WO2004095093A1 - Optical waveguide, optoelectric hybrid substrate, and optoelectric hybrid substrate producing method - Google Patents

Abstract

An optical waveguide in which a core section and a clad section are formed on a substrate, characterized in that the clad section is made of an activation-energy-ray-curable thermosetting solder resist compound having alkali developability.

Description

 Specification

Optical path, opto-electric hybrid board, and method of manufacturing the opto-electric hybrid board

Technical field

 The present invention relates to an optical waveguide, an opto-electric hybrid board provided with the optical waveguide, and a method for manufacturing the same. More specifically, the present invention is particularly useful as a waveguide that can be used in multi-mode at a communication wavelength of about 0.85 m. This is related to a simple optical waveguide.

Background technique

 With the practical application of optical communication systems by the development of low-loss optical fibers, the development of various optical communication components is desired, and optical wiring technology for mounting these optical components at high density, especially optical waveguide technology. It is hoped that this will be established. In general, optical waveguides are required to have the following conditions: (i) the refractive index difference between the core and the clad can be controlled; (ii) easy manufacture; and (i ii) small optical loss.

Until now, a core-cladding structure using a polymer with excellent transparency, such as polystyrene, as the core, and a polymer with a lower refractive index than the core material as the cladding material (See, for example, Japanese Patent Application Laid-Open No. 3-188402). On the other hand, the use of a polyimide, which is a transparent polymer having high heat resistance, has been proposed. yo is, still and heat resistance superior optical waveguide and has a low loss (for example, _JP-a-4 one ₉ 8 0 7 see JP.) this use of Futsui spoon poly Lee Mi de further click la head material As a result, an optical waveguide having a large difference in the refractive index between core curves is realized (see, for example, Japanese Patent Application Laid-Open No. 2002-224241). However, in these methods, when a core structure is formed on the surface of the cladding layer, irregularity processing such as reactive ion etching or the like is performed for each sheet through a photo resist pattern. Necessary and the process was complicated. In addition, reactive ion etching requires processing at wafer size and cannot be formed at a large size, and has a problem with mass productivity and cost reduction because the etching rate is low. . In addition, fluorine contained in polyfluoride has a problem that it has an environmental impact and is difficult to dispose.

 On the other hand, as a simple method of fabricating a polymer waveguide in the atmosphere, a polymer film for photobleaching is formed on a substrate on which a polymer film having a lower refractive index is formed. Then, a photomask on which a desired core pattern is drawn is placed on the photobleaching polymer film and irradiated with ultraviolet light, and the photobleaching polymer film irradiated with ultraviolet light is irradiated. The low refractive index of the polymer film for photobleaching is reduced by reducing the refractive index of the polymer to form side walls, and the area not exposed to ultraviolet light to the core layer without a decrease in the refractive index. A method for realizing a polymer waveguide by forming a polymer film for a high-efficiency clad is disclosed (for example, Japanese Patent Application Laid-Open No. 2002-182502). See the gazette.).

 However, in this technique, since the refractive index of the core and the cladding is controlled by the degree of photoreaction, the refractive index is unstable and the control is not easy. It was difficult to stably secure the difference in the refractive index between the core arcs.

It is also used in the production of polymer waveguides with low loss and high refractive index difference. In addition, there has been disclosed a technique in which a polysilane compound is used as a polymer material and a film made of the polysilane compound is heat-treated at a temperature of 350 ° C. or more (for example, see Japanese Patent Application Laid-Open No. 03-38583, JP-A-2003-57474). In this technique, a polysilane compound film is subjected to a heat treatment at a temperature of 350 ° C. or higher to promote mineralization, thereby obtaining a low loss and a high relative refractive index difference. However, it is necessary to use a substrate that can withstand a temperature of at least 350 ° C, and it is necessary to use a ceramic substrate, Si, G a It has a problem that it is limited to semiconductor substrates such as As and heat-resistant plastic substrates such as polyimide. Also, it is not desirable from the viewpoint of energy saving.

In addition to communication systems, with the spread of IT, the development of high-speed signal processing technologies such as computers and servers that perform faster signal processing is desired. In terminal equipment that performs high-speed signal processing by applying waveguide technology that is advantageous for signal propagation speed, ICs that perform signal processing operate on electrical signals. In addition, since a converter that operates on electricity from light to light or from light to electricity is required, research is also being conducted on opto-electric hybrid boards in which electric circuits are formed on the same substrate in addition to optical circuits. Specifically, an opto-electric hybrid board in which a waveguide film is adhered to an electric wiring board on which a solder resist layer is formed by using an adhesive has been realized (for example, (Japanese Patent Application Laid-Open Publication No. 2000-230360). However, in addition to the problem that optical coupling loss is likely to occur due to misalignment at the time of bonding, in addition to the problem that the adhesive is used as an auxiliary material, In addition, there were problems in terms of the need for a solder resist, mass production, and cost reduction.

Disclosure of the invention

 SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and it is easy to adjust the refractive index difference between cores, and it is possible to stably secure a desired high refractive index difference. It is an object of the present invention to provide a waveguide, and to provide a method for easily and inexpensively manufacturing an opto-electric hybrid board provided with the optical waveguide.

 As a result of intensive studies by the present inventors, the above-mentioned problems have been solved by using an active energy linear curable and thermosetting solder resist composition having alkaline developability as a cladding material. It has been found that the present invention can be solved, and the present invention has been completed.

 That is, according to the present invention, a core portion and a cladding portion are formed on a base material, and the refractive index of the cladding portion is lower than that of the core portion. An optical waveguide is provided, wherein the clad portion is formed of an active energy ray-curable / thermo-curable solder resist composition having alkaline developability.

 Further, according to the present invention, the core portion and the clad portion are formed on the base material having the conductor for solder connection on the surface, and the refractive index of the clad portion is reduced by the refractive index of the core portion. In the optical waveguide having a lower refractive index, the cladding portion is formed of an active energy linear curable / thermocurable solder resist composition having a renewable developing property. Wave paths are provided.

Also, according to the present invention, the solder resist layer and the solder A core portion and a cladding portion are formed on a printed wiring board having a connecting conductor and an optical waveguide in which the refraction index of the cladding portion is lower than that of the core portion. The opto-electric hybrid board, wherein the cladding portion is formed of an active energy linear curable / thermo-curable solder resist composition having a developing property. A hybrid board is provided.

 Further, according to the present invention, an optical waveguide having an optical waveguide formed by forming a core portion and a clad portion on a printed wiring board having a solder resist layer and a solder connection conductor on the surface is provided. A method of manufacturing an electric hybrid board, characterized in that the solder resist layer and the clad portion are simultaneously formed using an active energy linear curable / thermo curable solder resist composition. The method for manufacturing the opto-electric hybrid board described above is provided.

 In the manufacturing method, in a case where the cladding portion includes a lower layer, a middle layer, and an upper layer cladding, a groove portion for embedding a core portion is formed at a predetermined position of the middle layer cladding portion. After embedding the core in the groove, the upper cladding can be provided to form the optical waveguide. Alternatively, the optical waveguide can be formed by disposing the core portion at a predetermined position on the surface of the lower-layer cladding portion, and then providing the middle-layer and upper-layer cladding portions.

 In the present invention, it is preferable that the refractive index of the cladding is lower than the refractive index of the core by 0.5% or more in a value measured by a prism power bra.

In addition, the active energy ray-curable / thermo-curable solder resist composition having alkaline developability includes a carboxylic acid group. It may contain a compound, a (meth) acryloyl group-containing compound, a cyclic ether and a photopolymerization initiator.

 The use of the solder resist composition as a constituent material of the clad portion enables low-temperature curing, and also provides a light guide having a high refractive index difference between the core and the clad. It has become possible to provide a stable wave path. Further, by using the solder resist composition as a constituent material of the clad portion, it is possible to simultaneously form the solder resist layer and the clad portion. Therefore, the manufacturing process of the opto-electric hybrid board can be simplified and the cost can be reduced.

 According to the present invention, since a solder resist composition having a carboxyl group-containing compound and a cyclic (thio) ether group-containing compound is used, the reaction between the carboxylic acid group and the cyclic (thio) ether group is carried out. The adhesion to the substrate is improved due to the resulting 1 OH group and 1 SH group, and it is possible to adhere to the substrate without an adhesive layer.

BRIEF DESCRIPTION OF THE FIGURES

 FIG. 1 is a cross-sectional view schematically showing one embodiment of the printed wiring board of the present invention.

 FIG. 2 is a cross-sectional view schematically showing one embodiment of a manufacturing process of the opto-electric hybrid board of the present invention.

 FIG. 3 is a cross-sectional view schematically showing another embodiment of the manufacturing process of the opto-electric hybrid board of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention relates to an optical waveguide having a core portion and a clad portion. As a material constituting the cladding part, an active energy linear curable / thermocurable solder resist composition having developability is used.

(Hereinafter, also referred to as “solder resist composition of the present invention”), which stably provides a high refractive index difference between the core and the clad. This is particularly useful as an optical waveguide that can be used in multimode using a communication wavelength near 0.85 μπι.

 In a multi-mode waveguide, the number of modes increases and the light propagation improves as the width of the core increases and as the difference in the refractive index between the core and the clad increases. The difference in the refractive index is generally obtained by the following equation. In a multi-mode waveguide, the difference in the refractive index is preferably 0.5% or more, more preferably 1. 0% or more. As is clear from the examples described below, according to the present invention, it is possible to stably provide an optical waveguide having a refractive index difference exceeding 2%.

Refractive index difference = ( _{η ι} -η ₀ ) / n _{l X} 1 0 0 (%)

 (In the formula, represents the refractive index of the core, and n represents the refractive index of the cladding.)

 Although the dimensions of the core vary depending on the difference between the refractive index of the core and the cladding and the desired number of modes, the optical waveguide of the present invention can be multi-mode using a communication wavelength near 0.85 μm. When it is used for a metal, it is desirable to be in the range of 20 to 80 μπι.

 Next, adjustment of the refractive index of the core and the clad will be described.

Adjust the refractive index of the core and cladding composition to adjust the core and cladding composition. Obtain the refractive index difference of The refractive index of the composition can be adjusted from the refractive index of the molecule by changing the structure of the compound, in addition to the method of adjusting the refractive index of the bonding segment by changing the reaction system. The adjustment may be made using a method.

 A compound having a carboxyl group, a compound having a (meth) acryloyl group, a cyclic (thio) ether which may be an essential component of the solder resist composition of the present invention constituting the cladding portion. In a system containing a group-containing compound and a photopolymerization initiator, the refractive index is determined not by adjusting the amount of each reactive group but by adjusting the mother skeleton and the mixing ratio of the compound having each reactive group. It is easy to adjust and the effectiveness is high.

In order to increase the refractive index of an organic compound, it is effective to increase the molecular refraction or decrease the molecular volume. Specifically, a conjugated structure such as a benzene ring, sulfur, one COO— one COOH, S 0 _2, cs, introduction of halogens other than full Tsu element is valid. However, the introduction of bromine and chlorine is less desirable than environmental load.

In order to lower the refractive index of an organic compound, it is effective to decrease the molecular refraction or increase the molecular volume. Specifically, an aliphatic ring having 3 to 6 carbon atoms, mono-OH, — O —, C = C 1, NH ₂ , introduction of fluorine is effective, but fluorine-containing polymer has a problem in waste treatment, and cost of material cost And the introduction of fluorine is less desirable.

 The clad composition (the solder resist composition of the present invention) and the core composition will be specifically described below.

<Clad composition> << Carboxyl group-containing compound >>

 The carboxyl group-containing compound (A) is a compound having one or more carboxyl groups in the molecule, and is a carboxyl group-containing compound containing only a carboxyl group, and further has a photosensitive ethylenic property. Any of the carboxyl group-containing photosensitive resins having an unsaturated double bond can be used, and is not limited to a specific one. In particular, resins such as those listed below (polymer) And polymers may be used).

 (1) a carboxyl group-containing resin obtained by copolymerizing (a) an unsaturated carboxylic acid and (b) a compound having an unsaturated double bond,

 (2) A copolymer of (a) unsaturated carboxylic acid and (b) a compound having an unsaturated double bond may be added with an ethylenically unsaturated group (b ') as a pendant. A carboxyl group-containing photosensitive resin obtained by

 (3) (c) a copolymer of a compound having an epoxy group and an unsaturated double bond in one molecule and (b) a copolymer of a compound having an unsaturated double bond, and (d) an unsaturated monocarboxylic acid And (e) a carboxyl group-containing photosensitive resin obtained by reacting (e) a saturated or unsaturated polybasic acid anhydride with the generated secondary hydroxyl group,

(4) (f) a copolymer of an acid anhydride having an unsaturated double bond and (b) a copolymer of a compound having an unsaturated double bond, and (g) a hydroxyl group and an unsaturated double bond in one molecule. A carboxyl group-containing photosensitive resin obtained by reacting a compound having a bond, (5) (h) reacting a polyfunctional epoxy compound with (d) unsaturated monocarboxylic acid, and reacting the resulting hydroxyl group with (e) a saturated or unsaturated polybasic anhydride to obtain a hydroxyl group. Containing photosensitive resin,

 (6) (i) After reacting (e) a saturated or unsaturated polybasic acid anhydride with a hydroxyl group-containing polymer, (c) an epoxy group and an unsaturated double bond in one molecule are formed on the resulting carboxylic acid. A hydroxyl- and carboxyl-containing photosensitive resin obtained by reacting a compound having

(7) (h) a polyfunctional epoxy compound, (d) an unsaturated monocarboxylic acid, (j) at least one alcoholic hydroxyl group in one molecule, and an alcohol reacting with the epoxy group. (E) a carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a compound having one reactive group other than a hydroxyl group with a saturated or unsaturated polybasic anhydride, and

 (8) (k) A polyfunctional oxetane compound having at least two oxetane rings in one molecule is reacted with (d) an unsaturated monocarboxylic acid to obtain a modified oxetane resin. And (e) a carboxyl group-containing photosensitive resin obtained by reacting (e) a saturated or unsaturated polybasic acid anhydride with the primary hydroxyl group.

 Among these, a carboxyl group-containing photosensitive resin having two or more photosensitive unsaturated double bonds in one molecule, particularly the carboxyl group-containing photosensitive resin of the above (5) is preferable.

The carboxyl group-containing compound (A) as described above has a large number of free carboxyl groups in the side chain of the backbone polymer, and thus can be developed with a dilute aqueous solution. The acid value of the carboxyl group-containing compound (A) is preferably usually in the range of 45 to 20 Omg KOH / g. If the acid value of the carboxyl group-containing compound is less than 45 mg KOHZ g, alkali development becomes difficult, while if it exceeds 200 mg KOH / g, dissolution of the exposed area by the developer proceeds. As a result, the line becomes thinner than necessary, and in some cases, it dissolves and peels off with the developer without distinguishing between the exposed and unexposed areas, making it difficult to draw a normal resist pattern. Not preferred.

 The carboxyl group-containing resin (1) is obtained by copolymerizing (a) an unsaturated carboxylic acid and (b) a compound having an unsaturated double bond, and contains a carboxyl group. Therefore, it is soluble in aqueous alkaline solutions.

Specific examples of the unsaturated carboxylic acid (a) include acrylic acid, metaacrylic acid, itaconic acid, crotonic acid, maleic acid, and fumaric acid. Acids or their anhydrides, and acid anhydrides such as maleic anhydride, itaconic anhydride, pyromellitic anhydride, and 2—hydroxyxetil Hydroxyl-unsaturated compounds, such as hydroxyalkyl (meta) acrylates, such as hydroxypropyl (meta) acrylate, and 2-hydroxypropyl (meta) acrylate And ω-carboxy-polyproteratomer which can be produced by adding ε-proproratone to these unsaturated carboxylic acids. Tommono (meta) acrylate, etc., and these may be used alone or in combination of two or more. And this used in combination Ru can. Among these, acrylic acid and / or metaacrylic acid are preferred. In this specification, In this context, (meta) ata-relate is a general term for ata-relate and meth-a-relate, and the same applies to other similar expressions. .

 Specific examples of the compound (b) having an unsaturated double bond include styrene, chlorostyrene, α; —methylorethylene; and methyl, ethyl, n-propyl and i as substituents. Sopropyl, n-puccinole, i-sobutinole, t-butynole, aminole, 2-—ethynolehexyl, octyl, force pryl, noel, dodecyl, hexadecyl, octadecyl, shik hexyl (Meta) acrylate with (hydroxy) -pinole, 2-hydroxypropynole, 3-hydroxypro pinole, 3-hydroxypro-pinole, etc .; Mono (meta) acrylates of ethylene glycol recall or mono (meta) acrylate of polypropylene glycol; vinyl acetate, Butyl acid, vinyl benzoate; acrylamide, methacrylamide, N-hydroxymethyl acrylamide, N-hydroxymethyl methacrylamide, N-methyl Toximethyl acrylamide, N-ethoxy acrylamide, N_butoxymethyl acrylamide, acrylonitrile, butyl ether, or And the like, and these can be used alone or in combination of two or more. Among these compounds, styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isoptylene are preferably used.

The carboxyl group-containing photosensitive resin (2) is preferably a compound (b) having the unsaturated carboxylic acid (a) and the unsaturated double bond. A resin in which an ethylenically unsaturated group (b ') is pendant to a part of the carboxyl group of the copolymer of the above, and a photosensitive ethylenically unsaturated group (b,) is introduced into the side chain. You. Since a part of the carboxylic acid group of the copolymer remains unreacted, the obtained photographic resin containing a carboxylic acid group is soluble in an aqueous solution of an alkaline resin. Therefore, a film formed from a photosensitive resin composition containing such a resin can be stably developed with an aqueous alkali solution after selective exposure.

 Examples of the ethylenically unsaturated group (b ′) to be added as the pendant include a vinyl group, an aryl group, an atalylyl group, and a methacryloyl group. Such a method of adding an ethylenically unsaturated group to the above-mentioned copolymer is carried out by adding an ethylenically unsaturated compound having an epoxy group to a carboxyl group of the copolymer or a (meth) acrylate. For example, there is a method of performing an addition reaction with a phosphoric acid mouth light.

 Examples of the ethylenically unsaturated compound having an epoxy group or (meth) acrylic acid chloride include glycidyl (meth) acrylate, and arylglycidyl. Ether; 3-methylglycidyl (meta) acrylate, glycidyl ether crotonic acid, 3, 4-epoxysilicone hexylmethyl (meta) acrylate, ( (Meta) Acrylic acid chloride, crotonic acid chloride and the like. Of these, glycidyl (meta) acrylate is preferred.

The photosensitive resin having a carboxyl group of (3) is a copolymer of (c) a compound having an epoxy group and an unsaturated double bond in one molecule and a compound (b) having the unsaturated double bond in one molecule. Epoxy group (D) reacting the carboxyl group of the unsaturated monocarboxylic acid at a rate that improves the photocurability to the extent that a sufficient photocuring depth can be obtained, and the unsaturated double bond of the unsaturated monocarboxylic acid Is a resin in which (e) a saturated or unsaturated polybasic acid anhydride is added to the secondary hydroxyl group generated by the above addition reaction, and a carboxyl group is introduced into the side chain. .

 Specific examples of the compound (c) containing an epoxy group and an unsaturated double bond in one molecule described above include glycidyl (meth) atalylate and i3—methyl thiidyl ( Methacrylate), 3,4—epoxycyclohexylmethyl (meta) acrylate, etc. These can be used alone or in combination of two or more. You.

 Specific examples of the unsaturated monocarboxylic acid (d) include acrylic acid, metaacrylic acid, crotonic acid, ca-cinnamic acid, cyano-canoic acid, and ω-carpoxy. One polyprotonate mono (meta) acrylate is used, and these can be used alone or in combination of two or more.

 On the other hand, specific examples of the saturated or unsaturated polybasic acid anhydride (e) include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and hexahydroanhydride. Phthalic acid, methylhexahydrophthalic anhydride, itaconic anhydride, methylendmethylentetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. These can be used alone or in combination of two or more.

The (4) carboxyl group-containing photosensitive resin is (f) unsaturated (G) a hydroxyl group and an unsaturated double bond in one molecule are added to the acid anhydride group of the copolymer of the acid anhydride having a double bond and the compound (b) having an unsaturated double bond. This is a resin in which a hydroxyl group of a compound having the same is reacted to form a half ester, and the unsaturated double bond of the compound (g) is introduced into a side chain.

 Specific examples of the acid anhydride (f) having an unsaturated double bond include maleic anhydride, itaconic anhydride, and pyromellitic anhydride. 2-hydroxyalkyl (meta) acrylates such as hydroxypropyl (meta) acrylate and 2-hydroxypropyl (meta) acrylate Examples thereof include partial reaction products with an unsaturated compound having a hydroxyl group, and these can be used alone or in combination of two or more. Among these, maleic anhydride, which can stably synthesize a polymer, is preferable.

Specific examples of the compound ( _g ) having a hydroxyl group and an unsaturated double bond in one molecule thereof include 2—hydroxyshetyl (meta) phthalate and 2—hydroxypropyl Hydroxyalkyl (meta) acrylates such as (meta) acrylate; ratatone-modified hydroxyxethyl (meta) acrylate and the like; Or two or more types can be used in combination.

 The above-mentioned carboxyl group-containing photosensitive resins (2) to (4) are excellent in photocurability and contribute to dryness to the touch of the composition.

(5) The carboxyl group-containing photosensitive resin according to (5): The epoxy group of the functional epoxy compound is reacted with the carboxyl group of the unsaturated monocarboxylic acid (d) to generate epoxy acrylate, and the secondary hydroxyl group generated by the addition reaction is reacted with the saturated hydroxyl group. Alternatively, it is a resin in which a carboxyl group is introduced into a side chain by addition reaction of an unsaturated polybasic acid anhydride (e).

 As the polyfunctional epoxy compound (h), all epoxy resins can be used. Typical examples are bisphenol A type, hydrogenated bisphenol A type, bisphenol F type, bisphenol A type, and phenol phenolic. And common types such as phenolic type, cresol-no-polax type, bisphenol A novolak type, biphenol type, bixylene type, N-glycidyl type, etc. Epoxy compounds and EHPE-3150 manufactured by Daicel Co., Ltd. are preferred as commercially available products. Furthermore, a polyfunctional bisphenol obtained by reacting an epihalohydrin such as epichlorohydrin with a hydroxyl group of a solid bisphenol-type epoxy resin to obtain a polyfunctional polyfunctional bisphenol. And epoxy resin. Among these, it is particularly preferable to use a phenolic novolak type epoxy resin, a cresol novola type epoxy resin, or a polyfunctional bisphenol type epoxy resin which has many epoxy groups and is solid. These polyfunctional epoxy compounds (h) can be used alone or in combination of two or more.

The reaction between the polyfunctional epoxy compound (h) and the unsaturated monocarboxylic acid (d) is carried out by an equivalent number of epoxy groups, an equivalent number of carboxyl groups, SO.8-1.2, preferably 0.9-0.9. It is preferable to do so at a rate of 1.05. Equivalent number of epoxy groups / carbo If the equivalent number of the xyl group is less than 0.8, the unsaturated monocarboxylic acid (d) will remain, causing a problem of odor.On the other hand, if the equivalent number exceeds 1.2, a large amount of epoxy groups will remain. However, it is not preferred because it becomes easy to gel at the stage of reacting a saturated or unsaturated polybasic acid anhydride (e). The reaction ratio of the saturated or unsaturated polybasic anhydride (e) to the generated secondary hydroxyl group is preferably such that the acid value of the finally obtained resin is 45 to 16 Omg KOHZg. Adjust so that it is within the range. Generally, the acid anhydride group is in the range of 0.3 to 0.9 equivalent, preferably 1 equivalent of the hydroxyl group generated by the reaction of the polyfunctional epoxy compound (h) and the unsaturated monocarboxylic acid (d). 0.5 to 0.7 equivalent.

The compound containing a hydroxyl group and a hydroxyl group of the above (6) is obtained by reacting (i) a polymer containing a hydroxyl group with the saturated or unsaturated polybasic anhydride (e), and A resin in which a photosensitive group is introduced by reacting a compound ( _c ) having an unsaturated double bond with an epoxy group in one molecule. Polyvinyl acetal, cellulose or the like is used as the hydroxyl group-containing polymer (i), and the composition is adjusted by adjusting the reaction amount of the saturated or unsaturated polybasic anhydride (e). Water can be used as the diluent, and water can be used as the developer in addition to the dilute aqueous solution.

In the above (7), the reaction for synthesizing a photosensitive resin containing a carboxylic acid group is carried out by adding the unsaturated monocarboxylic acid (d) (or at least one alcohol per molecule) to the polyfunctional epoxy compound (h) A reactive hydroxyl group and a compound (j)) having one reactive group other than the alcoholic hydroxyl group that reacts with the epoxy group. A compound having at least one alcoholic hydroxyl group and one reactive group other than an alcoholic hydroxyl group that reacts with an epoxy group (j) (or unsaturated monocarboxylic acid (d)) ), And further reacting with a saturated or unsaturated polybasic acid anhydride (e); and a polyfunctional epoxy compound (g), an unsaturated monocarboxylic acid (h) and a small amount in one molecule. At least one alcoholic hydroxyl group and a compound (j) having one reactive group other than the alcoholic hydroxyl group that reacts with the epoxy group are simultaneously reacted, and then, the saturated or unsaturated polybasic anhydride is further reacted. There is a second method for reacting the substance (e). Either method may be used, but the second method is preferred. At least one hydroxyl group in one molecule and one reactive group other than the alcoholic hydroxyl group that reacts with the epoxy group (for example, a carboxyl group, a phenolic hydroxyl group, a secondary group) Specific examples of the compound (j) having an amino group) include glycolic acid, dimethylolpropionic acid, dimethylolacetic acid, dimethylolbutyric acid, dimethylolvaleric acid, dimethylolcaproate, and the like. (Bis) hydroxymethyl phenol, (bis) hydroxymethyltinolezone, P-hydroxyxenoninoleate 2 —methanoic acid , P — Hydroxifeninolate 3 — Propanolone, p — Hydroxifenethenoleanoleco / le, etc. Dial-aluminums such as diethanolamine and disopropanolamine.

The carboxyl group-containing photosensitive resin (8) is a polyfunctional resin which is a starting material of the carboxyl group-containing photosensitive resin (5). (K) A resin using a polyfunctional oxetane compound instead of the oxy resin (h).

 That is, an unsaturated monocarboxylic acid (d) is reacted with a polyfunctional oxetane compound (k), and the resulting primary or primary hydroxyl group is further saturated or unsaturated polybasic acid. It is a carboxyl group-containing photosensitive resin obtained by reacting an anhydride (d). As described above, the bonding site between the primary hydroxyl group and the acid anhydride is a resin that is hardly thermally cleaved and has excellent thermal stability. By using this, it is possible to prepare a photo-curable / thermo-curable resin composition which is excellent in heat resistance and thermal stability and is of a re-developing type.

 «(Meth) acryloyl group-containing compound >>

 As the (meth) atalyloyl group-containing compound, known reactive diluents such as monofunctional (meth) atalylates and poly- or polyfunctional (meth) atalylates can be used. Can be used. Specific examples are methyl (meta) acrylate, ethyl (meta) 'acrylate, n-butyl (meta) acrylate, isobutyl

(Meta) atalylate, 2-ethylhexyl (meta) atalylate, isodesyl (meta) atalylate, rauril (meta) atalylate, tri Decyl (meta) atalylate, stearyl (meta) atalylate, methoxypolyethylene recall

(Meta) atalylate, cyclohexyl (meta) atalylate, tetrahydrofurfuryl (meta) atelylate, isoboroninole (meta) ately Rate, benzyl (meta) atalylate, 2 — hydrokishetil (meta) atalylate, 2 — hidden Loxypropyl (meta) acrylate, 2-hydroxypropyl (meta) acrylate, dimethylethylaminoethyl (meta) acrylate, ethylene glycol (Metal) atalylate, diethyl glycol (meta) acrylate, 1,4-butanediol di (meta) acrylate, 1, 6 1 Hexane diol (meta) acrylate, trimethylol propane (meta) acrylate, grease rendition (meta) acrylate, pen Terythry tri (meta) acrylate, pentaerythry tetra (meta) aterate, dipentaerythry hex (meta) ) Acrylates, polyester acrylates, and And this include the reaction product of Al co Lumpur having a nucleotide acid anhydride and least one or more unsaturated group in one molecule Ru can.

 These (meta) atalyloyl group-containing compounds may be used alone or

Two or more of them are used in combination, and the compounding amount is 100 parts by mass or less, more preferably 10 to 70 parts by mass, based on 10 parts by mass of the compound containing the propyloxyl group. It is. When the content of the (meth) acryloyl group-containing compound exceeds 100 parts by mass, it becomes difficult to obtain the dryness to the touch required for contact exposure, and the coating film has heat resistance and the like. It is not preferable because the characteristics are deteriorated.

 《Cyclic (thio) ether group-containing compound》

 Examples of the cyclic (thio) ether group-containing compound include compounds having an oxirane ring, an oxetane ring, a thiirane ring, and the like, which are subjected to ring-opening addition polymerization with the above-mentioned carboxyl group-containing compound.

In this specification, a cyclic (thio) ether group-containing The term “compound” is a general term for a compound containing a cyclic ether group, a compound containing a cyclic thioether group, and a mixture thereof.

 Examples of the compound having an oxirane ring include bisphenol A, bisphenol F, bisphenol S, phenolic / phenolic resin, and cresolanolic resin. Active hydrogen-containing compounds such as polyphenols such as fats, polycarboxylic acids such as telephthalic acid, and polyamines such as diaminodiphenylmethane, and epichlorophyll Dalicidyl ethers, glycidyl esters, and glycidyl amins obtained by reacting water and z or methyl chlorohydrin are exemplified. Furthermore, rubber epoxy compounds and alicyclic compounds obtained by reacting perforacetic acid, etc. with cyclic compounds such as polybutadiene and cyclic olefin compounds such as polyhexene derivatives. Examples include epoxy compounds.

 Examples of the compound having an oxetane ring include oxetane alcohols, polycarboxylic acids such as terephthalic acid, or bisphenol A, bisphenol A, bisphenol A, and bisphenol A. Examples thereof include esterified products with polyphenols such as S, phenol-no-polak resin and cresol-no-polak resin.

 Examples of the compound having a thiirane ring include a reaction product of a compound having a thiirane ring such as] 3-epitipropylmercaptane and a polyfunctional thiosocyanate compound.

These cyclic (thio) ether group-containing compounds may be used alone or in combination of two or more. The compounding amount thereof is preferably 0.5 with respect to 1 equivalent of the carboxyl group of the carboxyl group-containing compound. ~ 4.0 equivalents, more preferably 1.2 ~ 1.0. 6 equivalents.

 《Photopolymerization initiator》

Examples of the photopolymerization initiator include benzophenone-based, acetate phenone-based, benzoin ether, benzoin olethanol, monoacrylphosphinoxide, polyester, and titanium. It is a radical photopolymerization initiator such as a nosene type. For example, specific examples of other photopolymerization initiators include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl enoate ether, and benzoin isopropinole ether; Set phenonone, 2, 2—Dimethoxy 2—Phenylacet phenone, 2, 2—Jetoxy 1 2—Pheninoleaset phenonone, 2, 2—Jet xy 2 —Acetatophenones such as phenylacetophenone and 1,1 dichloroacetophenonone; 2—Methylthio 1- [4- (methylthio) phene 2-morpholino-propane-one-one, 2-benzene-one 2-dimethylamino- 1-(4-mono-refino-phenyl) -butanone-one Setophenones; 2 — methyl Anthraquinones such as luantraquinone, 2-ethylentraquinone, 2-tertiary butylantraquinone, and 1-open mouth anthraquinone; 2, 4 —Dimethylthioxanthone, 2,4-diethylthioxanthone, 2—Chloxanthonones, such as chloroxanthoxantone, 2,4 diisopropropylthioxanthone; and acetophenonon dimethyl ketal, Benzene / Resimethione Ketanoles such as ketanore; benzophenones such as benzophenone; or xanthonones; (2,6-dimethoxybenzoyl) 1,2,4,4-pentyl Phosphine oxide, bis (2,4,6—trimethylbenzyl) monophenyl phosphine, 2,4,6, -trimethyl benzoin Phosphinides such as oxinside, ethinoleate 2, 4, 6-trimethinolebenzizolevinolephosphine; and various phosphides, and these are known. Conventional photopolymerization initiators can be used alone or in combination of two or more. The mixing ratio of these photopolymerization initiators is preferably in the range of 0.1 to 20 parts by mass per 100 parts by mass of the compound having a lipoxyl group.

 Optional ingredients

 (Sensitizers, etc.)

 Along with the photopolymerization initiator as described above, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-14-dimethylaminobenzoate, Photosensitizers such as tertiary amines such as lithilamin and triethanolamine can be used alone or in combination of two or more.

 Further, a titanocene-based photopolymerization initiator such as Ciba Specialty Chemicals Inc. Inoregacure 784, which initiates radical polymerization in the visible region, and a leuco dye are used as curing assistants. Can be used in combination.

However, if particles of 1 m or more are present in the clad composition, scattering loss due to inhomogeneity of the core structure is remarkable. Therefore, it is preferable not to include particles of 1 μπι or more. New The solder resist composition used in the present invention may further include, for example, an elastomer, an elastomer, for the purpose of relieving stress, preventing halation, imparting adhesion, and improving characteristics such as applicability. Dyes, adhesion-imparting agents, defoamers, leveling agents, solvents, thixotropic agents, organic nanoparticles, inorganic nanoparticles, polymerization inhibitors, antioxidants, surfactants, polymer dispersants Further optional components such as a compatibilizer, a thermosetting agent, and a thermosetting catalyst may be blended.

 Further, for the purpose of adjusting the refractive index, an organic compound not having a carboxyl group, a (meth) acryloyl group and a cyclic (thio) ether group is used so as not to impair the effects of the present invention. May be blended.

 The solder resist composition of the present invention comprises the above-mentioned carboxyl group-containing compound, (meth) acryloyl group-containing compound, cyclic (thio) ether group-containing compound, and a photopolymerization initiator as essential components. But containing both a carboxyl group and a (meth) acryloyl group, and containing both a Z or cyclic (thio) ether group and a (meth) atalyloyl group It may contain a compound.

 Core composition>

 As long as the composition serving as the core satisfies that the refractive index is lower than the refractive index of the cladding portion, a thermoplastic resin composition, a thermosetting resin composition, a photocurable resin composition, Any of a curable / thermosetting resin composition and a developable resin composition may be used, but it is preferable to use a composition which satisfies a refractive index measured by a prismatic power brush of at least 0.5%. New

Examples of the thermoplastic resin include polycarbonate resin and polycarbonate resin. Polycarbonate resin, Polycarbonate resin, Polyester resin, Polyester resin, Polyether resin, Polysulfide resin, Polysulfide resin, Polysulfone resin, Polysulfide resin Xide resin, polyether ketone resin, polyketone resin, polyurea resin, polyurethan resin, polyamide resin, polyimid resin, polysilane resin , Polysiloxane resin, acryl derivative resin, vinyl derivative resin, resin consisting of benzocyclobutene, tricyclodecane, cyclohexagen resin, norbornene resin, poly Examples include olefin-based resins and fluorine-containing resins.

 The thermosetting resin composition is, for example, a resin composition comprising a reaction system of epoxy, phenols, thiophenols, carboxylic acids, amines, and active esters. A resin composition comprising a reaction system of oxetane and phenols, thiophenols, carboxylic acids, amines, and active esters. Reaction system of thiirane with phenols, thiophenols, carboxylic acids, amines and active esters. Resin compositions comprising a reaction system of chetan and phenols, thiophenols, carboxylic acids, amines, and active esters are exemplified.

 Photocurable resin compositions include, for example, radically polymerizable compositions such as (meta) acrylates, epoxies, vinyl ethers, oxetanes, spirol orthoesters, thiiras. And cationically polymerizable compositions of thiethanes.

Examples of the photocurable and thermosetting resin composition include a system using both the photocurable composition and the thermosetting composition described above. The developable resin composition uses a difference in solubility between a photosensitive site irradiated with active energy and a non-photosensitive site to develop a resin composition capable of developing a pattern with an aqueous alkali solution or an organic solvent to form a pattern. If the refractive index satisfies that the refractive index is lower than the refractive index of the cladding part (preferably, it is lower than 0.5% in the refractive index measured by a prism power bra), A solder resist composition having a composition different from that of the pad composition can be used.

 The skeleton contained in the above-described thermoplastic resin composition, thermosetting resin composition, photocurable resin composition, photocurable / thermosetting resin composition, and developable resin composition includes Bisphenol A skeleton, Bisphenol F skeleton, Bisphenol S skeleton and its hydrogenated and fluorinated skeleton. A biphenyl skeleton, a novel skeleton, a fluorene skeleton, a methyl triphenyl skeleton, an alicyclic hydrocarbon skeleton, an aliphatic hydrocarbon skeleton, and hydrogenated and fluorine-containing skeletons thereof. Sulfur-containing and nitrogen-heterocyclic skeletons such as isocyanuric acid, triazine ring and benzoxazine ring. Hyperbranch polymers, dendrimers, and calixarene skeletons, as well as their hydrogenated, fluorine-containing, sulfur-containing, and nitrogen-heterocyclic skeletons.

Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view schematically showing one embodiment of the printed wiring board of the present invention. As shown in Fig. 1, on a substrate (printed wiring board) 100 having conductor pads 101a and 101b on the surface, an active energy linear curing / thermosetting solder is placed. Solder resist layer formed using resist composition 110a, 110 b, a clad part 102 a, 102 b, 102 c formed using the solder resist composition and a core part having a higher refractive index than the clad part An optical waveguide 104 having 103 and is formed.

FIG. 2 is a cross-sectional view schematically showing one embodiment of a manufacturing process of the opto-electric hybrid board of the present invention. As shown in FIG. 2, an active energy ray-curable and thermosetting solder resist composition was placed on a substrate 200 having a conductor pad 201 on the surface. After stacking (see Fig. 2 (b)), the required parts are irradiated with active energy rays (see Fig. 2 (c)), and the parts (unnecessary parts) that have not been irradiated with the active energy rays are washed with an aqueous alkali solution. Then, the lower layer 202a and the solder resist layer 210 are formed (see FIG. 2 (d)). Next, after laminating the solder resist composition on the substrate on which the lower cladding layer 202 is formed, a necessary portion is irradiated with active energy rays (see FIG. 2 (e)). The part (unnecessary part) which has not been irradiated with the active energy is removed by alkali development and cured by heat to form a middle-layer clad 202b having a concave groove 203 '. See Fig. 2 (f)). Embedding the middle click la head 2 0 2 b which is formed in the groove 2 0 3 ¹ to該Ku rats high de layer by Ri index core 2 0 3 (see FIG. 2 (g)). Next, after laminating the solder resist composition on the core 203 and necessary parts so as to cover the core 203 (see FIG. 2 (h)), the necessary parts are irradiated with active energy rays. The part (unnecessary part) that was not irradiated with the active energy was developed and removed with an aqueous alkali solution, cured by heat, and cured to form an upper layer layer. Is formed to obtain the opto-electric hybrid board 230 of the present invention (see FIG. 2 (i)). In FIG. 2, 204 is an optical waveguide.

 The upper cladding layer 202c can be formed by pattern printing without exposure and development, and curing by irradiation with active energy or heat.

 In the production method of the present invention, laminating the solder resist composition means that the composition is provided in liquid or film form, and in the case of liquid form, it is necessary at the time of coating or after coating. Perform more defoaming, drying, pressing and flattening. If the film is in the form of a film, after laminating it, heat-press it and perform vacuum pressing if necessary. Exposure can also be performed by drawing active energy rays through a mask or directly and curing the required portions. Further, development can be performed at 10 to 50 ° C. using an aqueous solution containing 0.1 to 30% by mass of a basic compound.

FIG. 3 is a cross-sectional view schematically showing another embodiment of the manufacturing process of the opto-electric hybrid board of the present invention. As shown in FIG. 3, on a substrate 300 having a conductor pad 301 on the surface, an active energy ray curable * thermosetting solder resist composition was placed on the substrate 300. After laminating (see Fig. 3 (b)), the required parts are irradiated with active energy rays (see Fig. 3 (c)), and the parts not exposed to the active energy rays (unnecessary parts) are developed with an aqueous alkali solution. Removed to form the lower cladding layer 302a and the solder resist layer 310 (see Fig. 3 (d)). Next, a composition for forming a core (for example, an optical fiber) is formed on the substrate on which the lower-layer clad 302 a is formed. After laminating the thermosetting type alkaline developing composition), the core pattern is irradiated with active energy rays (see Fig. 3 (e)), and the core is left (alkaline) developed and removed, and cured by heat. Then, a core 303 is formed (see FIG. 3 (f)). After laminating the solder resist composition on the core pattern so as to cover the core 303, a necessary portion is irradiated with active energy rays (see FIG. 3 (g)), and the active energy line is formed. The non-irradiated portion (unnecessary portion) is removed by development with an alkali and cured by heat to form the middle and upper clad layers 302 d, thereby providing the present invention. An opto-electric hybrid board 330 is obtained (see Fig. 3 (h)). In FIG. 3, reference numeral 304 denotes an optical waveguide. This cladding layer 302d can be formed by pattern printing without development and curing by irradiation with active energy or heat.

 Hereinafter, the effects that can be obtained by using the solder resist composition in a cloud are listed.

 (1) Two members of the clad and solder resist or three members of the clad, adhesive and solder resist can be formed by one member of the solder resist clad. it can.

 (2) Since the solder resist composition is three-dimensionally crosslinked by light and heat curing, it is not necessary to use an expensive thermoplastic polymer having a high Tg such as polyimide. Heat resistance can be realized, and the refractive index does not change even by heat treatment around 250 ° C.

(3) The refractive index of the solder resist composition can be widely adjusted (for example, 1.523 to 1.559) by changing the composition and the composition ratio, and the obtained refractive index is Manufacturing process of optical waveguide It is stable without being affected by the chemical reaction.

 (4) When forming an optical waveguide on a substrate, a soldering conductor or the like on the substrate can be used as a target mark for positioning and photolithography. The positional accuracy between the light or light-to-electricity converter and the optical waveguide is high, and the optical coupling loss can be suppressed.

 (5) It can be formed using existing printed wiring board manufacturing equipment.

 (6) Unlike reactive ion etching, it can be formed in a large size such as a printed wiring board, and has high design freedom and excellent productivity.

 (7) High productivity compared to reactive ion etching due to alkali development with a high etching rate (for example, reactive ion etching rate is 5 micron Zh, but 1 micron / S).

 (8) The general thermosetting temperature of the solder resist composition is about 150 ° C, and the carboxyl group and cyclic (thio) ether are thermoset at 100 to 250 ° C. Unlike the polysilane compound, the substrate does not require high heat resistance, and the range of usable substrates is wide.

It should be noted that the present invention is not limited to the above (each) embodiment, but can be variously modified in an implementation stage without departing from the gist of the invention. Furthermore, the above embodiments include inventions at various stages, and various inventions can be extracted by appropriate combinations of a plurality of disclosed constituent features. example For example, even if some components are deleted from all the components shown in the embodiment, the problem (at least one) described in the section of the problem to be solved by the invention can be solved. If (at least one of) the effects of the invention is obtained, a configuration in which this component is removed can be extracted as an invention. (Example)

 Hereinafter, the present invention will be described specifically with reference to Examples. However, it is needless to say that the present invention is not limited to the following Examples. In the following, “parts” and “%” all refer to “parts by mass” and “% by mass” unless otherwise specified.

 (Synthesis example 1)

To a 2-liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube, was charged 32.5 g of dipropylene glycol methanol methyl ether at 110 ° C. After heating to ω-force in a mixed atmosphere of air and nitrogen, ω-capillary monoprolate (ratatone η == 2, manufactured by Toagosei Co., Ltd. Μ— 5300) 157.5 g, methacrylic acid 12.7 g, methyl methacrylate 80.8 g, dipropyl pyrene glycol 1 retino methino oleate, 15 4 g, t-petit 9.8 g of norepoxy 21-ethylhexanoate (Nippon Oil & Fats Co., Ltd., Perptyl O) was added dropwise over 3 hours. After the addition, the mixture was stirred for 3 hours to synthesize a carboxyl group-containing polymer. Next, to the above polymer, 3,4-epoxycyclohexyl methylacrylate (A200, manufactured by Daicel Chemical Industries, Ltd.) 238.4 g, triphenylphosphine 1. Calorie 8 g, 1.2 g of methylnodroquinone, 100 ° C For 10 hours. As a result, it has a developability of a solid acid value of 63.6 mg KOH / g, an atalyloyl equivalent of 450, a weight average molecular weight (Mw) of 240,000, and a solid content of 55.2%. Resin A, a light and thermosetting resin solution, was obtained.

 (Synthesis example 2)

 To a 2-liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was charged 32.5 g of dipropylene glycol monomethyl ether, and the mixture was poured into the flask. After heating to C, 166.4 g of methacrylic acid, 121.4 g of methyl methacrylate, and 121.4 g of dimethyl propylene glycol in a mixed atmosphere of air and nitrogen were used. 5 g and 8.1 g of t-butynolenooxy-2-ethoxyethyl hexanoate (Nippon Oil & Fats Co., Ltd., perbutyl O) were added dropwise over 3 hours. After the dropwise addition, the mixture was stirred for 3 hours to synthesize a carboxyl group-containing polymer. Next, 2,4-epoxycycline hexinolemethine oleate acrylate (A200, manufactured by Daisenore Kagaku Kogyo Co., Ltd.) (242.7 g) was added to the above polymer, and trifluorphosphine 1.6 g and methyl hydroquinone (1.1 g) were reacted at 100 ° C for 10 hours. As a result, the photoacid having a solid acid value of 75.7 mg KOH / g, an atalyloyl equivalent of 380, an Mw of 1600, and a solid content of 47.4% was developed. (4) Resin B, which is a thermosetting resin solution, was obtained.

 (Synthesis example 3)

A cresol-no-block epoxy resin (Epiclon N-680, manufactured by Dainippon Ink and Chemicals, Inc.) was placed on a flask equipped with a thermometer, stirrer, dropping funnel, and reflux condenser. Epoxy equivalent = 0561S

33

 210 parts) and 96.4 parts of carbitol acetate were weighed out and heated and dissolved. Next, 0.1 parts of hydroquinone as a polymerization inhibitor and 2.0 parts of triphenylphosphine as a reaction catalyst were added. The mixture was heated to 95-105 ° C, and 72 parts of acrylic acid was gradually added dropwise, and the reaction was continued for about 16 hours until the acid value became 3.0 mg KOH / g or less. I let it. The reaction product is cooled to 80 to 90 ° C, 76.1 parts of tetrahydrophthalic anhydride is added, and the mixture is subjected to infrared absorption analysis.

 The reaction was continued for about 6 hours until the absorption peak (178 cm-) of the acid anhydride disappeared. To this reaction solution, added was Izomitsu Petrochemical Co., Ltd. aromatic solvent ibuzol # 1550.96.4 parts, diluted, and then removed. The resin compound (A) thus obtained, having two or more acryloyl groups and a carboxyl group, has a non-volatile content of 65% and an acid value of solid of 78 mg KOH / g. Resin C, a light and thermosetting resin solution having image properties, was obtained.

 Example 1

 <Clad composition>

130 g of the resin A having a carboxyl group and an acryloyl group obtained in Synthesis Example 1 was used, and 62 g of the resin B having a carboxyl group and an acryloyl group obtained in Synthesis Example 2 were used. 5 g, 5 g of Irgacure 907 manufactured by Chippas Chemical Chemical Co., 1 g of DETX-S manufactured by Nippon Kayaku Co., 0.3 g of BYK 310 manufactured by Vic Chemical Japan, 10 g of Dow Chemical's PMA was added in advance with carbitol acetate to give a resin solution with a solid content of 75%. 10.8 g of Nippon Kayaku Co., Ltd. was added and EP5.54 manufactured by Japan Epoxy Resin Co., Ltd. to which a resin solution having a solid content of 90% was previously added by adding carbitol acetate to 35.5. g, 20 g of DPHA manufactured by Nippon Kayaku Co., Ltd. are weighed, mixed, dispersed and filtered, and used as active-energy linear curable / thermo-curable, which has an alkali-defining property. A resist composition was obtained.

 A solder resist composition formed on a wafer with a film thickness of 10 μm was used at a temperature of 25 ° C and a wavelength of 83 The refractive index measured at a binding pressure of 30 PSI at 0 nm was as shown in Table 1 below.

 <Core composition>

 154 g of resin C having a carboxyl group and an acryloyl group obtained in Synthesis Example 3, 5 g of Irgacure 907 manufactured by Chipa Specialty Chemical Co., and KF 966 manufactured by Shin-Etsu Chemical Co., Ltd. -100 g of Nippon Kayaku Co., Ltd. with 3 g of CS, 5 g of PMA manufactured by Dow Chemical Company, and a resin solution with a solid content of 75% previously added with carbitol acetate 0.8 g, 35.5 g of EP8334, manufactured by Japan Epoxy Resin Co., which was previously added with carbitol acetate to give a resin solution having a solid content of 90%, and DPHA, manufactured by Nippon Kayaku Co., Ltd., of 20%. g The mixture was weighed, mixed, dispersed and filtered to obtain an active energy linear curing / thermosetting core composition 1 having alkaline developability.

The core composition 1 formed on the wafer with a film thickness of 10 μm was manufactured by using Metricon's PC-2010 prismatic plastic at 25 ° C and a wavelength of 830 ° C. The refractive index measured at nm and a bonding pressure of 30 PSI was as shown in Table 1 below. Gu's production>

80. Apply the solder resist composition on a PET film. C. The 30 μm film dried in 60 minutes was placed on a printed wiring board using a vacuum laminator. Laminated at 70 ° C for 60 seconds. Then, through the Negafu I Lum which shields the conductor pad isolation portion, a 600 mJ / cm ² using a main Taruharai de light source with UV radiation, 60 seconds l% Na ₂ C0 ₃ aqueous solution 30 ° C at a pressure of 0.2Mpa scan flop array developed, 180 ° C, 60 min heat curing reaction a high-pressure mercury lamp after UV with a light source lOOOmJ / cm ² was irradiated, smooth the solder Les Soo preparative conductor pad isolation portion is developed and removed The lower cladding was formed.

A 50 μm film obtained by applying the solder resist composition on a PET film and drying at 80 ° C for 60 minutes is applied to the lower layer using a vacuum laminator at 70 ° C. C, and La Mine preparative at 60 seconds, 50 mu m through the Negafu Irumu to shield line, and UV irradiation at 150 mJ / cm ² using a main Taruharai de the light source, 30 ° C for l% Na ₂ C0 ₃ the aqueous solution was 60 seconds scan flop rate at a pressure of 0.2Mpa development, after Tsu rows 180 ° C, 60 min heat curing reaction, a high pressure mercury lamp UV have use 1000 mJ / cm ² was irradiated to the light source, X-direction and Y An intermediate layer with a core groove of 50 μπι formed in the direction was formed on the lower layer.

The core composition 1 was buried with a squeegee into the groove for the core of the obtained middle layer clad, and dried at 80 ° C for 30 minutes. Fill seen write, and after the operation of the dried et to repeat twice, 5 0 ^ m a line on the core groove using Ficoll Lum exposing the main Taruharai de of 600m J / cm ² have use in the light source UV irradiation was performed. 30 ° C 1% Na ₂ C0 ₃ aqueous solution leaving 60 seconds scan flop array and the core portion at a pressure of 0.2Mpa development, then, a UV using a rear high-pressure mercury lamp after 1 80 ° C, 60 min heat curing reaction light source The core composition 1 was cured by irradiating 1000 mJ / cm ² .

After drying the solder resist composition to a thickness of 20 μm on the middle-layer cladding and core, use a metal halide as a light source through a negative film that shields unnecessary areas from light using a negative light source of 600 mJ / cm. exposure at ^2, 30 ° C for l% Na ₂ C0 ₃ aqueous developer removing unnecessary portion not 60 seconds spray and core periphery at a pressure of 0.2 Mpa, a 1 80 ° C, 60 min heat hardening reaction after Tsu line, a high pressure mercury lamp with UV have use in the optical source l OOOmJ / cm ² was irradiated, using a solder registry to click la head, click la head conductor pad isolation portion is developed and removed An opto-electric hybrid board having the obtained waveguide formed on a printed wiring board was obtained.

 Evaluation>

 A coating was applied to the obtained opto-electric hybrid board, dried, and floated on solder at 260 ° C for 10 seconds.After cooling, tape peeling was performed. Was not found. Solder adhesion to the conductor node was also confirmed.

 The obtained opto-electric hybrid board was once passed through a reflow furnace set to a maximum temperature of 275 ° C. After cooling, tape peeling was performed, but no peeling of the waveguide was observed. The obtained opto-electric hybrid board was subjected to electroless nickel plating, electroless plating, and tape peeling, but no peeling of the waveguide was observed. In addition, adhesion to the conductor pad was confirmed.

Replace the base material with a wafer, and replace the waveguide As a result of measurement using the cutback method, the loss was 0.81 dB / cm.

 The refractive index difference between the core and the clad was 2.1%. Example 2

 Clad composition>

 The active energy linear curing / thermosetting resist composition obtained in Example 1.

 <Core composition>

 Core composition 2 which is a thermosetting composition, which is prepared by weighing and mixing 100 g of EP 828 made by Jianno Epoxy Resin Co., Ltd. Got. The core composition 2 was formed with a thickness of 10 m on the wafer and subjected to a thermosetting reaction at 150 ° C for 60 minutes. The refractive index measured at 25 ° C., a wavelength of 830 nm, and a coupling pressure of 30 PSI was 1.577.

 <Production>

80. Apply the solder resist composition on a PET film. C. The 30 μm film dried in 60 minutes was placed on a printed wiring board with an 18 μm conductor pad formed on the surface using a vacuum laminator at 70 ° C. C, Laminated in 60 seconds. Then, through the negative film that shields the conductor pad isolation portion, main Taruharai de were UV irradiated with 600 mJ / cm ² using a light source, 60 seconds scan the l% Na ₂ C0 ₃ aqueous solution 30 ° C at a pressure of 0.2Mpa flop array developed, after 180 ° C, 60 min heat curing reaction, a high-pressure mercury lamp was lOOOmJ / cm ² irradiated with UV using a light source, a solder registry conductor pad isolation portion is developed A smooth underlayer was removed that formed.

A 50 μm film obtained by applying the solder resist composition on a PET film and drying at 80 ° C for 60 minutes was applied to the lower layer using a vacuum laminator. 70 ° C, and La Mi Natick preparative 60 seconds, 50 m line through Negafu I Lum to shield, and UV irradiation at 1 50 mJ / cm ² using a main Taruharai de the light source, the 30 ° C l% Na ₂ C0 ₃ aqueous solution for 60 seconds scan flop rate at a pressure of 0.2Mpa development, 1 80 ° C, after 60 minutes heat curing reaction was Tsu row, the UV have use a high-pressure mercury lamp as a light source l O OOmJ / cm ² Irradiation was performed to form a middle layer having a core groove of 50 / xm in the X and Y directions on the lower layer.

 The core composition 2 was embedded in the groove for the core of the obtained middle layer using a squeegee, and a thermosetting reaction was performed at 150 ° C. for 60 minutes to cure the core composition 2.

On middle click la head and core, the solder registry compositions 2 0 mu m and by bovine printing becomes dried, at 600 mJ / cm ² using the light source of the main Taruharai de via Negafu Ilm for blocking unnecessary portion exposure, l% Na ₂ C 0 ₃ aqueous developer removing unnecessary portion not 60 seconds spray and core periphery at a pressure of 0.2 Mpa, rows 1 80 ° C, 60 min heat hardening reaction of 30 ° C After that, using a high-pressure mercury lamp as a light source, UV irradiation was performed at l OOOmJ / cm ² , and the solder pad was developed and removed using a solder resist. An opto-electric hybrid board having a waveguide formed on a printed wiring board was obtained.

 <Evaluation>

Apply rosin flux to the obtained opto-electric hybrid board, dry it, float it on solder at 260 ° C for 10 seconds, and after cooling, remove the tape peel However, no peeling of the waveguide was observed. Solder adhesion to the conductor pad was also confirmed.

 The obtained opto-electric hybrid board was once passed through a reflow furnace set to a maximum temperature of 275 ° C, and after cooling, tape peeling was performed, but no peeling of the waveguide was observed.

The obtained opto-electric hybrid board was subjected to electroless nickel plating after electroless nickel plating and tape peeling, but no peeling of the waveguide was observed. In addition, the adhesion to the conductor pad was confirmed.

 The loss was 0.43 dB / cm as a result of measuring the waveguide formed by the above procedure using the cut-pack method after replacing the substrate with a wafer.

 In addition, the difference in refractive index between co-arcs was 3.3%. Example 3

 <Clad composition>

 The active energy ray-curable and thermosetting resist composition obtained in Example 1.

 <Core composition>

20 g of a polycarbonate of Mw 20,000 manufactured by Aldrich Co., and 80 g of a cross-hole form are weighed, mixed, dispersed, filtered, and a core composition which is a thermoplastic composition having a heat-drying property. Obtained thing 3. The core composition 3 was formed on the wafer with a dry film thickness of 10 βm, using a Metricon PC-210 prism power bra, at 25 ° C. The refractive index measured at a wavelength of 830 nm and a bonding pressure of 30 PSI was 1.585. <Preparation>

The 30 μm film obtained by applying the solder resist composition on a PET film and drying at 80 ° C. for 60 minutes was applied to form a 18 μm conductor pad on the surface. The laminate was laminated on a printed wiring board at 70 ° C for 60 seconds using a vacuum laminator. Then, through the Negafu I Lum was shielded conductor path Tsu isolation portion, the use Rere 600 mJ / cm ² UV-irradiated eyes Taruharai de light source, a l% Na ₂ C0 ₃ aqueous solution 30 ° C at a pressure of 0.2Mpa 60 seconds scan flop array developed, after 180 ° C, 60 min heat curing reaction, a high pressure mercury lamp was irradiated lOOOmJ / cm ² of UV used in the light source, the solder Les Soo preparative conductor pad isolation portion is developed and removed A smooth lower cladding was formed.

A 50 μm film obtained by applying the solder resist composition on a PET film and drying at 80 ° C for 60 minutes was applied to the lower layer using a vacuum laminator at 70 ° C. , and La Mine preparative at 60 seconds, 50 m line through Negafu I Lum for blocking, UV-irradiated at 150 mJ / cm ² using a main Taruharai de the light source, l% Na ₂ C0 ₃ aqueous solution 30 ° C was 60 seconds scan flop rate at a pressure of 0.2Mpa development, after Tsu rows 180 ° C, 60 min heat curing reaction, a high pressure mercury lamp UV have use lOOOmJ / cm ² was irradiated to the light source, X-direction及Pi Y An intermediate layer having a core groove of 50 μιη in the direction was formed on the lower layer.

 The core composition 3 was embedded in a core groove of the obtained middle layer using a squeegee, and dried at 80 ° C. for 30 minutes. The embedding and drying were repeated, and the solid content of the core composition 3 was filled in the grooves.

Apply the solder resist composition on the middle layer and core. 2 0 m and by bovine printing becomes dried, Yore the main Taruharai de via Negafu Ilm to shield the unnecessary portion in the light source, the exposure at 600 mJ / cm ^2, 0.2 Mpa of% Na ₂ C0 ₃ aqueous solution 30 ° C After spraying at 60 ° C for 60 seconds and removing unnecessary parts other than the core area by developing and removing, heat-hardening reaction at 180 ° C for 60 minutes, then apply UV using a high-pressure mercury lamp as a light source. / cm ² irradiation, and using a solder resist for the clad, obtains an opto-electric hybrid board with a printed circuit board on which the conductor-pattern clad developed and removed is formed on the printed wiring board Was.

 Evaluation>

 A coating flux was applied to the obtained opto-electric hybrid board, dried, floated on solder at 260 ° C for 10 seconds, and tape-peeled after cooling, but no peeling of the waveguide was observed. Solder adhesion to the conductor pad was also confirmed.

 The obtained opto-electric hybrid board was passed once through a reflow furnace set to a maximum temperature of 275 ° C, and after cooling, tape peeling was performed, but no peeling of the waveguide was observed. .

The obtained opto-electric hybrid board was subjected to electroless nickel plating, electroless plating, and tape peeling, but no peeling of the waveguide was observed. In addition, adhesion to the conductor pad was confirmed.

 The loss was 0.47 dB / cm as a result of measuring the waveguide formed by the above procedure using the cut-pack method after replacing the substrate with a wafer.

The difference in the refractive index between co-arcs was 3.9%. Example 4 <Clad composition>

 The active energy linear curing / thermosetting resist composition obtained in Example 1.

 <Core composition>

 Core composition 1 obtained in Example 1.

 Production>

The 30 μm film obtained by applying the above solder resist composition on a PET film and drying at 80 ° C. for 60 minutes was replaced with a 18 μm conductive pad formed on the surface. Using a vacuum laminator, lamination was performed at 70 ° C for 60 seconds. Then, through the negative film that shields the conductor pad isolation portion, main Taruharai de were UV irradiated with 600 mJ / cm ² using a light source, 60 seconds scan the l% Na ₂ C0 ₃ aqueous solution 30 ° C at a pressure of 0.2Mpa flop array developed, 180 ° C, 60 min heat curing reaction a high-pressure mercury lamp after UV with a light source lOOOmJ / cm ² was irradiated, smooth lower click the solder registry conductor pad isolation portion is developed and removed A lad was formed.

The core composition 1 was applied on PET and dried at 80 ° C. for 60 minutes to obtain a 50 μm film. The film of the core composition 1 was laminated on the obtained lower layer clad at 70 ° C. for 60 seconds using a vacuum laminator. Through a negative film that exposes a 50 μm line, irradiate with 200 mJ / cm ² using metal halide as a light source, and develop with 1% Na ₂ CO ₃ , 30 ° C, 0.2 Mpa, 60 seconds, 180 After a thermosetting reaction at 60 ° C for 60 minutes, UV irradiation was performed at 1000 mJ / cm ² using a high-pressure mercury lamp as a light source, to obtain a core nanotube with a width of 50 µm.

Apply the solder resist composition onto the PET film, 80. C, The 70 μm film dried in 60 minutes was laminated on the core pattern at 70 ° C. for 60 seconds using a vacuum laminator. Use Les the light source meta Ruharai de via Negafu I Lum to shield the unnecessary portions, 600 mJ / cm ² with exposure, scan 60 seconds l% Na ₂ C 0 ₃ aqueous 30 ° C at a pressure of 0.2Mpa flop Leh and current image removing unnecessary portion not core periphery, after 1 80 ° C, 60 min heat curing reaction, Yore a high pressure mercury lamp as a light source, UV was irradiated 1 000mJ / cm ^2, click rats An opto-electric hybrid board was obtained in which a printed circuit board was formed on a printed wiring board, using a solder resist as a soldering layer, in which the conductor pad portion was developed and removed.

 <Evaluation>

 A rosin flux was applied to the obtained opto-electric hybrid board, dried and floated on solder at 260 ° C for 10 seconds.After cooling, tape peeling was performed. I was not able to admit. Solder adhesion to the conductor pad was also confirmed.

The obtained opto-electric hybrid board was passed once through a reflow furnace set to a maximum temperature of 275 ° C, and after cooling, tape peeling was performed, but no peeling of the waveguide was observed. The obtained opto-electric hybrid board was subjected to electroless gold plating after electroless nickel plating and tape peeling, but no peeling of the waveguide was observed. In addition, adhesion to the conductor pad was confirmed.

 The substrate was replaced with a wafer, and the waveguide formed by the above procedure was measured using the cutback method. As a result, the loss was 0.86 dB / cm.

The difference in the refractive index between co-arcs was 2.1%. table 1

(mJ / cm ² ) 200 100 600 1000 200 200 200

 Thermosetting temperature (.C) 150 150 150 150 165 180 150

 Heat curing time (min) 60 60 60 60 60 60 30

 Sample history

UV after heat curing (mJ / cm ² ) 1000 1000 1000 1000 1000 1000 1000

 Heat treatment after formation / 175 ° C, 2 hours None None None None None None None

 1 riff opening 1 1 1 1 1 1 1 ^ Solder resist composition Refractive index (TE) 1.524 1.525 1.525 1.524 1.524 1.525 1.524

 (Clad composition) Refractive index (TM) 1.523 1.523 1.524 1.523 1.523 1.524 1.523

 Refractive index (TE) 1.558 1.558 1.558 1.558 1.558 1.558 1.559

 Core composition 1

Refractive index (TM) 1.556: 1.556 1.556 1.555 1.555 1.556 1.557

Table "I (continued)

Tatsuri (mJ / cm ² ) 200 200 200 100 100 600 600 Thermosetting temperature (° C) 150 150 150 150 150 180 180 Thermosetting time (min) 60 _; 60 60 60 60 60 60 Sample history

UV after heat curing (mJ / cm ² ) 0 2000 1000 1000 1000 1000 1000 Heat treatment after formation / 175 ° C, 2 hours None None Yes None None None None Number of reflows 1 1 1 0 3 0 3 Solder resist composition Refraction Rate (TE) 1.525 1.524 1.525 1.526 1.524 1.526 1.525

(Clad composition) Refractive index (TM) 1.524 1.523 1.523 1.525 1.523 1.525 1.523 Refractive index (TE) 1.559 1.558 1.558 1.559 1.559 1.559 1.559 Core composition 1

 Refractive index (TM) 1.557 1.556 1.556 1.558 1.556 1.558 1.556

Claims

The scope of the claims

 1. In a light guide in which a core portion and a cladding portion are formed on a base material and the refractive index of the cladding portion is lower than the refractive index of the core portion, the cladding portion is formed. An optical waveguide characterized in that the light guide portion is made of an active energy linear developing curable solder resist composition having developability.

 2. An optical waveguide in which the core and the cladding are formed on a substrate having a solder connection conductor on the surface, and the refractive index of the cladding is lower than that of the core. 3. The optical waveguide according to claim 1, wherein said cladding portion is made of an active energy linear curable / thermocurable solder resist composition having a renewable property.

 3. The optical waveguide according to claim 1, wherein the refractive index of the cladding portion is lower than the refractive index of the core portion by 0.5% or more in a value measured by a prism camera.

 4. The solder resist composition according to claim 1, wherein the solder resist composition contains a compound containing a carboxyl group, a compound containing a (meth) atalyloyl group, a compound containing a cyclic (thio) ether group, and a photopolymerization initiator. An optical waveguide according to any one of the preceding claims.

5. A core part and a clad part are formed on a printed wiring board having a solder resist layer and a solder connection conductor on the surface, and the refractive index of the clad part is In an opto-electric hybrid board provided with an optical waveguide having a refractive index lower than a refractive index of a portion, at least a part of the solder resist layer has a cladding of an optical waveguide having a core portion and a cladding portion. And the solder resist layer An opto-electric hybrid board comprising an active energy ray-curable / thermo-curable solder resist composition having developability.

 6. The opto-electric hybrid board according to claim 5, wherein the refractive index of the cladding portion is lower than the refractive index of the core portion by at least 0.5% in a value measured by a prism camera.

 7. The solder resist composition contains a carboxyl group-containing compound, a (meth) acryloyl group-containing compound, a cyclic (thio) ether group-containing compound, and a photopolymerization initiator. 6. The opto-electric hybrid board according to 6.

 8. Manufacture of an opto-electric hybrid board with an optical waveguide formed by forming a core and a clad on a printed wiring board having a solder resist layer and a solder connection conductor on the surface A method for simultaneously forming the solder resist layer and the clad portion using an active energy linear curable and thermosetting solder resist composition. Manufacturing method of opto-electric hybrid board.

 9. In the manufacturing method according to claim 8, the cladding portion includes a lower layer, a middle layer, and an upper layer cladding, and a groove for embedding the core portion is provided at a predetermined position in the middle layer cladding portion. A manufacturing method in which an optical waveguide is formed by forming and embedding a core portion in these grooves, and then providing an upper-layer clad portion.

10.The manufacturing method according to claim 8, wherein the cladding portion includes a lower layer, a middle layer, and an upper layer cladding, and after arranging the core portion at a predetermined position on the surface of the lower cladding portion, Middle and upper layer A manufacturing method characterized by providing an optical waveguide.