JP2003177260A - Composition for optical waveguide resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for an optical waveguide resin having high activity (fast polymerizing property and fast curing property) by irradiation of active energy rays and/or heating and easily controllable of the refractive index. <P>SOLUTION: The composition for an optical waveguide resin contains (a) an alicyclic compound having at least one oxetanyl group in the molecule and (b) compound initiating cation polymerization by irradiation of active energy rays and/or heating. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a curable composition for forming an optical waveguide through which an optical signal can propagate, an optical waveguide obtained by curing the composition, and the optical waveguide. Regarding the used optical materials.

[0002]

2. Description of the Related Art IC (Integrated circuit)
Due to technological advances in LSIs and large scale integrated circuits (LSIs), their operating speeds and integration scales have been improved, and high performance of microprocessors and large capacity of memory chips have been rapidly achieved. Conventionally, information transmission over a relatively short distance such as between boards in a device or between chips in a board has been mainly performed by electric signals. In the future, in order to further improve the performance of integrated circuits, it is necessary to further speed up signals and increase the density of signal wiring, but in electric signal wiring, these speeding up and high density are reaching their limits. CR of wiring
(C: capacitance of wiring, R: resistance of wiring) Signal delay due to time constant is a problem. In addition, EMI (Electromagneti)
c Interference) It causes noise, and its countermeasures are also indispensable.

Therefore, as a solution to these problems, attention has been paid to optical wiring (optical interconnection). The optical wiring is considered to be applicable to various locations such as between devices, between boards within a device, or between chips within a board. In particular, for signal transmission over a short distance such as between chips, it is preferable to form an optical waveguide on a substrate on which the chip is mounted and construct an optical transmission / communication system using this as a transmission path. It is believed that there is.

The waveguide used here is, in addition to optical wiring,
Optical switches, optical connectors used in the field of optical components,
It can be used for optical devices such as optical passive components such as optical demultiplexer-multiplexer, optical demultiplexer coupler, optical attenuator, and optical isolator, and optical circuit components. Regarding these optical devices, "Latest Market of Transparent Plastics", CMC Publishing, 1999, p.
161-175. Hereinafter, all of the waveguides used for the optical material will be collectively described as an optical waveguide.

Conventionally, an inorganic glass such as quartz has been used as an optical waveguide of this type. However, when forming an optical waveguide using inorganic glass, it is necessary to perform heat treatment at high temperature, so the optical waveguide is formed on a substrate such as a semiconductor substrate or a plastic substrate that is difficult to perform heat treatment at high temperature. It could not be formed.

On the other hand, in recent years, an optical waveguide using a polymer material has been proposed and put into practical use. A polymer material is easier to process than an inorganic material, and can be easily formed into a large area or formed into a film. In addition, since it is flexible, it has various advantages such as wide application and easy adjustment of the refractive index. Among them, the ultraviolet curable resin is a material that can be mass-produced, and thus is expected as a material for an optical waveguide. An epoxy resin is widely known as such an ultraviolet curable resin.

An optical waveguide using an epoxy resin is generally formed by applying a resin on a supporting substrate, selectively exposing the resin, and then subjecting the uncured portion of the resin to a wet etching process.

However, since the epoxy resin has a low polymerizability, a large amount of energy is required to cure the resin when the optical waveguide is formed using the epoxy resin, resulting in poor production efficiency. There was a problem.

On the other hand, it is known that when an oxetane compound is mixed with an epoxy compound, cationic curing is significantly improved. From the above, Japanese Patent Laid-Open No. 2000-
Japanese Patent No. 356720 discloses compositions for optical waveguide resins using these oxetane compounds, but at present it cannot be said that they have a sufficient curing rate for actual use in optical waveguides.

[0010]

The present invention has been made in view of the above problems, and provides a composition for an optical waveguide resin having excellent polymerizability, an optical waveguide using the same, and a method for producing the same. Especially.

[0011]

Means for Solving the Problems As a result of intensive studies on the solution of the above-mentioned problems, the present inventors have identified a specific cationically polymerizable compound and a compound that initiates cationic polymerization by irradiation with active energy rays and / or heating. It has been found that a composition for an optical waveguide resin containing the above can solve the above problems, and has completed the present invention.

That is, the present invention provides the following [1] to [1]
[9] The composition for an optical waveguide resin shown in [9], an optical waveguide using the same, and a method for producing the same.

[1] A composition for an optical waveguide resin, which contains an alicyclic compound (a) having at least one oxetanyl group in the molecule.

[2] The optical waveguide resin according to [1], wherein the alicyclic compound (a) having at least one oxetanyl group in the molecule is a compound represented by the general formula (1). Composition.

[Chemical 4] (In the formula, R is a hydrogen atom, or an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a halogenated alkyl group, m is an integer of 0 to 2, and n is 0. Is 2, and the others are 1.) [3] The compound represented by the general formula (1) is 2-oxaspiro [3.5] non-6-ene or 5-methyl-2-.
The composition for an optical waveguide resin according to [2], which is oxaspiro [3.5] non-6-ene.

[4] The optical waveguide resin according to [1], wherein the alicyclic compound (a) having at least one oxetanyl group in the molecule is a compound represented by the general formula (2). Composition.

[Chemical 5] (In the formula, R is a hydrogen atom, or an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a halogenated alkyl group, m is an integer of 0 to 2, and n is 0. Is 2, and the others are 1.) [5] The compound represented by the general formula (2) is 2-oxaspiro [3.5] nonane or 5-methyl-2-oxaspiro [3.5] nonane. [4] The composition for an optical waveguide resin according to [4].

[6] The optical waveguide resin according to [1], wherein the alicyclic compound (a) having at least one oxetanyl group in the molecule is a compound represented by the general formula (3). Composition.

[Chemical 6] (In the formula, R is a hydrogen atom, or an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a halogenated alkyl group, m is an integer of 0 to 2, and n is 0. Is 2, otherwise is 1.)

[7] The compound represented by the general formula (3) is 7,8-epoxy-5-methyl-2-oxaspiro [3.5] nonane, 6,7-epoxy-2-oxaspiro [3.5]. The composition for an optical waveguide resin according to [6], which is nonane. [8] The alicyclic compound (a) having at least one oxetanyl group in the molecule is represented by the general formula (1) or the general formula (2).
And at least one selected from the compounds represented by the general formula (3): the composition for an optical waveguide resin according to [1]. [9] The composition for optical waveguide resin according to any one of [1] to [8], which contains the compound (b) having one or more epoxy groups and not having an oxetanyl group. .

[10] having one or more epoxy groups,
The composition for an optical waveguide resin according to [9], wherein the compound (b) having no oxetanyl group has a fluorine atom. [11] The composition for an optical waveguide resin according to any one of [1] to [10], which contains a compound (c) that initiates cationic polymerization by irradiation with active energy rays and / or heating. . [12] The compound (c) which initiates cationic polymerization upon irradiation with active energy rays and / or heating is one or more selected from sulfonium salts, iodonium salts, phosphonium salts and diazonium salts. The composition for optical waveguide resin of.

[13] The composition for an optical waveguide resin according to any one of [1] to [12], which contains a radically polymerizable compound (d). [14] The composition for an optical waveguide resin according to any one of [1] to [13], which comprises a photo radical initiator (e). [15] The refractive index of the cured product against sodium D line at 25 ° C. is a value within the range of 1.40 or more and 1.70 or less. 15. The composition for optical waveguide resin of.

[16] An optical waveguide obtained by curing the optical waveguide resin composition according to any one of [1] to [15]. [17] It has a core part and a clad part, and at least one of the core part and the clad part is [1] to [1.
[5] An optical waveguide obtained by curing the composition for an optical waveguide resin according to any one of [5].

[18] Composition for optical waveguide resin containing alicyclic compound (a) having at least one oxetanyl group in the molecule and compound (c) which initiates cationic polymerization by irradiation with active energy rays and / or heating A method for producing an optical waveguide, in which an optical waveguide is formed by a development treatment for selectively curing the composition by selectively irradiating a layer using the object with an active energy ray and removing an uncured portion. [19] An optical device using the optical waveguide according to [16].

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below.

The alicyclic compound (a) having at least one oxetanyl group in the same molecule of the present invention (hereinafter abbreviated as compound (a)) is represented by general formula (1), general formula (2) or general formula (2). The alicyclic compound represented by the formula (3) is preferable. General formula (1), (2), (3)
In the formula, R is each independently a hydrogen atom, a linear or branched alkyl group, aryl group, aralkyl group, or halogenated alkyl group having 1 to 12 carbon atoms. Among these, a hydrogen atom and a linear alkyl group are preferable, and a hydrogen atom and a methyl group are particularly preferable. m is 0 to 2
And n is 2 when m is 0 and 1 otherwise. m = 0 means that there is no crosslinking by methylene chains.

Linear or branched having 1 to 12 carbon atoms,
Examples of the alkyl group, aryl group and aralkyl group include a methyl group, an ethyl group, an isopropyl group, a phenyl group and a benzyl group.

Examples of the halogenated alkyl group include a fluoroalkyl group, a chloroalkyl group and a bromoalkyl group. Each of these alkyl groups may be linear or branched, and the number of each halogen atom may be 1 or more.

As the compound represented by the general formula (1),
2-Oxaspiro [3.5] non-6-ene, 9-methyl-2-oxaspiro [3.5] non-6-ene, 2-
Oxa-9-phenylspiro [3.5] non-6-ene, 9-trifluoromethyl-2-oxaspiro [3.
5] Nona-6-ene, spiro [bicyclo [2.2.1]]
Hepta-5-ene-2,3'-oxetane], spiro [3-methylbicyclo [2.2.1] hept-5-ene-2,3'-oxetane] and the like can be mentioned. Among these, 2-oxaspiro [3.5] non-6-ene, 9-
Methyl-2-oxaspiro [3.5] non-6-ene is preferred.

These compounds have an oxetanyl group and a carbon-carbon double bond, and are not only cationically polymerizable but also
It also has excellent radical polymerizability and contributes to the improvement of the curing speed. Further, since it has an alicyclic structure, the cured product of the composition of the present invention has excellent heat resistance. Furthermore, since most of the compounds represented by the general formula (1) are liquid at room temperature, it becomes possible to reduce the viscosity of the composition of the present invention and improve coatability.

As the compound represented by the general formula (2),
2-oxaspiro [3.5] nonane, 7-methyl-2-
Oxaspiro [3.5] nonane, 5-methyl-2-oxaspiro [3.5] nonane, 2-oxa-5-phenylspiro [3.5] nonane, 5-trifluoromethyl-2
-Oxaspiro [3.5] nonane, spiro [adamantan-2,3'-oxetane], spiro [bicyclo [2.
2.1] heptane-2,3′-oxetane], spiro [bicyclo [2.2.2] octane-2,3′-oxetane], spiro [7-oxabicyclo [2.2.1] heptane-2. , 3′-oxetane], spiro [3-methylbicyclo [2.2.1] heptane-2,3′-oxetane] and the like. Among these, 2-oxaspiro [3.5] nonane and 5-methyl-2-oxaspiro [3.5] nonane are preferable.

These compounds are excellent in cationic polymerizability and have the effect of improving the curing rate of the composition. Further, the alicyclic structure imparts heat resistance to the cured product of the composition of the present invention. Furthermore, since most of the compounds represented by the general formula (2) are liquid at room temperature, it is possible to reduce the viscosity of the composition of the present invention and improve coatability.

As the compound represented by the general formula (3),
7,8-Epoxy-5-methyl-oxaspiro [3.
5] nonane, 7,8-epoxy-5-ethyl-2-oxaspiro [3.5] nonane, 7,8-epoxy-2-oxa-5-phenylspiro [3.5] nonane, 7,8-
Epoxy-5-trifluoromethyl-2-oxaspiro [3.5] nonane, 6,7-epoxy-2-oxaspiro [3.5] nonane, spiro [5,6-epoxynorbornane-2,3'-oxetane ], Spiro [5,6-epoxy-3-methylnorbornane-2,3′-oxetane] and the like. Among these, 7,8-epoxy-5
Methyl-2-oxaspiro [3.5] nonane, 6,7-
Epoxy-2-oxaspiro [3.5] nonane is preferred.

Since these compounds have both an oxetanyl group and an epoxy group, they have excellent cationic polymerizability and contribute to the improvement of the curing rate of the composition. In addition, it has an alicyclic structure and enhances the heat resistance of the cured product.

The compounds (a) including alicyclic compounds having one or more oxetanyl groups in the molecule represented by the general formulas (1), (2) and (3) may be used alone or in combination of two kinds. It can be used as a mixture of the above. The compounding amount of these compounds (a) (when two or more kinds are used together, the total amount thereof) is preferably 1 to 90 in the composition for an optical waveguide resin of the present invention.
It is mass%, more preferably 10 to 60 mass%.

As the compound (b) having one or more epoxy groups in the molecule of the present invention and not having an oxetanyl group, known and commonly used epoxy compounds can be used. This epoxy compound is not particularly limited as long as it has one or more epoxy groups in one molecule and does not have an oxetanyl group.

Specifically, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether,
Bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, novolac type epoxy resin (for example, phenol novolac type epoxy resin, cresol novolac type epoxy resin, Brominated phenol / novolak type epoxy resin), hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether,
Triglycidyl isocyanurate or the like can be used.

As the aliphatic epoxy compound,
(3,4-epoxycyclohexyl) methyl-3 ′,
4'-epoxy cyclohexyl carboxylate, 2-
(3,4-epoxycyclohexyl-5,5-spiro-
3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-)
6-methylcyclohexylmethyl) adipate, 3,4
-Epoxy-6-methylcyclohexyl-3 ', 4'-
Epoxy-6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, limonene diepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,3) 4-epoxycyclohexanecarboxylate)
Is mentioned.

Further, epoxy dioctyl hexahydrophthalate, di-2-ethylhexyl epoxy hexahydrophthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether,
1 for aliphatic polyhydric alcohols such as glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol, propylene glycol and glycerin
Or polyglycidyl ethers of polyether polyols obtained by adding two or more alkylene oxides; diglycidyl ethers of aliphatic long-chain dibasic acids; monoglycidyl ethers of higher aliphatic alcohols; butylglycidyl ether, Phenyl glycidyl ether, cresol glycidyl ether, nonyl phenyl glycidyl ether, glycidyl methacrylate;
Phenol, cresol, butylphenol or monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxides to these; glycidyl esters of higher fatty acids; epoxidized soybean oil; butyl epoxystearate, octyl epoxystearate, epoxidized linseed Examples thereof include oil and epoxidized polybutadiene.

Further, a fluorinated epoxy compound having a fluorine atom can be used to adjust the refractive index of the optical waveguide of the present invention. The fluorinated epoxy compound has a smaller refractive index than a hydrocarbon type epoxy compound having a similar structure, and can be adjusted to a desired refractive index by mixing with a resin composition for an optical waveguide. .

Specifically, "Applied Physics Vol. 68, No. 1 (1
999), p. 4 to 13 ", examples of the following compounds are described, but the present invention is not limited thereto.

[Chemical 7]

[Chemical 8]

[Chemical 9]

[Chemical 10]

[Chemical 11]

The compound (b) having one or more epoxy groups in the molecule and not having an oxetanyl group can be used alone or in combination of two or more kinds.

The compounding amount of the compound (b) (when two or more kinds are used in combination, the total amount thereof) is 1 to 10,000 based on 100 parts by mass of the total amount of the compound (a) in the present invention.
A mass part is preferable and a 10-1,000 mass part is especially preferable.

The compound (c) which is used in the present invention to initiate cationic polymerization by irradiation with active energy rays and / or heating is changed by heating or irradiation with active energy rays such as ultraviolet rays to initiate cationic polymerization of acids and the like. It can be a compound that produces a substance. Therefore, the compound (c) is a kind of cationic polymerization initiator and is also referred to as "acid generator" in the art. Hereinafter, in the present invention, the compound (c) is also referred to as an acid-generating cationic polymerization initiator.

The acid-generating type cationic polymerization initiator is a compound (a) of the present invention when heated or irradiated with light such as ultraviolet rays.
It accelerates the cationic polymerization of the compound (b) and other cationically polymerizable substances (compounds containing an oxetanyl group, etc.) to smoothly cure the composition for an optical waveguide resin of the present invention.

The acid-generating type cationic polymerization initiator referred to in the present invention is a compound which changes by heating or irradiation with active energy rays such as ultraviolet rays to produce a substance such as an acid which initiates cationic polymerization. Thus, compounds that are in the acid form from the beginning are not included.

As the acid-generating type cationic polymerization initiator, known sulfonium salts, iodonium salts, phosphonium salts,
Examples thereof include diazonium salts, ammonium salts and ferrocenes. Specific examples are shown below, but the present invention is not limited to these compounds.

Examples of the sulfonium salt-based acid-generating type cationic polymerization initiator include bis [4- (diphenylsulfonio)]
Phenyl] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate, bis [4- (diphenylsulfonio) phenyl] sulfide bistetrafluoroborate, bis [4- (diphenylsulfone) Nio) phenyl] sulfide tetrakis (pentafluorophenyl) borate, diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, diphenyl-4- (phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetra Fluoroborate, diphenyl-4- (phenylthio) phenylsulfonium tetrakis (pentafluorophenyl) borate, tri Phenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfo Nio) phenyl] sulfide bishexafluorophosphate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bishexafluoroantimonate, bis [4
-(Di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bistetrafluoroborate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide tetrakis ( Pentafluorophenyl) borate, and the like.

Examples of the iodonium salt-based acid-generating type cationic polymerization initiator include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, and bis (dodecylphenyl). ) Iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1) −
Methylethyl) phenyliodonium hexafluorophosphate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, 4
-Methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl)
Examples include borate.

Examples of the phosphonium salt-based acid-generating type cationic polymerization initiator include ethyltriphenylphosphonium tetrafluoroborate, ethyltriphenylphosphonium hexafluorophosphate, ethyltriphenylphosphonium hexafluoroantimonate, tetrabutylphosphonium tetrafluoroborate and tetra Examples thereof include butylphosphonium hexafluorophosphate and tetrabutylphosphonium hexafluoroantimonate.

Examples of the diazonium salt-based acid-generating cationic polymerization initiator include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrakis (pentafluorophenyl) borate. .

Examples of the ammonium salt-based acid-generating type cationic polymerization initiator include 1-benzyl-2-cyanopyridinium hexafluorophosphate and 1-benzyl-2-
Cyanopyridinium hexafluoroantimonate,
1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzyl-2-cyanopyridinium tetrakis (pentafluorophenyl) borate, 1-
(Naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) -2-
Cyanopyridinium hexafluoroantimonate,
1- (naphthylmethyl) -2-cyanopyridinium tetrafluoroborate, 1- (naphthylmethyl) -2-
Examples include cyanopyridinium tetrakis (pentafluorophenyl) borate, and the like.

As the ferrocene-based acid-generating type cationic polymerization initiator, (2,4-cyclopentadiene-1-yl) [(1-methylethyl) benzene] -Fe (II) hexafluorophosphate, (2,4 -Cyclopentadiene-1-yl) [(1-methylethyl) benzene]-
Fe (II) hexafluoroantimonate, 2,4-cyclopentadiene-1-yl) [(1-methylethyl)
Benzene] -Fe (II) tetrafluoroborate, 2,
4-cyclopentadiene-1-yl) [(1-methylethyl) benzene] -Fe (II) tetrakis (pentafluorophenyl) borate, and the like.

Of these acid-generating type cationic polymerization initiators, sulfonium salt and iodonium salt type initiators are preferable from the viewpoints of curing rate, stability and economy. As commercial products, SP-150, SP-170, CP manufactured by Asahi Denka Co., Ltd.
-66, CP-77; CYRA manufactured by Union Carbide
CURE-UVI-6990, UVI-6974; Nippon Soda Co., Ltd. CI-2855, CI-2638; Sanshin Chemical Industry Co., Ltd., San-Aid SI-60; "Irgacure 261".
(Ciba Specialty Chemicals (2,4-cyclopentadien-1-yl) [(1-methylethyl)
Benzene] -Fe (II) hexafluorophosphate), “RHODORSIL 207
4 "; (4-methylphenyl-4 manufactured by Rhone-Poulin)
-(1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate), and the like.

These acid-generating type cationic polymerization initiators may be selected from the above-mentioned materials and used alone or in combination of two or more kinds.
The preferred range of the amount of the acid-generating cationic polymerization initiator used is
There is no particular limitation, but the total compounding amount of the compound (a) and the compound (b) (when the other cationically polymerizable compound described later is used together, the total amount thereof) is 100 parts by mass. 05 to 25 parts by mass, preferably 1 to 20 parts by mass. If the amount added is less than 0.05 parts by mass, the sensitivity will be poor, and remarkably large light irradiation energy and high temperature treatment for a long time are required for sufficient curing. Further, even if added in excess of 25 parts by mass, the sensitivity is not improved, which is economically unfavorable. On the contrary, the amount of uncured components remaining in the composition may increase and the physical properties of the cured product may deteriorate.

In the present invention, the following cationically polymerizable monomers can also be added to the composition for optical waveguide resins of the present invention within a range that does not affect the curability and the physical properties of the cured product. This cationically polymerizable monomer is a compound that causes a polymerization initiation reaction or a crosslinking reaction by the acid generated by the acid-generating cationic polymerization initiator and is classified into compounds other than the compound (a) and the compound (b). For example, trimethylene oxide, 3,3-dimethyloxetane, 3,3-dichloromethyloxetane, 3-ethyl-3-phenoxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane (manufactured by Toagosei Co., Ltd .; trade name EOXA) , Bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene (also known as xylylenedioxetane; manufactured by Toagosei Co., Ltd .; trade name XDO), tri [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, bis [ (3-Ethyl-3-oxetanylmethoxy) methylphenyl] ether, 3-
Oxetane compounds having an oxetanyl group in addition to alicyclic compounds such as ethyl-3-[(oxiranylmethoxy) methyl] oxetane and (3-ethyl-3-oxetanylmethoxy) oligodimethylsiloxane; tetrahydrofuran, 2,3 An oxolane compound such as dimethyltetrahydrofuran; trioxane, 1,3-dioxolane,
Cyclic acetal compounds such as 1,3,6-trioxanecyclooctane; cyclic lactone compounds such as β-propiolactone and ε-caprolactone; ethylene sulfide
Thiirane compounds such as 1,2-propylene sulfide and thioepichlorohydrin; Thiethane compounds such as 3,3-dimethylthietane; Vinyl ether compounds such as ethylene glycol divinyl ether, triethylene glycol divinyl ether, trimethylolpropane trivinyl ether; Examples thereof include spiro orthoester compounds which are reaction products of epoxy compounds and lactones; ethylenically unsaturated compounds such as vinylcyclohexane, isobutylene and polybutadiene; cyclic ether compounds; cyclic thioether compounds; vinyl compounds and the like.

These cationically polymerizable monomers may be added alone or in combination of two or more. The amount of these cationically polymerizable monomers (when two or more kinds are used in combination, the total amount thereof) is 1 to 10,000 parts by mass, preferably 10 parts by mass, relative to 100 parts by mass of the compound (a) of the present invention. ~
1,000 parts by mass. Of the above-mentioned cationically polymerizable monomers, the compound having only one cationically polymerizable group in the molecule is 20 per 100 parts by mass of the compound (a).
If it is added in an amount of 0 part by mass or more, the curability is lowered and the energy required for curing is increased, which is not preferable.

A radically polymerizable compound (d) may be added to the composition for an optical waveguide resin of the present invention in order to improve light (active energy ray) curability within a range not impairing the object of the present invention. Is. The compound (d) is not particularly limited, but (meth) acrylic acid ester-based known and commonly used radically polymerizable monomers can be used. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth ) Acrylate, phenoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol mono (meth) acrylate, etc. Functional (meth) acrylate compound; ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra ( Data) acrylate, dipentaerythritol penta (meth) acrylate, multifunctional epoxy (meth) acrylate resin, a polyfunctional urethane (meth) acrylate resin.

For the purpose of adjusting the refractive index of the optical waveguide of the present invention, a (meth) acrylate monomer having a fluorine atom can be used as the compound (d).
Specifically, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, pentafluoropropyl (meth) acrylate, hexafluoroisopropyl (meth) acrylate, Octafluoropentyl (meth) acrylate and the like can be mentioned.

The addition amount of the compound (d) is 5 to 100 parts by mass of the total amount of the compound (a), the compound (b), the compound (c) of the present invention and the above-mentioned other cationically polymerizable compounds. 200 parts by mass, preferably 10 to 100 parts by mass. If the amount added exceeds 200 parts by mass, the dryness to the touch will deteriorate. In addition, since the ratio of cross-linking of the (meth) acrylic group increases during curing, the heat resistance of the obtained cured product
Chemical resistance decreases.

In order to smoothly promote the radical polymerization of the radically polymerizable compound (d), it is desirable to add a photoradical initiator (e), and a known and conventional one which is sensitive to light and generates a radical can be used. . Here, “light” means visible rays, ultraviolet rays, far ultraviolet rays, X-rays, electron rays, and other radiation. Examples of the photo radical initiator (e) include benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2, 2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-
Methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-
[4- (methylthio) phenyl] -2-morpholinopropan-1-one (manufactured by Ciba Specialty Chemicals; Irgacure 907), 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, Benzophenone, p-phenylbenzophenone,
4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, 2-
Methylthioxanthone, 2-ethylthioxanthone, 2
-Chlorothioxanthone, 2,4-diethylthioxanthone, benzyl dimethyl ketal, p-dimethylamine benzoate, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (BASF; Lucillin TPO), bis (2,6- Dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide-containing initiator (manufactured by Ciba Specialty Chemicals; Irgacure 1700,149,1800),
Examples thereof include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by Ciba Specialty Chemicals; Irgacure 819). These can be used alone or as a mixture of two or more.

The amount of the photo-radical initiator (e) used is 0.007 with respect to 1 equivalent of the radical-polymerizable functional group such as the (meth) acrylic group of the radical-polymerizable compound (d) in the composition.
~ 0.5 mol can be used.

The composition for an optical waveguide resin of the present invention may contain an ion trap agent, if necessary. The ion trap agent reacts with impurities such as anions and cations, and can be converted into a substance that makes it harmless.

The composition for an optical waveguide resin of the present invention may further contain an aliphatic polyol. Such an aliphatic polyol imparts flexibility to the optical waveguide resin of the present invention and enhances the completion of the reaction at room temperature aging after the curing reaction. Examples of the aliphatic polyol include (poly) alkylene glycols such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol and butylene glycol,
Glycerin, polyglycerin, pentaerythritol,
Examples thereof include polycaprolactone polyol. The blending amount is the component (a) in the composition for an optical waveguide resin of the present invention.
5 to 50 parts by weight, preferably 10 to 30 parts by weight, per 100 parts by weight of the total of (e) and other cationically polymerizable monomer components.

When the composition for an optical waveguide resin of the present invention is polymerized and cured by ultraviolet rays which is one of active energy rays,
A sensitizer can also be used to improve the polymerization rate. Examples of the sensitizer used for such a purpose include pyrene, perylene, 2,4-diethylthioxanthone,
2,4-dimethylthioxanthone, 2,4-dichlorothioxanthone, phenothiazine and the like can be mentioned. When the sensitizer is used in combination, the amount used is preferably in the range of 0.1 to 100 parts by mass with respect to 100 parts by mass of the photoacid-generating cationic polymerization initiator.

Further, if necessary, an antifoaming agent such as a silicone-based, fluorine-based or polymer-based defoaming agent; a leveling agent; an adhesion-imparting agent such as an imidazole-based, thiazole-based, triazole-based or silane coupling agent, for example, Shin-Etsu Silicone. Silane coupling agent, KBM303, KBM403,
KBM402; Use of well-known and commonly used additives such as flame retardants such as antimony trioxide, phosphoric acid ester, red phosphorus, and nitrogen-containing compounds such as melamine resin, and stress relaxation agents such as silicone oil and silicone rubber powder. You can

The composition for an optical waveguide resin of the present invention is a stirrer with blades, a stirrer / kneader, a paint shaker, a kneader for the constituent substances such as the compound (a), the compound (b) and the compound (c) described above. , A three-roll mill or the like can be used for mixing. The mixing device is not particularly limited as long as it is a device capable of uniformly mixing the constituent substances, but it is necessary to select it in consideration of the viscosity of the composition and the like.

The composition for an optical waveguide resin in the present invention can be polymerized (cured) by irradiation with active energy rays and / or heating. The active energy ray here means ultraviolet rays, X-rays, electron rays, γ rays and the like. Examples of the light source for irradiation with ultraviolet rays include metal halide lamps, mercury arc lamps, xenon arc lamps, fluorescent lamps, carbon arc lamps, tungsten-halogen copying lamps, and sunlight.

When the composition for an optical waveguide resin of the present invention is cured by heating, the heating condition is preferably about 50-2.
The conditions may be about 0.2 to 60 minutes, preferably about 0.5 to 20 minutes, more preferably about 1 to 10 minutes at 50 ° C, more preferably about 75 to 200 ° C.

The refractive index of the optical waveguide of the present invention is preferably 1.40 to 1.70 with respect to the D line of sodium at 25 ° C., and the core portion or the cladding portion of the optical waveguide is formed in this range. Therefore, the refractive index of the optical waveguide resin composition is also preferably 1.40 to 1.70.
The core portion and the cladding portion forming the optical waveguide have a refractive index of 1.
If the difference in refractive index between the core portion and the cladding portion is about 0.001 or more in the single mode and about 0.01 to 0.1 or more in the multi mode at about 5, the light propagation characteristics It is possible to form an excellent optical waveguide.

Generally, the composition for an optical waveguide resin is a mixture of an oxetane compound, an epoxy compound and the like as described above. These oxetane compounds and epoxy compounds have a refractive index of about 1.40 to 1.70, and it is possible to arbitrarily control the refractive index of the optical waveguide resin by appropriately selecting these compounds or changing the compounding ratio. Is possible.

Next, an example of a method of manufacturing an optical waveguide using the composition for an optical waveguide resin will be described with reference to FIG.

First, as shown in FIG. 1 (A), a composition for an optical waveguide clad portion is applied onto a substrate 10 made of silicon so that the thickness after curing is about 30 μm, and a clad portion is formed. The composition layer 11a is formed.

Next, as shown in FIG. 1 (B), the cladding layer composition layer 11a is irradiated with ultraviolet rays for 60 seconds at an output of 25 mW / cm ² using an ultrahigh pressure mercury lamp. By doing so, the composition for the optical waveguide clad portion is cured. As a result, as shown in FIG. 1C, the clad portion 11 of the optical waveguide is formed. When the composition layer 11a is completely cured, the refractive index is, for example, 0.0
It becomes about 25 larger. A photo-curing method can be used to cure the clad portion, but a thermo-cation curing agent can be used to cure the entire surface.

Next, as shown in FIG. 1D, the composition for the optical waveguide core portion is applied onto the cladding portion 11 so that the thickness after curing is about 30 μm, and the composition layer 12a. To form.

Further, the composition layer 12a is irradiated with ultraviolet rays through the photomask 21 having a stripe-shaped opening. Specifically, the photomask 21 is arranged on the composition layer 12a for the core portion so as not to come into contact with the composition layer 12a for the core portion, and ultraviolet rays are directed from the photomask 21 side toward the composition layer 12a. Irradiate. Ultraviolet irradiation is performed with an ultra-high pressure mercury lamp at 20 to 200 mW /
Perform for 5 to 120 seconds at an output of cm ² . As a result,
As shown in (E), in the portion 12a1 of the core portion composition layer 12a corresponding to the opening of the photomask 21, the optical waveguide core portion composition is cured.

Here, the uncured core portion composition layer 12a
When ultraviolet rays are irradiated in a state where the photomask 21 and the photomask 21 are in close contact with each other, the composition layer 12a for the core portion and the photomask 21 are adhered to each other.
Need to be arranged so as not to contact the core portion composition layer 12a. Examples of such a method include a proximity exposure method in which a gap of about 100 μm is provided between the mask and the exposed object to perform exposure, and a mask and the exposed object are separated from each other to form an optical image. There is a projection exposure method for performing exposure.

After a predetermined time has passed from the irradiation of the ultraviolet rays, the photomask 21 does not irradiate the ultraviolet rays,
The uncured portion 12a2 is dissolved and removed with a developing solution such as acetone. At this time, since the crosslink density of the cured portion 12a1 of the clad portion 11 and the core portion composition layer 12a is high, there is little possibility that these regions are dissolved.

Next, the hardened material layer 12a is washed with isopropyl alcohol as a rinse liquid to obtain a hardened material layer 12a.
Acetone that has penetrated into the interior of the resin to swell the cured product layer 12a is removed. Thereby, as shown in FIG. 1F, the core portions 12 of the plurality of optical waveguides each having a strip shape in a plan view and a refractive index of about 1.56 are formed.

Finally, as shown in FIG. 1G, the cladding portion 1 is formed on the exposed surface of the cladding portion 11 and the core portion 12.
The same material as that of No. 1 is used to form the cladding section 13 by the same method as that of the cladding section 11 to complete the embedded optical waveguide including the core section 12 and the cladding sections 11 and 13.

In the optical waveguide manufactured in this way,
When an optical signal is incident on one end face, the optical signal propagates inside and is emitted from the other end face.

The developer used in the method for producing an optical waveguide according to the present invention is a solvent which is excellent in solubility in an uncured portion, that is, in a composition for an optical waveguide resin and which has little influence on the cured portion. It is preferable to use. Such solvents include ethyl acetate,
Esters such as butyl acetate, γ-butyrolactone, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate; ether alcohols such as ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether; acetone Ketones such as methyl ethyl ketone and methyl isobutyl ketone; ethers such as dioxane and tetrahydrofuran; benzene;
Examples thereof include aromatic hydrocarbons such as toluene and xylene. These may be used alone or in combination of two or more. Moreover, you may adjust the swelling property of a hardened | cured material by adding a solvent with low solubility of the composition for optical waveguide resins, for example, water or alcohol, to these solvents. Of these solvents, acetone is preferable because it has low toxicity and a low boiling point, and thus has the advantage that it is easy to handle overall.

When isopropyl alcohol is used as the rinse liquid used in the method for producing an optical waveguide of the present invention, the cured core portion is hardly attacked and is easily compatible with the developer, so that the uncured portion is completely removed. This is because the hardened core portion can be left almost in a perfect shape and the upper surface of the substrate can be finished without leaving dust.

The rinsing liquid used for such a purpose varies depending on the kind of the developing solution, but methanol,
Lower alcohols such as ethanol, isopropyl alcohol and butanol are preferred. Furthermore, isopropyl alcohol is preferable.

[0082]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In addition, "part" in Examples and Comparative Examples
Is parts by mass unless otherwise specified.

Among the materials used in Examples and Comparative Examples, the commercially available products are as follows, and without purification:
Used as is. POX: Toagosei Co., Ltd., 3-ethyl-3-phenoxymethyloxetane XDO: Toagosei Co., Ltd., 1,4-bis [(3-ethyl-
3-oxetanylmethoxy) methyl] benzene 3000: manufactured by Daicel Chemical Industries, Ltd. (trade name Celoxide 3000), limonendioxide 2110: manufactured by Asahi Denka Industry (trade name KRM-2110),
Bifunctional alicyclic epoxy resin 828: manufactured by Yuka Shell Epoxy Co., Ltd.
28), bisphenol A type epoxy resin M-309: Toagosei Co., Ltd., trimethylolpropane triacrylate 3000A: Kyoeisha Chemical Co., Ltd. epoxy ester 3000.
A, bisphenol A diglycidyl ether acrylic acid adduct SI-60L: Sanshin Chemical Industry Co., Ltd.
I-60L), thermal cationic polymerization initiator (sulfonium salt) 6990: manufactured by Union Carbide (trade name UVI-6).
990), a cationic photopolymerization initiator 907: manufactured by Ciba Specialty Chemicals (trade name Irgacure 907), a photopolymerization initiator

As the compounds not commercially available, those chemically synthesized by the inventor were used. That is, 7,8-epoxy-5
Methyl-2-oxaspiro [3.5] nonane and 6,
The 7-epoxy-2-oxaspiro [3.5] nonane was synthesized by the present inventor with reference to the method described in US Pat. No. 3,388,105. Specifically, 7,8-epoxy-5-
Methyl-2-oxaspiro [3.5] nonane was synthesized as follows.

<6-methyl-3-cyclohexene-1,
Synthesis of 1-dimethanol> In a three-necked flask, 327 g of 2-methyl-4-cyclohexene-1-carbaldehyde, which is a Diels-Alder reaction product of butadiene and crotonaldehyde, 600 ml of methanol and 729 g of 37% formalin water. Charge and stir this solution 6
The temperature was raised to 0 ° C. Then, 252 g of KOH was added to 60 parts of distilled water.
The solution dissolved in 0 ml was added dropwise over 2 hours. After continuing stirring for 7 hours, the reaction solution was concentrated under reduced pressure to obtain a bilayer residue. The oil layer concentrated to about 150 ml was washed with 300 ml of distilled water. After the oil layer was concentrated under reduced pressure, 50 mg of 3,5-di (t-butyl) -4-hydroxytoluene (BHT) was added and distilled under reduced pressure to give 6-colorless crystals.
Methyl-3-cyclohexene-1,1-dimethanol 3
11 g (yield 82%) was obtained.

<6-methyl-3-cyclohexene-1,
Synthesis of 1-dimethanol cyclic carbonic acid ester> A 3-necked flask was charged with 310 g (1.99 mol) of 6-methyl-3-cyclohexene-1,1-dimethanol, 894 g of dimethyl carbonate (DMC) and 0.93 g of potassium carbonate, The temperature was raised to 90 ° C. and the mixture was refluxed for 4 hours. The reaction solution was returned to room temperature and potassium carbonate was filtered off. BHT 120mg
After adding, the remaining DMC and methanol are adjusted to 2 kPa.
(15 mmHg) was removed under reduced pressure, followed by vacuum distillation to obtain 326 g of 6-methyl-3-cyclohexene-1,1-dimethanol cyclic carbonic acid ester, which is a room temperature colorless crystal.
(Yield 89.4%) was obtained.

<9-Methyl-2-oxaspiro [3.5]
Synthesis of nona-6-ene (CHEO)> In a three-neck flask, 6-methyl-3-cyclohexene-1,1-dimethanol cyclic carbonic acid ester 321.15 g, BHT642 mg
(0.2 mass%) and LiCl (1.93 g) were charged, and the mixture was heated and stirred at 275 ° C. using a mantle heater. The product was immediately discharged under reduced pressure of about 8 kPa (60 mmHg) to the outside of the system, and heating was continued for 4 hours until distilling stopped. BHT (600 mg) was added to the product, and vacuum distillation was performed to obtain 187 g (yield 71%) of CHEO as a colorless transparent liquid.

<Synthesis of 7,8-epoxy-5-methyl-2-oxaspiro [3.5] nonane (ECHO)> CH
50 g of EO was dissolved in 150 ml of dichloromethane and then charged into the reactor. m-chloroperbenzoic acid 93.7
What was suspended in 400 ml of dichloromethane was added dropwise over 1 hour so that the reaction solution did not exceed 40 ° C. The precipitated m-chlorobenzoic acid was filtered off and washed well with cold dichloromethane. Calcium hydroxide 1 in the organic layer
After adding 5.0 g and stirring for 30 minutes, the precipitated crystals were separated by filtration and washed with cold dichloromethane. The organic layer is 5% Na
After washing with HSO4 water and saturated saline solution and concentrating, 38.1 g of colorless semi-solid ECHO at room temperature by vacuum distillation.
(Yield 73.7%) was obtained.

<Synthesis of 7,8-epoxy-5-ethyl-2-oxaspiro [3.5] nonane (EECHO)> E
Instead of the Diels-Alder reaction product of butadiene and crotonaldehyde used in the synthesis of CHO, a Diels-Alder reaction product of butadiene and trans-2-pentenal, 6-ethyl-3-cyclohexene-1-carbo Synthesized by the present inventor using an aldehyde by a procedure similar to the above.

<7,8-Epoxy-5-trifluoromethyl-2-oxaspiro [3.5] nonane (EFCH
O) Synthesis> Instead of the Diels-Alder reaction product of butadiene and crotonaldehyde used in the synthesis of ECHO, Diels-Alder reaction product of butadiene and trans-4,4,4-trifluoro-2-butenal Was synthesized by the present inventor by a procedure similar to the above.

<5-methyl-2-oxaspiro [3.
5] Synthesis of nonane (CHO)> Obtained by hydrogenating the above-mentioned 6-methyl-3-cyclohexene-1,1-dimethanol in 1L three-necked flask in toluene with hydrogen gas using 5% palladium / activated carbon as a catalyst. 2-methylcyclohexane-1,1-dimethanol (474 g), dimethyl carbonate (405 g) and potassium carbonate (1.4 g) were added, and the mixture was heated with stirring at a temperature of 100 ° C. in an oil bath, and the produced methanol was distilled out of the system under normal pressure. The reaction was carried out for 14 hours. Finally, the pressure inside the reaction vessel was reduced to 10 mmHg to obtain the corresponding carbonate ester in a yield of 95%.

The cyclic ester carbonate thus obtained was used as it was for 25
The mixture was heated and stirred at 0 ° C., and the generated carbon dioxide gas was discharged from the upper part of the cooling device to the outside of the system to carry out the reaction for 10 hours. The reaction solution was purified by distillation to obtain 230 g of CHO.

<2-oxa-5-phenylspiro [3.
5] Synthesis of Nonane (PCHO)> Instead of 2-methylcyclohexane-1,1-dimethanol used in the synthesis of CHO, a Diels-Alder reaction product of butadiene and trans-cinnamic aldehyde was used in toluene. Using 2-phenylcyclohexane-1,1-dimethanol obtained by hydrogenating hydrogen gas with% palladium / activated carbon as a catalyst, the present inventor synthesized the same procedure as above.

<Synthesis of Spiro [bicyclo [2.2.1] heptane-2,3'-oxetane] (NRBO)> CH
Di of butadiene and crotonaldehyde used during O synthesis
Instead of 6-methyl-3-cyclohexene-1,1-dimethanol obtained from the els-Alder reaction product, a reaction product of cyclopentadiene and acrolein, bicyclo [2.2.1] hept-5-ene. A completely similar reaction is carried out using bicyclo [2.2.1] heptane-1,1-dimethanol hydrogenated with hydrogen gas using 5% palladium / activated carbon as a catalyst in 1,1-dimethanol in toluene. As a result, the present inventors synthesized the same procedure as above.

<Synthesis of bis (1,1,1,3,3,3-hexafluoroisopropyl) cyclohexane diglycidyl ether (fluorinated epoxy resin A)>

[Chemical 12] Macromolecules 1996, 29, 20
It was synthesized according to 06-2010. The obtained fluorinated epoxy resin A has 100% of repeating units having n of 0,
Cyclohexane having 1,3 bonds of 85%, 1,
A 15% mixture of 4 was used.

<Examples 1 to 8 and Comparative Examples 1 to 3> First, the photocurability of the compositions for optical waveguide resins was examined. Table 1
An oxetane compound, an epoxy compound, a photocationic polymerization initiator and the like were mixed in the composition shown in (in the table, the numerical values are parts by mass) to obtain a composition for each optical waveguide resin.

A photocurability test was conducted on each of the optical waveguide resin compositions thus obtained in the following manner. The composition layer was applied onto a glass substrate so as to have a thickness of 100 μm. Then, the composition layer was cured by irradiating with a metal halide lamp at an output of 24 mW / cm ² for 10 seconds. The tackiness of the cured composition layer was examined with a fingertip, and the obtained results are shown in Table 1. Here, when there was no tack in the cured product layer, “◯” was given, when there was some tack, “Δ” was given, and when tack was present, “X” was given.

Although Examples 1 to 8 are mixtures of the alicyclic compound (a) having an oxetanyl group of the present invention and an epoxy compound, it is understood that the mixture has excellent curability.

On the other hand, Comparative Example 1 was a composition containing only an epoxy compound, but was not cured at all and showed a remarkable tack. Comparative Examples 2 and 3 are examples in which an oxetane compound having no alicyclic structure was used as the oxetane compound. It was confirmed that the curability was improved as compared with the composition containing only the epoxy compound, but the curability was slightly inferior as compared with the examples in which the alicyclic compound (a) having an oxetanyl group of the present invention was mixed. Example 4 is a mixed example of the oxetane compound of the present invention and other oxetane compounds, but it was sufficiently cured. The curability of the alicyclic compound (a) having an oxetanyl group of the present invention is reflected. Example 5
In this example, a radical polymerizable compound and a radical polymerization initiator were mixed, but this example was also sufficiently cured.

As described above, it can be seen that the composition for an optical waveguide resin containing the alicyclic compound (a) having an oxetanyl group of the present invention has excellent curability.

Further, the refractive index of sodium to the D line at 25 ° C. was measured for each of the obtained optical waveguide resin compositions after complete curing (further cured by irradiation with light). The results are shown in Table 1. Refractive index is Ab
be Refractometer (Abbe Refractometer 1 manufactured by Atago Co., Ltd.
Type). It was found that the refractive index can be changed from 1.465 to 1.550 and can be adjusted as a composition for the clad portion and the core portion.

[0102]

[Table 1]

<Examples 9 to 11, Comparative Examples 4 to 6> The thermosetting properties of the optical waveguide resin compositions were examined. Example 1
.About.8, the compositions for optical waveguide resins were prepared in the same manner except that the cationic photopolymerization initiator of Comparative Examples 1 to 3 was changed to the thermal cationic polymerization initiator SI-60L. The blending amount (parts by mass) is shown in Table 2.

Each of the optical waveguide resin compositions thus obtained was subjected to a thermosetting test as follows. Each composition was put in a sample bottle and immersed in an oil bath at 80 ° C. The thermosetting property of each composition after being cured for 1 minute was evaluated as follows. Those with almost no change in viscosity are “x”, those with increased viscosity are “Δ”, and those with complete curing are “◯”.

The results are shown in Table 2. The composition containing the alicyclic compound (a) having an oxetanyl group of the present invention has remarkably high thermosetting property as compared with the epoxy compound alone or other oxetane compounds.

It is possible to use thermosetting in the clad portion of the optical waveguide, if necessary, but it was found that the composition for optical waveguide resin of the present invention has sufficient curability even in thermosetting. It was

[0107]

[Table 2]

Example 12 Production Example of Optical Waveguide / Clad Part Composition ECHO 40 parts by mass, 2110 10 parts by mass, 828
10 parts by mass, cationic photopolymerization initiator UVI-6990
3 parts by mass were mixed so as to be sufficiently uniform. Further, by filtering to remove dust and the like, a composition for an optical waveguide clad portion was obtained. In addition, each material used the thing of the same product name as what was described in Examples 1-8.

Composition for core part ECHO 30 parts by mass, 2110 10 parts by mass, 828
60 parts by mass, cationic photopolymerization initiator UVI-6990
3 parts by mass were mixed so as to be sufficiently uniform. Further, by filtering to remove dust and the like, a composition for an optical waveguide core portion was obtained. In addition, each material is
The product having the same product name as that described in Examples 1 to 8 was used.

Next, the production of the optical waveguide will be described.
As shown in FIG. 1A, the substrate 10 made of silicon is used.
And the composition layer 1 made of the composition for the optical waveguide clad portion is formed on the entire surface of the substrate 10 by spin coating.
1a was formed. After that, as shown in FIG.
25 by using an ultra-high pressure mercury lamp for the composition layer 11a
It was irradiated with ultraviolet rays of 00 mJ / cm ² . Composition layer 11a
Clad portion 11 was formed by curing
(C)). At this time, the thickness of the clad portion 11 is 30 μm.
Met. Further, the refractive index of the clad portion 11 with respect to the D line of sodium at 25 ° C. was measured to be 1.5
It was 12.

Next, as shown in FIG. 1D, a composition layer 12a was formed on the cladding portion 11 by applying a composition for an optical waveguide core portion by a spin coating method.

Further, a photomask 21 having a stripe-shaped opening with a width of 30 μm is formed 10 times from the surface of the substrate 10.
The layers were arranged so as to be separated by 0 μm, and the composition layer 12a was irradiated with ultraviolet rays of 1500 mJ / cm ² through the photomask 21 by using an ultrahigh pressure mercury lamp (proximity exposure method). As a result, as shown in FIG. 1E, in the portion 12a1 of the composition layer 12a corresponding to the opening of the photomask, the composition for the optical waveguide core forming the composition layer 12a was cured. At this time, the thickness of the cured composition layer 12a was 30 μm. Moreover, the refractive index of sodium at 25 ° C. with respect to the D line was measured and found to be 1.558, and the difference in refractive index from the cladding portion 11 was 0.
It was 046.

After irradiating with ultraviolet rays, the photomask 21
UV rays are not radiated by the uncured portion 12a2
Was removed by dissolution with acetone. Subsequently, the cured product layer 12a (12a1) was washed with isopropyl alcohol. In this way, as shown in FIG.
A plurality of core portions 12 each having a strip shape in a plan view were formed.

Finally, as shown in FIG. 1G, the same composition as that of the cladding portion 11 was used on the exposed surface of the cladding portion 11 and the core portion 12 by the same method as that of the cladding portion 11. The clad portion 13 was formed and an embedded optical waveguide was manufactured.

<Example 13> A photomask 21 having a 50 μm wide stripe-shaped opening (see FIG. 1D).
Except that a core portion having a width of 50 μm is formed using
An optical waveguide was produced in the same manner as in Example 12.

<Embodiment 14> Using a photomask 21 having a stripe-shaped opening having a width of 70 μm, a width of 70 μm is obtained.
An optical waveguide was produced in the same manner as in Example 12 except that the core portion of m was formed.

Examples 12 to 14 thus obtained
Each of the optical waveguides was tested for optical propagation loss. This test uses wavelengths of 790 nm and 650 n
TE (Transverse Elect
Propagation loss in the ro) mode and TM (Transverse Magnetic) mode was measured by the cutback method (method of measuring the output power of the optical waveguide while gradually cutting the optical waveguide short). The results obtained are shown in Table 3.

The TE mode is a mode in which the electric field component exists only in the cross section of the optical waveguide and the magnetic field component exists in the light propagation direction. The TM mode is a mode in which a magnetic field component exists only in the cross section of the optical waveguide and an electric field component exists in the light propagation direction.

As can be seen from Table 3, Examples 12 to 1
In the optical waveguide of No. 4, a small value of 0.22 to 0.37 dB / cm was obtained in both the TE mode and the TM mode, and it was a good optical waveguide loss.

[0120]

[Table 3]

[0121]

The composition for an optical waveguide resin containing the alicyclic compound (a) having an oxetanyl group of the present invention has high reactivity in both cases of photocationic curing and thermal cation curing, and is capable of rapid curing. You can proceed.

The alicyclic compound (a) having an oxetanyl group of the present invention can change the refractive index by being mixed with an epoxy compound or another oxetane compound, and cores having different refractive indexes can be used. The composition for the clad part and the clad part can be made arbitrarily.

[0123]

[Brief description of drawings]

FIG. 1 is a diagram showing an example of a process for producing an optical waveguide using the composition for an optical waveguide resin of the present invention.

[0124]

[Explanation of symbols]

11a Composition layer for optical waveguide resin for clad portion 10 Substrate 11 Clad portion (cured product of optical waveguide resin for clad) 21 Photomask 12a Core portion Optical waveguide resin composition layer 12a ₁ Core portion optical waveguide Cured product of resin composition 12a ₂ Optical waveguide for core part Uncured product of resin composition 12 Core part 13 Clad part

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kiyotaka Ishida             1-1-1, Onodai, Midori-ku, Chiba City, Chiba Prefecture             Showa Denko Co., Ltd. (72) Inventor Ryuji Kadota             1-1-1, Onodai, Midori-ku, Chiba City, Chiba Prefecture             Showa Denko Co., Ltd. F-term (reference) 2H047 PA02 QA05 TA41                 4J005 AA07 AA11 BA00 BB01 BB02

Claims (19)

[Claims] 1. A composition for an optical waveguide resin, which comprises an alicyclic compound (a) having at least one oxetanyl group in the molecule. 2. The optical waveguide resin according to claim 1, wherein the alicyclic compound (a) having at least one oxetanyl group in the molecule is a compound represented by the general formula (1). Composition. [Chemical 1] (In the formula, R is a hydrogen atom, or an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a halogenated alkyl group, m is an integer of 0 to 2, and n is 0. Is 2, otherwise is 1.) 3. A compound represented by the general formula (1) is 2-oxaspiro [3.5] non-6-ene or 5-methyl-
The composition for an optical waveguide resin according to claim 2, which is 2-oxaspiro [3.5] non-6-ene. 4. The optical waveguide resin according to claim 1, wherein the alicyclic compound (a) having at least one oxetanyl group in the molecule is a compound represented by the general formula (2). Composition. [Chemical 2] (In the formula, R is a hydrogen atom, or an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a halogenated alkyl group, m is an integer of 0 to 2, and n is 0. Is 2, otherwise is 1.) 5. The compound according to claim 4, wherein the compound represented by the general formula (2) is 2-oxaspiro [3.5] nonane or 5-methyl-2-oxaspiro [3.5] nonane. The composition for optical waveguide resin of. 6. The optical waveguide resin according to claim 1, wherein the alicyclic compound (a) having at least one oxetanyl group in the molecule is a compound represented by the general formula (3). Composition. [Chemical 3] (In the formula, R is a hydrogen atom, or an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a halogenated alkyl group, m is an integer of 0 to 2, and n is 0. Is 2, otherwise is 1.) 7. A compound represented by the general formula (3) is 7,8-
Epoxy-5-methyl-2-oxaspiro [3.5] nonane, 6,7-epoxy-2-oxaspiro [3.5]
It is nonane, The composition for optical waveguide resins of Claim 6 characterized by the above-mentioned. 8. An alicyclic compound (a) having at least one oxetanyl group in the molecule is at least selected from compounds represented by general formula (1), general formula (2) and general formula (3). It is one kind, The composition for optical waveguide resins of Claim 1 characterized by the above-mentioned. 9. The composition for an optical waveguide resin according to claim 1, further comprising a compound (b) having at least one epoxy group and not having an oxetanyl group. . 10. The composition for an optical waveguide resin according to claim 9, wherein the compound (b) having at least one epoxy group and not having an oxetanyl group has a fluorine atom. 11. The composition for an optical waveguide resin according to claim 1, further comprising a compound (c) which initiates cationic polymerization by irradiation with active energy rays and / or heating. . 12. The compound (c) which initiates cationic polymerization by irradiation with active energy rays and / or heating is one or more selected from sulfonium salts, iodonium salts, phosphonium salts and diazonium salts. The composition for an optical waveguide resin according to 1. 13. The composition for an optical waveguide resin according to claim 1, which contains a radically polymerizable compound (d). 14. The composition for an optical waveguide resin according to claim 1, further comprising a photo radical initiator (e). 15. A cured product of sodium D at 25 ° C.
The optical waveguide resin composition according to any one of claims 1 to 14, wherein the refractive index with respect to a line is a value within a range of 1.40 to 1.70. 16. An optical waveguide obtained by curing the composition for optical waveguide resin according to any one of claims 1 to 15. 17. A product having a core part and a clad part, wherein at least one of the core part and the clad part is obtained by curing the optical waveguide resin composition according to any one of claims 1 to 15. An optical waveguide characterized by: 18. A composition for an optical waveguide resin comprising an alicyclic compound (a) having at least one oxetanyl group in the molecule and a compound (c) which initiates cationic polymerization by irradiation with active energy rays and / or heating. A method for producing an optical waveguide, in which the composition is selectively cured by selectively irradiating the layer using the composition with an active energy ray, and an optical waveguide is formed by a development treatment for removing an uncured portion. 19. An optical device using the optical waveguide according to claim 16.