene so as to be 30 wt%. (1.02 × 10 ⁻³ g, 1.88 × 10 ⁻⁶ mol, in 0.1 mL of methylene chloride) and, as a photoacid generator, RHODORSIL 2074 (7.67 × 10 ⁻³ g, 7.54) Varnish V44 was prepared by adding × 10 ⁻⁶ mol in 0.1 mL of methylene chloride.
The varnish was used after being filtered through a 0.2 μm pore filter.

<< Preparation of Varnish V45 >>
SiX (50.0 g, 0.164 mol) was weighed and placed in a glass bottle.

  To this monomer solution, IRGANOX 1076 (0.5 g) and IRGAFOS 168 (0.125 g) were added as antioxidants to obtain a monomer antioxidant solution.

In a solution (30.0 g) of the above polymer P20 dissolved in toluene so as to be 30 wt%, a monomer antioxidant solution (1.44 g), and Pd545 (1.02 × 10 ⁻³ g, 1.88 × 10 ⁻⁶ mol in methylene chloride 0.1 mL), and RHODORSIL 2074 (7.67 × 10 ⁻³ g, 7.54 × 10 ⁻⁶ mol, methylene chloride 0. In 1 mL) was added to prepare varnish V45.
This varnish V45 was used after being filtered with a 0.2 μm pore filter.

<< Preparation of Varnish V46 >>
SiX (50.0 g, 0.164 mol) was weighed and placed in a glass bottle.

  To this monomer solution, IRGANOX 1076 (0.5 g) and IRGAFOS 168 (0.125 g) were added as antioxidants to obtain a monomer antioxidant solution.

In a solution (30.0 g) of the above-described polymer P21 dissolved in toluene so as to be 30 wt%, a monomer antioxidant solution (1.44 g) and Pd545 (1.02 × 10 ⁻³ g, 1.88 × 10 ⁻⁶ mol in methylene chloride 0.1 mL), and RHODORSIL 2074 (7.67 × 10 ⁻³ g, 7.54 × 10 ⁻⁶ mol, methylene chloride 0. In 1 mL) was added to prepare varnish V46.
This varnish V46 was used after being filtered with a filter having a pore size of 0.2 μm.

<< Preparation of Varnish V47 >>
HxNB (16.64 g, 0.093 mol) and SiX (33.36 g, 0.110 mol) were weighed and placed in a glass bottle.

  To this monomer solution, IRGANOX 1076 (0.5 g) and IRGAFOS 168 (0.125 g) were added as antioxidants to obtain a monomer antioxidant solution.

In a solution (30.0 g) of the above polymer P17 dissolved in toluene so as to be 30 wt%, a monomer antioxidant solution (2.16 g), and Pd785 (1.47 × 10 ⁻³ g, 1.88 × 10 ⁻⁶ mol, in 0.1 mL of methylene chloride), and TAG-372R (6.86 × 10 ⁻³ g, 7.54 × 10 ⁻⁶ mol, methylene chloride 0) as a photoacid generator In 1 mL) to prepare varnish V47.
This varnish V47 was used after being filtered with a filter having a pore size of 0.2 μm.

<< Preparation of Varnish V48 >>
SiX (50.0 g, 0.164 mol) was weighed and placed in a glass bottle.

  To this monomer solution, IRGANOX 1076 (0.5 g) and IRGAFOS 168 (0.125 g) were added as antioxidants to obtain a monomer antioxidant solution.

In a solution (30.0 g) of the above polymer P20 dissolved in toluene so as to be 30 wt%, a monomer antioxidant solution (1.44 g), and Pd545 (1.02 × 10 ⁻³ g, 1.88 × 10 ⁻⁶ mol in 0.1 mL of methylene chloride) and TAG-372R (6.86 × 10 ⁻³ g, 7.54 × 10 ⁻⁶ mol, methylene chloride 0) as a photoacid generator In 1 mL) to prepare varnish V48.
This varnish V48 was used after being filtered with a 0.2 μm pore filter.

<< Preparation of Varnish V63 >>
SiX (50.0 g, 0.164 mol) was weighed and placed in a glass bottle.

  To this monomer solution, IRGANOX 1076 (0.5 g) and IRGAFOS 168 (0.125 g) were added as antioxidants to obtain a monomer antioxidant solution.

In a solution (30.0 g) of the above polymer P24 dissolved in toluene so as to be 30 wt%, a monomer antioxidant solution (1.44 g) and Pd785 (1.47 × 10 ⁻³ g, 1.88 × 10 ⁻⁶ mol in methylene chloride 0.1 mL), and RHODORSIL 2074 (7.67 × 10 ⁻³ g, 7.54 × 10 ⁻⁶ mol, methylene chloride 0. In 1 mL) was added to prepare varnish V63.
This varnish V63 was used after being filtered with a filter having a pore size of 0.2 μm.

<< Preparation of Varnish V64 >>
TMSENB (20.2 g, 0.0834 mol) and SiX (29.80 g, 0.0979 mol) were weighed and placed in a glass bottle.

  To this monomer solution, IRGANOX 1076 (0.5 g) and IRGAFOS 168 (0.125 g) were added as antioxidants to obtain a monomer antioxidant solution.

In a solution (30.0 g) of the above polymer P26 dissolved in toluene so as to be 30 wt%, a monomer antioxidant solution (2.16 g), and Pd785 (1.47 × 10 ⁻³ g, 1.88 × 10 ⁻⁶ mol in methylene chloride 0.1 mL), and RHODORSIL 2074 (7.67 × 10 ⁻³ g, 7.54 × 10 ⁻⁶ mol, methylene chloride 0. In 1 mL) was added to prepare varnish V64.
This varnish V64 was used after being filtered with a 0.2 μm pore filter.

<< Preparation of Varnish V65 >>
TMSENB (20.2 g, 0.0834 mol) and SiX (29.80 g, 0.0979 mol) were weighed and placed in a glass bottle.

  To this monomer solution, IRGANOX 1076 (0.5 g) and IRGAFOS 168 (0.125 g) were added as antioxidants to obtain a monomer antioxidant solution.

In a solution (30.0 g) of the above polymer P14 dissolved in mesitylene so as to be 30 wt%, as a monomer antioxidant solution (2.16 g), Pd785 (1.47 × 10 ⁻³ g, 1.88 × 10 ⁻⁶ mol in methylene chloride 0.1 mL), and RHODORSIL 2074 (7.67 × 10 ⁻³ g, 7.54 × 10 ⁻⁶ mol, methylene chloride 0. In 1 mL) was added to prepare varnish V65.
This varnish V65 was used after being filtered with a 0.2 μm pore filter.

<< Preparation of Varnish V66 >>
To the polymer P14 (5 g), mesitylene (20 g), IRGANOX 1076 (0.05 g) and IRGAFOS 168 (1.25 × 10 ⁻² g) as antioxidants, and RHODORSIL 2074 as a photoacid generator. (4.0 × 10 ⁻³ g in 0.1 mL of methylene chloride) was added to prepare varnish V66.
This varnish V66 was used after being filtered through a filter having a pore size of 0.2 μm.
The compositions of the varnishes prepared above are summarized in Tables 2 to 4 below.

  Moreover, as shown below, each varnish V21-V31, V51-V55, V61, and V62 were prepared, respectively. Each varnish was prepared under a yellow light because it contained a photosensitive material.

<< Preparation of Varnish V21 >>
To the above polymer P12 (5 g), mesitylene (20 g), Irganox 1076 (0.05 g) and Irgafos 168 (0.0125 g) as antioxidants, and RHODORSIL 2074 (release agent) as a photoacid generator (release agent) 4.0 × 10 ⁻³ g in 0.1 mL of methylene chloride) was added to prepare varnish V21.
This varnish V21 was passed through a 0.2 μm pore filter for use.

<< Preparation of Varnish V22 >>
To the above polymer P13 (5 g), mesitylene (20 g), Irganox 1076 (0.05 g) and Irgafos 168 (0.0125 g) as antioxidants, and RHODORSIL 2074 (4.0 ×) as a photoacid generator. 10 ⁻³ g in 0.1 mL of methylene chloride) was added to prepare varnish V22.
This varnish V22 was passed through a 0.2 μm pore filter for use.

<< Preparation of Varnish V23 >>
Varnish V23 was prepared by adding mesitylene (20 g) and Irganox 1076 (0.05 g) and Irgafos 168 (0.0125 g) as an antioxidant to the polymer P14 (5 g).
This varnish V23 was passed through a 0.2 μm pore filter for use.

<< Preparation of Varnish V24 >>
To the polymer P11 (0.9 g) above, mesitylene (3.6 g), Irganox 1076 (9.0 × 10 ⁻³ g) and Irgafos 168 (2.3 × 10 ⁻³ g) as antioxidants, and As a photoacid generator, RHODORSIL 2074 (1.1 × 10 ⁻³ g, in 0.1 mL of methylene chloride) was added to prepare varnish V24.
This varnish V24 was passed through a 0.2 μm pore filter for use.

<< Preparation of Varnish V25 >>
To the polymer P11 (0.9 g) above, mesitylene (3.6 g), Irganox 1076 (9.0 × 10 ⁻³ g) and Irgafos 168 (2.3 × 10 ⁻³ g) as antioxidants, and As a photoacid generator, RHODORSIL 2074 (7.5 × 10 ⁻⁴ g, in 0.1 mL of methylene chloride) was added to prepare varnish V25.
This varnish V25 was passed through a 0.2 μm pore filter for use.

<< Preparation of Varnish V26 >>
To the polymer P11 (0.9 g) above, mesitylene (3.6 g), Irganox 1076 (9.0 × 10 ⁻³ g) and Irgafos 168 (2.3 × 10 ⁻³ g) as antioxidants, and As a photoacid generator, TAG-372R (7.5 × 10 ⁻⁴ g, in 0.1 mL of methylene chloride) was added to prepare varnish V26.
This varnish V26 was passed through a 0.2 μm pore filter for use.

<< Preparation of Varnish V27 >>
To the polymer P11 (0.9 g), mesitylene (3.6 g), Irganox 1076 (9.0 × 10 ⁻³ g) and Irgafos 168 (2.3 × 10 ⁻³ g) as an antioxidant, light RHODORSIL 2074 (1.1 × 10 ⁻³ g, in 0.1 mL of methylene chloride) was added as an acid generator to prepare varnish V27.
This varnish V27 was passed through a 0.2 μm pore filter for use.

<< Adjustment of varnish V28 >>
To the above polymer P11 (0.9 g), mesitylene (3.6 g), Irganox 1076 (9.0 × 10 ⁻³ g) and Irgafos 168 (2.3 × 10 ⁻³ g) as antioxidants, and As a photoacid generator, TAG-372R (7.5 × 10 ⁻⁴ g, in 0.1 mL of methylene chloride) was added to prepare varnish V27.
This varnish V28 was passed through a 0.2 μm pore filter for use.

<< Preparation of Varnish V29 >>
To the polymer P11 (0.9 g) above, mesitylene (3.6 g), Irganox 1076 (9.0 × 10 ⁻³ g) and Irgafos 168 (2.3 × 10 ⁻³ g) as antioxidants, and As a photoacid generator, TAG-372R (1.1 × 10 ⁻³ g, in 0.1 mL of methylene chloride) was added to prepare varnish V29.
This varnish V29 was passed through a 0.2 μm pore filter for use.

<< Preparation of Varnish V30 >>
To the polymer P11 (0.9 g) above, mesitylene (3.6 g), Irganox 1076 (9.0 × 10 ⁻³ g) and Irgafos 168 (2.3 × 10 ⁻³ g) as antioxidants, and As a photoacid generator, RHODORSIL 2074 (7.5 × 10 ⁻⁴ g, in 0.1 mL of methylene chloride) was added to prepare varnish V30.
This varnish V30 was passed through a 0.2 μm pore filter for use.

<< Preparation of Varnish V31 >>
To the polymer P11 (0.9 g) above, mesitylene (3.6 g), Irganox 1076 (9.0 × 10 ⁻³ g) and Irgafos 168 (2.3 × 10 ⁻³ g) as antioxidants, and As a photoacid generator, TAG-372R (1.1 × 10 ⁻³ g, in 0.1 mL of methylene chloride) was added to prepare varnish V31.
This varnish V31 was passed through a 0.2 μm pore filter for use.

<< Preparation of Varnish V51 >>
RHODORSIL 2074 (1.56 × 10 ⁻³ g, 1.54 × 10 ⁻⁶ mol) was used as a photoacid generator in a solution (4.0 g) of the above polymer P15 dissolved in toluene so as to be 30 wt%. Varnish V51 was prepared by adding 0.1 mL of methylene chloride).
This varnish V51 was passed through a 0.2 μm pore filter for use.

<< Adjustment of Varnish V52 >>
TAG-372R (1.56 × 10 ⁻³ g, 1.54 × 10 ⁻⁶ mol) was used as a photoacid generator in a solution (4.0 g) in which the polymer P15 was dissolved in toluene so as to be 30 wt%. In 0.1 mL of methylene chloride) to prepare varnish V52.
The varnish V52 was passed through a 0.2 μm pore filter for use.

<< Preparation of Varnish V53 >>
TAG-371 (1.56 × 10 ⁻³ g, 1.54 × 10 ⁻⁶ mol) was used as a photoacid generator in a solution (4.0 g) of the above polymer P15 dissolved in toluene so as to be 30 wt%. In 0.1 mL of methylene chloride) to prepare varnish V53.
This varnish V53 was passed through a 0.2 μm pore filter for use.

<< Preparation of Varnish V54 >>
TTBPS-TPFPB (1.56 × 10 ⁻³ g, 1.54 × 10 ⁻⁶ mol) was used as a photoacid generator in a solution (4.0 g) in which the polymer P15 was dissolved in toluene so as to be 30 wt%. In 0.1 mL of methylene chloride) to prepare varnish V54.
This varnish V54 was passed through a 0.2 μm pore filter for use.

<< Preparation of Varnish V55 >>
NAI-105 (1.56 × 10 ⁻³ g, 1.54 × 10 ⁻⁶ mol) was used as a photoacid generator in a solution (4.0 g) of the above polymer P15 dissolved in toluene so as to be 30 wt%. In 0.1 mL of methylene chloride) to prepare varnish V55.
This varnish V55 was passed through a 0.2 μm pore filter for use.

<< Preparation of Varnish V61 >>
IRGANOX 1076 (0.05 g) and IRGAFOS 168 (1.25 × 10 ⁻² g) as antioxidants in a solution (16.7 g) of the above polymer P24 dissolved in toluene so as to be 30 wt%, and As a photoacid generator, RHODORSIL 2074 (0.1 g in 0.5 mL of methylene chloride) was added to prepare varnish V61.
This varnish V61 was used after being filtered with a 0.2 μm pore filter.

<< Preparation of Varnish V62 >>
IRGANOX 1076 (0.05 g) and IRGAFOS 168 (1.25 × 10 ⁻² g) as antioxidants in a solution (16.7 g) of the above polymer P24 dissolved in toluene so as to be 30 wt%, and As a photoacid generator, TAG-372R (0.1 g, in 0.5 mL of methylene chloride) was added to prepare varnish V62.
This varnish V62 was used after being filtered with a 0.2 μm pore filter.
The composition of each varnish prepared above is summarized in Table 5 below.

4). Fabrication of optical waveguide and measurement of light propagation loss <Samples WG11 to 18>
4-1-1. Production Samples WG11 to 18 were produced as described below.

<< Sample WG11 >>
As a core layer forming material, filtered varnish V24 was poured onto a glass substrate and spread to a substantially constant thickness with a doctor blade.

  The glass substrate was then placed on a ventilated horizontal platform overnight to evaporate the solvent and form a substantially dry solid film.

The film was irradiated with UV light (wavelength: 365 nm) through a photomask (irradiation amount = 6 J / cm ² ), then heated in an oven at 85 ° C. for 30 minutes, and further heated at 150 ° C. for 60 minutes. Thereby, a core layer (single-layer optical waveguide) was obtained.
In addition, the pattern of the core part was able to be confirmed visually after the 1st heating.

<< Sample WG12 >>
As a core layer forming material, the filtered varnish V25 was poured onto a SiO ₂ coating plate and spread to a substantially constant thickness with a doctor blade.

  The coated plate was then placed on a ventilated level table overnight to evaporate the solvent and form a substantially dry solid film.

The film was irradiated with UV light (wavelength: 365 nm) through a photomask (irradiation amount = 3 J / cm ² ), then heated in an oven at 85 ° C. for 30 minutes, and further heated at 150 ° C. for 60 minutes. Thereby, a core layer (single-layer optical waveguide) was obtained.
In addition, the pattern of the core part was able to be confirmed visually after the 1st heating.

<< Sample WG13 >>
As a core layer forming material, the filtered varnish V26 was poured onto a SiO ₂ coating plate and spread to a substantially constant thickness with a doctor blade.

  The coated plate was then placed on a ventilated level table overnight to evaporate the solvent and form a substantially dry solid film.

The film was irradiated with UV light (wavelength: 365 nm) through a photomask (irradiation amount = 6 J / cm ² ), then heated in an oven at 85 ° C. for 30 minutes, and further heated at 150 ° C. for 60 minutes. Thereby, a core layer (single-layer optical waveguide) was obtained.
In addition, the pattern of the core part was able to be confirmed visually after the 1st heating.

<< Sample WG14 >>
As a material for forming the core layer, filtered varnish V27 was poured onto a SiO ₂ coating plate and spread to a substantially constant thickness with a doctor blade.

  The coated plate was then placed on a ventilated level table overnight to evaporate the solvent and form a substantially dry solid film.

The film was irradiated with UV light (wavelength: 365 nm) through a photomask (irradiation amount = 3 J / cm ² ), then heated in an oven at 85 ° C. for 30 minutes, and further heated at 150 ° C. for 60 minutes. Thereby, a core layer (single-layer optical waveguide) was obtained.
In addition, the pattern of the core part was able to be confirmed visually after the 1st heating.

<< Sample WG15 >>
As a core layer forming material, the filtered varnish V28 was poured onto a SiO ₂ coating plate and spread to a substantially constant thickness with a doctor blade.

  The coated plate was then placed on a ventilated level table overnight to evaporate the solvent and form a substantially dry solid film.

The film was irradiated with UV light (wavelength: 365 nm) through a photomask (irradiation amount = 3 J / cm ² ), then heated in an oven at 85 ° C. for 30 minutes, and further heated at 150 ° C. for 60 minutes. Thereby, a core layer (single-layer optical waveguide) was obtained.
In addition, the pattern of the core part was able to be confirmed visually after the 1st heating.

<< Sample WG16 >>
As a material for forming the core layer, the filtered varnish V29 was poured onto a SiO ₂ coating plate and spread to a substantially constant thickness with a doctor blade.

  The coated plate was then placed on a ventilated level table overnight to evaporate the solvent and form a substantially dry solid film.

The film was irradiated with UV light (wavelength: 365 nm) through a photomask (irradiation amount = 3 J / cm ² ), then heated in an oven at 85 ° C. for 30 minutes, and further heated at 150 ° C. for 60 minutes. Thereby, a core layer (single-layer optical waveguide) was obtained.
In addition, the pattern of the core part was able to be confirmed visually after the 1st heating.

<< Sample WG17 >>
As a core layer forming material, the filtered varnish V30 was poured onto a SiO ₂ coating plate and spread to a substantially constant thickness with a doctor blade.

  The coated plate was then placed on a ventilated level table overnight to evaporate the solvent and form a substantially dry solid film.

The film was irradiated with UV light (wavelength: 365 nm) through a photomask (irradiation amount = 6 J / cm ² ), then heated in an oven at 85 ° C. for 30 minutes, and further heated at 150 ° C. for 60 minutes. Thereby, a core layer (single-layer optical waveguide) was obtained.
In addition, the pattern of the core part was able to be confirmed visually after the 1st heating.

<< Sample WG18 >>
As a core layer forming material, the filtered varnish V31 was poured onto a SiO ₂ coating plate and spread to a substantially constant thickness with a doctor blade.

  The coated plate was then placed on a ventilated level table overnight to evaporate the solvent and form a substantially dry solid film.

The film was irradiated with UV light (wavelength: 365 nm) through a photomask (irradiation amount = 6 J / cm ² ), then heated in an oven at 85 ° C. for 30 minutes, and further heated at 150 ° C. for 60 minutes. Thereby, a core layer (single-layer optical waveguide) was obtained.
In addition, the pattern of the core part was able to be confirmed visually after the 1st heating.

4-1-2. Measurement of Light Propagation Loss The light propagation loss in each sample WG11-18 was measured using the “cutback method”.

This is because light (wavelength: 830 nm) generated from a laser diode is input from one end of the core through an optical fiber, the output from the other end is measured, and the length of the core is cut into several steps. The light output was measured for each length.
The total optical loss in each length of the core part is expressed by the following formula.

Total optical loss (dB) = -10 log (Pn / Po)
Where Pn is the measured output at the other end of each core portion of length P1, P2,... Pn, and Po is at the end of the optical fiber before coupling the optical fiber to one end of the core portion. This is the measurement output of the light source.

  Next, the total optical loss is plotted as shown in FIG. 14 (Chart 1). The regression line of this data is expressed by the following equation.

y = mx + b
In the formula, m represents a light propagation loss, and b represents a coupling loss.
The results of each sample WG11-18 are shown in Table 6 below.

  Moreover, as for the core layer of each sample WG11-18, all were formed with the high dimensional accuracy in which the pattern of a core part respond | corresponds to the mask pattern.

<Sample WG32-36>
4-2-1. Production Samples WG32 to WG36 were produced as shown below.

<< Sample WG32 >>
As a core layer forming material, filtered varnish V51 was poured on a quartz glass plate and spread to a substantially constant thickness with a doctor blade.

  The quartz glass plate was then placed on a ventilated level table overnight to evaporate the solvent and form a substantially dry solid film.

The film was irradiated with UV light (wavelength: 365 nm) through a photomask (irradiation amount = 3000 mJ / cm ² ), then heated in an oven at 85 ° C. for 30 minutes, and further heated at 150 ° C. for 60 minutes. Thereby, a core layer (single-layer optical waveguide) was obtained.
In addition, the pattern of the core part was able to be confirmed visually after the 1st heating.

<< Sample WG33 to 36 >>
A core layer (single-layer optical waveguide) was produced in the same manner as Sample WG32 except that the varnish used as the core layer forming material and the irradiation amount of UV light were changed as shown in Table 7.

4-2-2. Measurement of Light Propagation Loss Light propagation loss in each sample WG32 to 36 was measured in the same manner as described above.
The results of samples WG32 to 36 are shown in Table 8 below.

  Moreover, as for the core layer of each sample WG32-36, the pattern of the core part corresponded to the mask pattern, and all were formed with high dimensional accuracy.

5. 5. Production and evaluation of optical waveguide structure 5-1. Production of optical waveguide structure (Example 1)
In the same manner as the sample WG11, a core layer (core part width 50 μm) having an average thickness of 50 μm was formed.

  Two clad layers with an average thickness of 50 μm were formed using varnish V23 as a clad layer forming material.

The core layer was sandwiched between the two clad layers and heated in an oven at 150 ° C. for 1 hour while applying a pressure of 10 MPa. Thereby, an optical waveguide was obtained.
The optical waveguide was linear with a width of 0.5 cm and a length of 10 cm.

  Next, a copper layer (conductor layer) having an average thickness of 45 μm was formed on both surfaces of the optical waveguide by a low temperature plasma CVD method, respectively, to produce an optical waveguide structure.

(Example 2)
An optical waveguide structure was manufactured in the same manner as in Example 1 except that the core layer was formed in the same manner as in the sample WG12.

(Example 3)
An optical waveguide structure was manufactured in the same manner as in Example 1 except that the core layer was formed in the same manner as in the sample WG13.

(Example 4)
An optical waveguide structure was manufactured in the same manner as in Example 1 except that the core layer was formed in the same manner as in Sample WG14.

(Example 5)
In the same manner as the sample WG15, a core layer having an average thickness of 50 μm (core portion width of 50 μm) was formed.

  Two clad layers with an average thickness of 50 μm were formed using varnish V23 as a clad layer forming material.

The core layer was sandwiched between the two clad layers and heated in an oven at 150 ° C. for 1 hour while applying a pressure of 10 MPa. Thereby, an optical waveguide was obtained.
The optical waveguide was linear with a width of 0.5 cm and a length of 10 cm.

  Next, a copper layer (conductor layer) having an average thickness of 45 μm was formed on both surfaces of the optical waveguide by an electroless plating method, thereby producing an optical waveguide structure.

(Example 6)
An optical waveguide structure was manufactured in the same manner as in Example 5 except that the core layer was formed in the same manner as in Sample WG16.

(Example 7)
An optical waveguide structure was manufactured in the same manner as in Example 5 except that the core layer was formed in the same manner as in Sample WG17.

(Example 8)
An optical waveguide structure was manufactured in the same manner as in Example 5 except that the core layer was formed in the same manner as in the sample WG18.

Example 9
In the same manner as the sample WG32, a core layer (core part width 50 μm) having an average thickness of 50 μm was formed.

  Two clad layers with an average thickness of 50 μm were formed using varnish V23 as a clad layer forming material.

The core layer was sandwiched between the two clad layers and heated in an oven at 150 ° C. for 1 hour while applying a pressure of 10 MPa. Thereby, an optical waveguide was obtained.
The optical waveguide was linear with a width of 0.5 cm and a length of 10 cm.

  Next, a copper layer (conductor layer) having an average thickness of 45 μm was bonded to both surfaces of the optical waveguide by a roll laminating method to produce an optical waveguide structure.

(Example 10)
An optical waveguide structure was manufactured in the same manner as in Example 9 except that the core layer was formed in the same manner as in Sample WG33.

Example 11
An optical waveguide structure was manufactured in the same manner as in Example 9 except that the core layer was formed in the same manner as in Sample WG34.

Example 12
An optical waveguide structure was manufactured in the same manner as in Example 9 except that the core layer was formed in the same manner as in Sample WG35.

(Example 13)
An optical waveguide structure was manufactured in the same manner as in Example 9 except that the core layer was formed in the same manner as in the sample WG36.

(Comparative Example 1)
As a clad layer forming material, a varnish containing a branched polysilane having an aliphatic hydrocarbon group is applied on a glass substrate that has been subjected to a release treatment, and dried at 80 ° C. for 20 minutes to obtain an average thickness of 50 μm. A clad layer was formed.

  Next, a varnish containing a branched polyphenylsilane having an aromatic hydrocarbon group having a refractive index higher than that of the branched polysilane is applied as a material for forming a core layer thereon, at 80 ° C. for 20 minutes. Dried.

  Thereafter, the core is exposed to an ultra-high pressure mercury lamp through a photomask provided with a shielding portion at the core portion, and is heat-treated at 250 ° C. A layer was formed.

  On top of that, the same polysilane varnish as described above was applied as a clad layer forming material and heat treated at 300 ° C. to form a clad layer having an average thickness of 50 μm.

  The optical waveguide was produced as described above. The optical waveguide was linear with a width of 0.5 cm and a length of 10 cm.

  Next, a copper layer (conductor layer) having an average thickness of 45 μm was bonded to both surfaces of the optical waveguide by a roll laminating method to produce an optical waveguide structure.

(Comparative Example 2)
As a clad layer forming material, a UV curable epoxy resin varnish (E3129 manufactured by NTT-AT) is spin-coated on a release-treated glass substrate and then cured by UV irradiation to obtain a clad layer having an average thickness of 50 μm. Formed.

  Next, a UV curable epoxy resin (E3135 manufactured by NTT-AT) having a refractive index higher than that of the UV curable epoxy resin is spin-coated thereon as a core layer forming material, and the core is directly formed by photolithography. The part (width 50 μm × thickness 50 μm) was patterned.

  Thereafter, the same UV curable epoxy resin varnish as described above was spin-coated as a cladding layer forming material, and then cured by UV irradiation to form a cladding layer having an average thickness of 50 μm.

  The optical waveguide was produced as described above. The optical waveguide was linear with a width of 0.5 cm and a length of 10 cm.

  Next, a copper layer (conductor layer) having an average thickness of 45 μm was bonded to both surfaces of the optical waveguide by a roll laminating method to produce an optical waveguide structure.

5-2. Evaluation Each conductor layer of the optical waveguide structure produced in each example and each comparative example was patterned to form a wiring, and a light emitting element and a light receiving element were mounted at predetermined locations to produce a composite device. .

  When these composite devices were operated, the composite devices using the optical waveguide structures of the examples were faster than the composite devices using the optical waveguide structures of the comparative examples. It was confirmed that the operation is possible.

1 is a perspective view (partially cut away) showing an embodiment of an optical waveguide structure of the present invention. It is sectional drawing which shows typically the process example of the 1st manufacturing method of the optical waveguide structure of this invention. It is sectional drawing which shows typically the process example of the 1st manufacturing method of the optical waveguide structure of this invention. It is sectional drawing which shows typically the process example of the 1st manufacturing method of the optical waveguide structure of this invention. It is sectional drawing which shows typically the process example of the 1st manufacturing method of the optical waveguide structure of this invention. It is sectional drawing which shows typically the process example of the 1st manufacturing method of the optical waveguide structure of this invention. It is sectional drawing which shows typically the process example of the 1st manufacturing method of the optical waveguide structure of this invention. It is sectional drawing which shows typically the example of a process of the 4th manufacturing method of the optical waveguide structure of this invention. It is sectional drawing which shows typically the example of a process of the 4th manufacturing method of the optical waveguide structure of this invention. It is sectional drawing which shows typically the example of a process of the 4th manufacturing method of the optical waveguide structure of this invention. It is sectional drawing which shows typically the example of a process of the 4th manufacturing method of the optical waveguide structure of this invention. It is sectional drawing which shows typically the example of a process of the 4th manufacturing method of the optical waveguide structure of this invention. It is sectional drawing which shows typically the example of a process of the 4th manufacturing method of the optical waveguide structure of this invention. It is a chart which shows the change of the total optical loss accompanying the change of the length of a core part.

Explanation of symbols

DESCRIPTION OF SYMBOLS 9 Optical waveguide structure 90 Optical waveguide 91,92 Clad layer 93 Core layer 94 Core part 95 Clad part 901,902 Conductor layer 900 Core layer formation material 910 Layer 915 Polymer 920 Additive 925 Irradiation area 930 Active radiation 935 Mask 9351 Opening 940 Unirradiated region 951, 952 Support substrate 1000 Support substrate 1110 First layer 1120 Second layer 1130 Third layer 2000 Laminate

Claims (16)

An optical waveguide structure having an optical waveguide having a core layer including a core portion, a cladding portion having a refractive index lower than that of the core portion, and a conductor layer provided on at least one surface side of the optical waveguide. ,
The core layer includes a substance that is activated by irradiation with actinic radiation, a main chain and a branch that is branched from the main chain, and at least a part of the molecular structure can be detached from the main chain by the activated substance. Forming a layer containing a polymer having a functional group,
Thereafter, by selectively irradiating the layer with the actinic radiation, the substance is activated in the irradiation region irradiated with the actinic radiation, and the leaving group of the polymer is released, By producing a refractive index difference between the irradiation region and the non-irradiation region of the active radiation, either the irradiation region or the non-irradiation region was obtained as the core portion, and the other was obtained as the cladding portion. Is,
The substance includes a compound that generates a cation and a weakly coordinating anion upon irradiation with the active radiation,
The leaving group causes a decrease in the refractive index of the polymer due to the leaving, and has a -O-Si-diphenyl structure,
The optical waveguide structure, wherein the polymer is mainly a norbornene-based polymer.   The optical waveguide structure according to claim 1, wherein the core layer is obtained by performing heat treatment on the layer after the irradiation with the active radiation.   The optical waveguide structure according to claim 1, wherein the active radiation has a peak wavelength in a range of 200 to 450 nm. The dose of the actinic radiation is, the optical waveguide structure according to any one of claims 1 a 0.1~9J / cm ² 3.   The optical waveguide structure according to claim 1, wherein the active radiation is applied to the layer through a mask.   The optical waveguide structure according to claim 1, wherein the layer further contains an antioxidant.   The optical waveguide structure according to claim 1, wherein the layer further contains a sensitizer.   The optical waveguide structure according to any one of claims 1 to 7, wherein the leaving group is an acid leaving group that is released by the action of the cation. The optical waveguide according to any one of claims 1 to 8 , wherein the core portion and the clad portion have different refractive indexes due to different numbers of the leaving groups bonded to the main chain. Structure. The optical waveguide structure according to any one of the norbornene-based polymer, claims 1 is an addition polymer 9. The norbornene polymer, the optical waveguide structure according to any one of 10 the claims 1 to those containing repeating units of diphenylmethyl norbornene methoxysilane. The norbornene polymer, the optical waveguide structure according to any one of claims 1 to 11 is intended to include alkyl norbornene repeating units. The optical waveguide structure according to any one of claims 1 to 12 , wherein the norbornene-based polymer includes a repeating unit of hexyl norbornene. The optical waveguide structure according to any one of claims 1 to 13 , wherein the optical waveguide has a cladding layer that is provided in contact with at least one surface of the core layer and has a refractive index lower than that of the core portion. The average thickness of the conductive layer, the optical waveguide structure according to any one of the optical waveguide of the average 10 to 90% of the thickness of claims 1 to 14. The optical waveguide structure according to any one of claims 1 to 15 , wherein the conductor layer is formed by at least one of a dry plating method, a wet plating method, and a joining of conductive sheet materials. .

Images