WO2015083584A1 - 光導波路および光・電気混載基板 - Google Patents
光導波路および光・電気混載基板 Download PDFInfo
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- WO2015083584A1 WO2015083584A1 PCT/JP2014/081144 JP2014081144W WO2015083584A1 WO 2015083584 A1 WO2015083584 A1 WO 2015083584A1 JP 2014081144 W JP2014081144 W JP 2014081144W WO 2015083584 A1 WO2015083584 A1 WO 2015083584A1
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- WIPO (PCT)
- Prior art keywords
- optical waveguide
- optical
- epoxy resin
- layer
- resin composition
- Prior art date
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
- G02B6/12—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type of the integrated circuit kind
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/14—Macromolecular materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1488—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
- C08G59/3272—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/02—Optical fibres with cladding with or without a coating
- G02B6/02033—Core or cladding made from organic material, e.g. polymeric material
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/24—Coupling light guides
- G02B6/42—Coupling light guides with opto-electronic elements
- G02B6/43—Arrangements comprising a plurality of opto-electronic elements and associated optical interconnections
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0274—Optical details, e.g. printed circuits comprising integral optical means
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
Definitions
- the present invention relates to an optical waveguide widely used in optical communication, optical information processing, and other general optics, and an optical / electrical hybrid substrate.
- Optical waveguides are incorporated in optical waveguide devices, optical integrated circuits, and optical wiring boards, and are widely used in the fields of optical communication, optical information processing, and other general optics.
- the development of optical / electrical hybrid boards has attracted attention with the trend toward higher information capacity and higher speed transmission.
- the optical / electrical hybrid substrate include those in which various optical waveguides are formed on an electrical wiring substrate.
- Patent Document 1 if the optical waveguide film is covered with a flame retardant film, the manufacturing cost increases, and the thickness of the entire optical waveguide film increases, resulting in poor folding resistance. There's a problem.
- the present invention has been made in view of such circumstances, and an object thereof is to provide an optical waveguide and an optical / electrical hybrid substrate that are excellent in flame retardancy and can be thinned.
- the present invention provides an optical waveguide in which at least one of a core layer and a cladding layer of the optical waveguide is made of a transparent resin composition containing a phosphorus-containing epoxy resin and a photopolymerization initiator.
- the second aspect of the present invention is an optical / electrical hybrid substrate including the optical waveguide according to the first aspect.
- the present inventor has conducted extensive research to solve the above problems, and as a result, at least one of the core layer and the cladding layer of the optical waveguide is made of a transparent resin composition containing a phosphorus-containing epoxy resin and a photopolymerization initiator.
- the present inventors have found that the intended purpose can be achieved without obtaining a desired flame retardant effect without taking measures such as covering with a flame retardant film as in the prior art, and reached the present invention.
- the optical waveguide and the optical / electrical hybrid substrate according to the present invention are flame retardant because at least one of the core layer and the cladding layer is made of a transparent resin composition containing a phosphorus-containing epoxy resin and a photopolymerization initiator. It can be thinned because it is excellent in the properties and the installation of the flame retardant film is unnecessary. Further, along with the above-mentioned thinning, it is possible to achieve lighter optical waveguides and improved folding resistance.
- the optical waveguide of the present invention is formed with, for example, a base material, a clad layer (under clad layer) formed in a predetermined pattern on the base material, and a predetermined pattern for propagating an optical signal on the clad layer. And a clad layer (over clad layer) formed on the core layer.
- at least one of the core layer and the cladding layer is formed of a transparent resin composition containing a phosphorus-containing epoxy resin and a photopolymerization initiator.
- the transparent resin composition for both the under clad layer forming material and the over clad layer forming material.
- the optical waveguide of the present invention can achieve a desired flame retardant effect without providing a flame retardant cover layer, and thus can be reduced in thickness by not having a flame retardant cover layer.
- the cladding layer needs to be formed so as to have a refractive index smaller than that of the core layer.
- the phosphorus-containing epoxy resin contained in the transparent resin composition for example, it is preferable to use an epoxy resin containing a phenyl phosphate skeleton represented by the following general formula (1).
- the content of phosphorus in the phenyl phosphate skeleton structure represented by the general formula (1) is preferable for an epoxy resin component containing 20% by weight or more of a novolak type epoxy resin as an epoxy resin.
- a phosphorus-containing epoxy resin contained in an amount of 1 to 5% by weight that is, when the phosphorus content is within the above range, the solubility of the phosphorus-containing epoxy resin is ensured and flame retardancy is obtained.
- Such a phosphorus-containing epoxy resin is disclosed in, for example, Japanese Patent No. 3613724 and Japanese Patent No. 3533973.
- the epoxy resin component is not limited to the novolak type epoxy resin as long as it is a curable epoxy resin. Besides this, bisphenol type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, resorcin type epoxy resin And a polyglycol type epoxy resin. These may be used alone or in combination of two or more.
- the content of the phosphorus-containing epoxy resin is preferably set in the range of 1 to 80% by weight, more preferably 10 to 25% by weight, based on the entire transparent resin composition. That is, if the content of the phosphorus-containing epoxy resin is less than the above range, the solder heat resistance tends to be insufficient, and if it exceeds the above range, the alkali developability tends to decrease.
- Examples of the photopolymerization initiator used together with the phosphorus-containing epoxy resin include substituted or unsubstituted polynuclear quinones (2-ethylanthraquinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2 , 3-diphenylanthraquinone, etc.), ⁇ -ketaldonyl alcohols (benzoin, pivalon, etc.), ethers, ⁇ -hydrocarbon-substituted aromatic acyloins ( ⁇ -phenyl-benzoin, ⁇ , ⁇ -diethoxyacetophenones, etc.) ), Aromatic ketones (benzophenone, 4,4′-bisdialkylaminobenzophenone such as N, N′-tetraethyl-4,4′-diaminobenzophenone), thioxanthones (2-methylthioxanthone
- the content of the photopolymerization initiator is preferably set in the range of 0.1 to 10% by weight, more preferably 2 to 8% by weight of the whole transparent resin composition. That is, if the content of the photopolymerization initiator is less than the above range, the curability tends to be insufficient, and if it exceeds the above range, the physical properties of the transparent resin composition tend to decrease.
- the transparent resin composition contains a phosphorus-containing epoxy resin and a photopolymerization initiator, if necessary, a cyclic phosphazene compound, a carboxyl group-containing linear polymer, an ethylenically unsaturated group-containing polymerizable compound, and the like. Is done.
- cyclic phosphazene compound for example, a compound having a structure represented by the following general formula (2) is used.
- R is an organic group having a urethane (meth) acrylate structure represented by the general formula (3).
- the specific cyclic phosphazene compound can be prepared, for example, as follows. That is, hydroquinone is added to a phenoxy cyclic phosphazene compound and heated to dissolve. Next, it can be prepared by adding (meth) acryloyloxyethyl isocyanate to this and optionally adding a catalyst to react.
- the content of the cyclic phosphazene compound is preferably set in the range of 5 to 30% by weight, more preferably 10 to 20% by weight, based on the entire transparent resin composition. That is, by including the cyclic phosphazene compound at such a ratio, it becomes more excellent in flame retardancy.
- the carboxyl group-containing linear polymer can be obtained, for example, by copolymerizing (meth) acrylic acid and another monomer having a carboxyl group.
- the linear polymer is easy to design physical properties such as glass transition temperature (Tg) due to abundant raw material monomer types.
- Examples of the other monomer having a carboxyl group include alkyl esters of (meth) acrylic acid such as (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) 2-ethylhexyl acrylate, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, styrene, ⁇ -styrene, vinyltoluene, N-vinylpyrrolidone, Examples include 2-hydroxyethyl (meth) acrylate, acrylamide, acrylonitrile, methacrylonitrile, N-phenylmaleimide, cyclohexylmaleimide, and the like. These may be used alone or in combination of two or more.
- the weight average molecular weight of the carboxyl group-containing linear polymer is preferably in the range of 3000 to 50000, more preferably 4000 to 40000, and still more preferably 5000 to 30000. That is, if the weight average molecular weight is less than the above range, the solder heat resistance tends to deteriorate, and if it exceeds the above range, the alkali developability tends to deteriorate.
- the said weight average molecular weight is measured by polystyrene conversion of a gel permeation chromatography (GPC), for example.
- the acid equivalent of the carboxyl group-containing linear polymer is preferably in the range of 200 to 900, more preferably in the range of 250 to 850, and still more preferably in the range of 300 to 800. That is, if the acid equivalent is less than the above range, the oxidation of copper under high temperature and high humidity is accelerated, which is not preferable, and if it exceeds the above range, alkali developability tends to be deteriorated.
- the carboxyl group-containing linear polymer preferably has a structural unit represented by the following general formula (4).
- x, y and z represent the weight ratio in random copolymerization, x is 0.1 to 0.3, y is 0 to 0.9, and z is 0 to 0.6. It is.
- the carboxyl group-containing linear polymer having the structural unit represented by the general formula (4) includes, for example, a monomer having the structural unit represented by the general formula (4) in the main skeleton, and (meth) acrylic acid. And the other monomer having a carboxyl group is copolymerized.
- the content of the carboxyl group-containing linear polymer is preferably set in the range of 20 to 60% by weight, more preferably 30 to 50% by weight of the whole transparent resin composition. That is, the developability is improved by including the carboxyl group-containing linear polymer in such a ratio.
- the copolymerization amount of (meth) acrylic acid as the copolymer component is preferably set in the range of 10 to 30% by weight, more preferably 15 to 25% by weight, based on the total amount of the copolymer components. . That is, if the amount of copolymerization is less than the lower limit at such a ratio, the development time tends to be long and the workability tends to decrease, and if it exceeds the above range, the tendency to promote the oxidation of copper under high temperature and high humidity This is because of
- ethylenically unsaturated group-containing polymerizable compound for example, it is possible to use a bisphenol A di (meth) acrylate compound represented by the following general formula (5): solder heat resistance, folding resistance, alkali development From the point which is excellent in property etc., it is preferable.
- examples of the alkylene group having 2 to 6 carbon atoms include ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, pentylene group, neopentylene group, and hexylene group.
- an ethylene group is preferable.
- the isopropylene group is a group represented by —CH (CH 3 ) CH 2 —, and is bonded at — (O—Y 1 ) — and — (Y 2 —O) — in the above general formula (5).
- One direction may be used, or two types of bonding directions may be mixed. Good.
- Y 1 and 2 or more Y 2 may be the same or different from each other. May be.
- Y 1 and Y 2 are composed of two or more alkylene groups, two or more of — (O—Y 1 ) — and — (Y 2 —O) — may be present at random. However, it may exist in blocks.
- the substitutable positions of the two benzene rings may have one or more substituents, and in the case of having two or more substituents, These substituents may be the same as or different from each other.
- substituents include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 14 carbon atoms, amino groups, nitro groups, cyano groups, mercapto groups, An allyl group, an alkyl mercapto group having 1 to 10 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, a carboxyalkyl group having 1 to 10 carbon atoms in an alkyl group, an acyl group having 1 to 10 carbon atoms in an alkyl group, Examples thereof include an alkoxy group having 1 to 20 carbon atoms or a group containing a heterocyclic ring.
- the repetition numbers p and q are positive integers selected such that p + q is 4 to 40, more preferably positive integers selected so that p + q is 4 to 15. Particularly preferably, it is a positive integer selected such that p + q is 5 to 13. That is, when p + q is less than the above range, bending resistance tends to be reduced, and when p + q exceeds the above range, the entire system of the transparent resin composition exhibits hydrophilicity, and the insulation reliability under high temperature and high humidity. This is because the tendency to be inferior is seen.
- bisphenol A di (meth) acrylate compound represented by the general formula (5) examples include 2,2′-bis [4- (meth) acryloxydiethoxyphenyl] propane, 2,2 '-Bis [4- (meth) acryloxytetraethoxyphenyl] propane, 2,2'-bis [4- (meth) acryloxypentaethoxyphenyl] propane, 2,2'-bis [4- (meth) acrylic Roxydiethoxyoctapropoxyphenyl] propane, 2,2′-bis [4- (meth) acryloxytriethoxyoctapropoxyphenyl] propane and the like. These may be used alone or in combination of two or more.
- the content of the ethylenically unsaturated group-containing polymerizable compound is preferably set in the range of 5 to 50% by weight, more preferably 10 to 40% by weight of the whole transparent resin composition. That is, by including the ethylenically unsaturated group-containing polymerizable compound at such a ratio, the sensitivity tends to be insufficient if the amount is less than the lower limit, and if the above range is exceeded, the alkali developability tends to decrease. This is because of
- the transparent resin composition for forming an optical waveguide of the present invention if necessary, a filler such as silica, barium sulfate, talc, an antifoaming agent, a leveling agent, a flame retardant, Additives such as stabilizers, adhesion imparting agents, rust preventives such as benzotriazole, thermal crosslinking agents such as epoxy resins and blocked isocyanates can be appropriately blended. These may be used alone or in combination of two or more. These additives are preferably used within the range of 0.01 to 20% by weight of the whole transparent resin composition.
- the above-mentioned transparent resin composition is obtained by blending and mixing the above components so as to have a predetermined content. And it mixes with an organic solvent as needed, and uses it as a transparent resin composition liquid.
- the organic solvent include diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, trimethylolpropane triacrylate, solvent naphtha, N-methylpyrrolidone, ⁇ -butyrolactone, butyl cellosolve, ethyl cellosolve. , Methyl cellosolve, toluene, xylene, mesitylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, or a mixed solvent thereof can be used.
- the amount of the organic solvent used can be mixed with about 0 to 200 parts by weight with respect to 100 parts by weight of the transparent resin composition.
- the refractive index of the clad layer (cured product) formed using the transparent resin composition is preferably 1.56 or less, particularly preferably 1.55 or less.
- cured material) is measured as follows, for example. That is, a clad layer (cured product) having a thickness of about 10 ⁇ m is produced on a smooth surface of a silicon wafer, and the refractive index of the cured clad layer at 850 nm is measured using a prism coupler (SPA-4000 model number) manufactured by SAIRON TECHNOLOGY. .
- the optical waveguide can be manufactured through the following processes, for example. That is, a base material is prepared, and a photosensitive varnish composed of the transparent resin composition is applied onto the base material. By arranging a photomask for exposing a predetermined pattern (optical waveguide pattern) on the varnish coating, irradiating light such as ultraviolet rays through the photomask, and further performing a heat treatment if necessary. Harden. Thereafter, the unexposed portion of the light irradiation is dissolved and removed using a developer, thereby forming an under cladding layer (a lower portion of the cladding layer) having a predetermined pattern.
- a predetermined pattern optical waveguide pattern
- a core forming layer (uncured layer) is formed by applying a core layer forming material (varnish) on the under cladding layer.
- a photomask for exposing a predetermined pattern (optical waveguide pattern) is disposed on the surface of the core forming layer, irradiated with light such as ultraviolet rays through the photomask, and further subjected to heat treatment as necessary. Do. Thereafter, the core layer having a predetermined pattern is formed by dissolving and removing unexposed portions of the core forming layer using a developer.
- the over clad layer (the upper part of the clad layer) is irradiated with light such as ultraviolet rays and further subjected to heat treatment as necessary. Form.
- the target optical waveguide can be manufactured.
- Examples of the base material include a silicon wafer, a metal substrate, a polymer film, and a glass substrate.
- the metal substrate include stainless steel plates such as SUS.
- Specific examples of the polymer film include a polyethylene terephthalate (PET) film, a polyethylene naphthalate film, and a polyimide film. The thickness is usually set in the range of 3 ⁇ m to 3 mm.
- ultraviolet irradiation is performed.
- the ultraviolet light source in the ultraviolet irradiation include a low pressure mercury lamp, a high pressure mercury lamp, and an ultrahigh pressure mercury lamp.
- the irradiation amount of ultraviolet rays is usually 10 to 20000 mJ / cm 2 , preferably 100 to 15000 mJ / cm 2 , more preferably about 500 to 10000 mJ / cm 2 .
- a heat treatment may be further performed in order to complete the curing by the photoreaction.
- the heat treatment conditions are usually 80 to 250 ° C., preferably 100 to 150 ° C., for 10 seconds to 2 hours, preferably 5 minutes to 1 hour.
- examples of the core layer forming material include a solid polyfunctional aromatic epoxy resin, a solid (viscous) fluorene-containing bifunctional epoxy resin, Includes a resin composition appropriately containing the above-mentioned various photopolymerization initiators. Furthermore, in order to prepare and apply
- organic solvent examples include ethyl lactate, methyl ethyl ketone, cyclohexanone, ethyl lactate, 2-butanone, N, N-dimethylacetamide, diglyme, ethylene diglycol acetate, diethylene glycol methyl ethyl ether, propylene glycol methyl acetate, propylene glycol monomethyl ether , Tetramethylfuran, dimethoxyethane and the like. These organic solvents are used alone or in combination of two or more in an appropriate amount so as to obtain a viscosity suitable for coating.
- a coating method using the forming material of each layer on the base material for example, a method using a spin coater, a coater, a circular coater, a bar coater, or the like, a screen printing, a gap using a spacer, or the like.
- a method of forming and injecting by capillary action, a method of coating continuously by a roll-to-roll process with a coating machine such as a multi-coater, and the like can be used.
- the optical waveguide can also be made into a film-like optical waveguide by peeling and removing the substrate.
- the optical / electrical hybrid substrate of the present invention is provided with the optical waveguide formed as described above, for example, with respect to the back surface of the substrate in which electrical wiring is formed on one side by copper printing or the like. As described above, it can be manufactured by forming an under cladding layer, a core layer, and an over cladding layer.
- the optical / electrical hybrid board has the following modes. That is, after forming the under clad layer on one side of the substrate as described above, a core layer is formed on the under clad layer, and electrical wiring is also formed by copper printing or the like. By forming the overcladding layer as described above, an optical / electrical hybrid substrate having a configuration different from the above can be manufactured.
- Cyclic phosphazene compound represented by the following structural formula (6) (SPB-100, manufactured by Otsuka Chemical Co., Ltd.)
- a varnish for forming a core layer was prepared as follows, and was used with the varnish for forming a clad layer to produce an FPC integrated optical waveguide as described below.
- Comparative examples 1 and 2 A varnish for forming a clad layer is coated on the back surface of a flexible printed circuit board substrate (FPC substrate) having a total thickness of 22 ⁇ m using a spin coater, and UV irradiation machine [5000 mJ / cm 2 (I-line filter)].
- an under-cladding layer was formed on the FPC base material, a core layer having a predetermined pattern was formed on the under-cladding layer, and an over-cladding layer was further formed on the core layer.
- an FPC integrated optical waveguide (waveguide total thickness 80 ⁇ m) was obtained.
- the optical waveguides of the examples obtained excellent results in the evaluation of the flame retardancy test.
- the optical waveguide of the comparative example did not satisfy VTM-0, resulting in inferior evaluation in the flame retardancy test.
- optical waveguide and the optical / electrical hybrid substrate of the present invention are excellent in flame retardancy and can be thinned, they can be applied to various uses such as a flexible printed substrate for optical transmission.
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Abstract
Description
東都化成社製、FX-305(リン含有率3重量%)
DIC社製、EPICLONEXA-4816
DIC社製、EHPE-3150
下記の合成方法により得られた、前記一般式(4)で表される構造単位を有するポリマー〔式(4)中、繰り返し単位x,y,zの重量比は、x:y:z=20:31:49、GPC測定(ポリスチレン換算)による重量平均分子量(Mw)は、2.3×104〕
溶媒としてのエチレンジグリコールアセテート135.1gを窒素雰囲気下で500ミリリットルのセパラブルフラスコに入れ、攪拌しながら100℃に加温した。1時間保温した後、モノマーとしてフェノキシエチルアクリレート144.9g、メタクリル酸58.0g、メタクリル酸メチル86.9g、溶媒としてのエチレンジグリコールアセテート70.4g、触媒としてのアゾビスイソブチロニトリル4.6gを混合溶解した溶液を、3時間かけてセパラブルフラスコ内に滴下し反応させた。さらに、100℃で2時間攪拌した後、冷却し、その溶液から固形分(ポリマー)を得た。
エチレンオキサイド変性ビスフェノールA型メタクリレート〔前記式(5)中のp+q=10、BIS-A系アクリレート:新中村化学社製,BPE500〕
トリメチロールプロパントリアクリレート
チバガイギー社製、Irgacure907
日本化薬社製、KAYACURE DETX-S
アデカ社製、SP170
<クラッド層形成用ワニスの調製>
遮光条件下にて、上記各成分を、後記の表1~表2に示す割合で配合し、混合することにより、実施例および比較例のクラッド層形成用ワニスを作製した。
遮光条件下にて、o-クレゾールノボラックグリシジルエーテル(新日鉄住金化学社製、YDCN-700-10)50重量部と、ビスフェノキシエタノールフルオレンジグリシジルエーテル(大阪ガスケミカル社製、オグゾールEG)50重量部と、光重合開始剤(アデカ社製、SP170)1重量部と、乳酸エチル(武蔵野化学研究所社製)50重量部とを混合し、85℃加熱下にて撹拌完溶させ、その後室温(25℃)まで冷却した後、直径1.0μmのメンブレンフィルタを用いて加熱加圧濾過を行うことにより、コア層形成用ワニスを調製した。
〔アンダークラッド層の作製〕
・実施例1~3
総厚22μ厚のフレキシブルプリント基板用基材(FPC基材)の裏面上に、クラッド層形成用ワニスをスピンコーターにて塗工し、ホットプレート上にて有機溶剤を乾燥させた(130℃×30分間)後、UV照射機〔200mJ/cm2(I線フィルタ)〕により所定のマスクパターン〔パターン幅/パターン間隔(L/S)=50μm/200μm〕を介して露光を行った。その後、30℃の1重量%炭酸ナトリウム水溶液を用いて圧力0.2MPaで90秒間現像し、ついで水道水にて90秒間洗浄した後、露光後加熱を行った(650mJ/cm2(I線フィルタ)、140℃×30分間)。このようにして、アンダークラッド層(厚み20μm)を作製した。
・比較例1、2
総厚22μ厚のフレキシブルプリント基板用基材(FPC基材)の裏面上に、クラッド層形成用ワニスをスピンコーターにて塗工し、UV照射機〔5000mJ/cm2(I線フィルタ)〕により所定のマスクパターン〔パターン幅/パターン間隔(L/S)=50μm/200μm〕を介して露光を行い、後加熱を行った(130℃×10分間)。その後、γ-ブチロラクトン中にて現像(25℃×3分間)し、水洗いをした後、ホットプレート上で水分を乾燥(120℃×10分間)させることにより、アンダークラッド層(厚み20μm)を作製した。
・実施例1~3、比較例1,2
形成されたアンダークラッド層上に、スピンコーターを用いて、コア層形成用ワニスを塗工した後、ホットプレート上にて有機溶剤を乾燥させる(130℃×5分間)ことにより、未硬化フィルム状態のコア形成層を形成した。形成された未硬化のコア形成層をUV照射機〔9000mJ/cm2(I線フィルタ)〕により所定のマスクパターン〔パターン幅/パターン間隔(L/S)=50μm/200μm〕を介して露光を行い、後加熱を行った(130℃×10分間)。その後、γ-ブチロラクトン中にて現像(25℃×4分間)を行い、水洗し、ホットプレート上にて水分を乾燥(120℃×10分間)させることにより、所定パターンのコア層(厚み50μm)を作製した。
・実施例1~3
総厚22μ厚のフレキシブルプリント基板用基材(FPC基材)の裏面上に、クラッド層形成用ワニスをスピンコーターにて塗工し、ホットプレート上にて有機溶剤を乾燥させた(130℃×30分間)後、UV照射機〔200mJ/cm2(I線フィルタ)〕により所定のマスクパターン〔パターン幅/パターン間隔(L/S)=50μm/200μm〕を介して露光を行った。その後、30℃の1重量%炭酸ナトリウム水溶液を用いて圧力0.2MPaで90秒間現像し、ついで水道水にて90秒間洗浄した後、露光後加熱を行った(650mJ/cm2(I線フィルタ)、140℃×30分間)。このようにして、オーバークラッド層(厚み10μm)を作製した。
・比較例1、2
形成されたコア層上に、スピンコーターを用いて、クラッド層形成用ワニスを塗工して、未硬化状態のオーバークラッド層を形成した。形成された未硬化のオーバークラッド層をUV照射機〔5000mJ/cm2(I線フィルタ)〕にて露光を行い、後加熱を行った(130℃×10分間)。その後、γ-ブチロラクトン中にて現像(25℃×3分間)し、水洗いをした後、ホットプレート上で水分を乾燥(120℃×10分間)させることにより、オーバークラッド層(厚み10μm)を作製した。
上記各光導波路を、難燃性試験規格UL94に準拠した装置(東洋精機製作所社製、No.1031、HVUL UL燃焼テストチャンバー)、方法(VTM法)に従って難燃性を評価し、下記の基準にて示した。
○:VTM-0であった。
×:VTM-0を満たさなかった。
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EP14868315.4A EP3059621A1 (en) | 2013-12-04 | 2014-11-26 | Light-guide path and optical/electric hybrid board |
KR1020167012208A KR20160098181A (ko) | 2013-12-04 | 2014-11-26 | 광도파로 및 광·전기 혼재 기판 |
CN201480061535.8A CN105723260A (zh) | 2013-12-04 | 2014-11-26 | 光波导和光电混载基板 |
US15/157,041 US20160266310A1 (en) | 2013-12-04 | 2016-05-17 | Optical waveguide, and opto-electric hybrid board |
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KR (1) | KR20160098181A (ja) |
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WO2017170668A1 (ja) * | 2016-03-31 | 2017-10-05 | 日産化学工業株式会社 | 高屈折率硬化膜形成用樹脂組成物 |
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JP7224802B2 (ja) * | 2018-07-31 | 2023-02-20 | 日東電工株式会社 | 光導波路形成用感光性エポキシ樹脂組成物、光導波路形成用感光性フィルムおよびそれを用いた光導波路、光・電気伝送用混載フレキシブルプリント配線板 |
CN115210208A (zh) | 2020-06-18 | 2022-10-18 | 丸善石油化学株式会社 | 高纯度4-羟基苯乙烯溶液、其制造方法、及4-羟基苯乙烯系聚合物的制造方法 |
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- 2014-11-26 KR KR1020167012208A patent/KR20160098181A/ko not_active Application Discontinuation
- 2014-11-26 CN CN201480061535.8A patent/CN105723260A/zh active Pending
- 2014-11-26 TW TW103141017A patent/TW201529322A/zh unknown
- 2014-11-26 WO PCT/JP2014/081144 patent/WO2015083584A1/ja active Application Filing
- 2014-11-26 EP EP14868315.4A patent/EP3059621A1/en not_active Withdrawn
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US20160266310A1 (en) | 2016-09-15 |
CN105723260A (zh) | 2016-06-29 |
KR20160098181A (ko) | 2016-08-18 |
TW201529322A (zh) | 2015-08-01 |
EP3059621A1 (en) | 2016-08-24 |
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