JP2000066051A - Production of optical waveguide and optical waveguide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process capable of rapidly and easily producing an optical waveguide having low waveguide loss and excellent heat resistance and an optical waveguide by this process. SOLUTION: At least one of the lower clad layer 13, core portion 15 and upper clad layer in the process for producing the optical waveguide consisting of a substrate 12, the lower clad layer 13, the core portion 15 and the upper clad layer are formed by means of applying a radiation curing compsn. and curing this compsn. by irradiation with radiation. The core portion 15 is preferably formed by irradiating the thin film obtd. by application of the radiation curing compsn. with the radiation according to a prescribed pattern, thereby removing unexposed parts. The radiation curing compsn. preferably contains (A) at least one compd. selected from the group consisting of a specific hydrolyzable silane compd., its hydrolyzate and its condensate, (B) a photo acid generator and (c) a dehydrating agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing an optical waveguide for producing an optical circuit used in the optical communication field, optical information processing field, and the like, and an optical waveguide using the same.

[0002]

2. Description of the Related Art In the era of multimedia, transmission systems using light as a transmission medium have become public communication networks and LANs (local area networks) due to the demand for large-capacity and high-speed information processing in optical communication systems and computers. , FA (Factory Automation), interconnects between computers, home wiring, and the like. The optical waveguide is a basic component in an optical device, an optical integrated circuit (OEIC), an optical integrated circuit (optical IC), and the like for realizing a large-capacity information transmission such as a movie or a moving image, an optical computer, and the like. Since there is a great demand for this optical waveguide, in recent years, a particularly high-performance and low-cost product has been demanded.

Conventionally, polymer-based optical waveguides and quartz-based optical waveguides have been known as optical waveguides.
No. 1 and JP-A-7-159630 exemplify a method of manufacturing an optical waveguide using an ultraviolet curable resin. This polymer-based optical waveguide has an advantage that it can be manufactured easily and at low cost by using means such as photolithography as compared with a quartz-based optical waveguide, but the performance is generally that of the waveguide. There is a disadvantage that the loss is large and the heat resistance is low. In particular, there is a problem that the waveguide loss is large for light having a wavelength of 650 to 1600 nm used for communication.

On the other hand, as a method of manufacturing a silica-based waveguide,
A lower cladding layer made of a glass film is formed on a silicon substrate by means of flame deposition (FHD), CVD, or the like, and an inorganic thin film having a different refractive index from the lower cladding layer is formed on the lower cladding layer. A typical method is to form a core portion by patterning using a reactive ion etching (RIE) method, and then form an upper clad layer by a flame deposition method. However, in this method, the implementation of each step is considerably complicated, and
Since a vitrification step of heating to a temperature of 1000 ° C. or more is required to make each constituent layer transparent vitrified, it takes a long time to manufacture and costs are high.

On the other hand, Japanese Patent Application Laid-Open No. Hei 6-250036 discloses a method of manufacturing a quartz optical waveguide by forming an inorganic thin film using a so-called sol-gel method. In this method, compared to the flame deposition method,
A thin film can be formed in a short time at low temperature,
This is the same in that the process such as the reactive ion etching requires a long time, and as a result, the cost is high. As described above, according to the conventional method for manufacturing a silica-based optical waveguide, an optical waveguide having low waveguide loss and excellent heat resistance can be obtained, but the manufacturing process is complicated, the efficiency is low, and the cost is low. There was a problem of high.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has a low waveguide loss with respect to light ranging from the visible region to the infrared region and has excellent heat resistance. To provide a method that can be manufactured in a short time and with a simple process, and to provide an optical waveguide by this method.

[0007]

The above object is achieved by the following manufacturing method. That is, the method for manufacturing an optical waveguide according to the present invention comprises the steps of: forming a substrate, a lower cladding layer formed on the substrate, a core portion formed on the lower cladding layer, and forming the core portion and the lower cladding layer on the lower cladding layer; A method of manufacturing an optical waveguide comprising an upper clad layer, wherein at least one of a lower clad layer, a core portion, and an upper clad layer is coated with a radiation-curable composition and cured by irradiation with radiation. It is characterized by being formed by means including.

In the above method, a thin film obtained by applying a radiation-curable composition for forming a core portion is irradiated with radiation according to a predetermined pattern, and then the unexposed portion is removed. It is preferred to form a part. The radiation-curable composition for forming the core portion is a radiation-curable composition in which the refractive index of the core portion formed thereby is higher than the refractive indices of the lower cladding layer and the upper cladding layer. .

In the above method, the radiation-curable composition for forming the lower cladding layer, the core portion and the upper cladding layer preferably contains the following components (A) to (C). (A) at least one compound selected from the group consisting of a hydrolyzable silane compound represented by the general formula (1), a hydrolyzate thereof and a condensate thereof; a general formula (1) (R ¹ ) _p Si (X) _{4 -p} [wherein, R ¹ is a non-hydrolyzable organic group having 1 to 12 carbon atoms, X is a hydrolyzable group, and p is an integer of 0 to 3. (B) Photoacid generator (C) Dehydrating agent Here, R ¹ in the general formula (1) preferably has a radical polymerizable group or a cationic polymerizable group.

An optical waveguide according to the present invention is manufactured by the above method.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described specifically. FIG. 1 is an explanatory sectional view showing a basic configuration of an optical waveguide manufactured by the method of the present invention. As shown in FIG. 1, the optical waveguide 10 includes a substrate 12 extending in a direction perpendicular to the plane of the paper, a lower cladding layer 13 formed on the surface of the substrate 12, and a lower cladding layer 13 formed on the lower cladding layer 13. A core portion 15 having a specific width;
And an upper cladding layer 17 formed by stacking on the lower cladding layer 13 including
The whole is composed of the lower cladding layer 13 and the upper cladding layer 1
7 is buried in the stack.

According to a preferred embodiment of the method of the present invention, the optical waveguide 10 is manufactured as follows. That is, FIG.
As shown in (a), a substrate 12 having a flat surface is prepared. As the substrate 12, although not particularly limited, a silicon substrate, a glass substrate, or the like can be used. On the surface of the substrate 12, the lower cladding layer 1
3 is formed. Specifically, as shown in FIG. 2B, a composition for forming a lower cladding layer (hereinafter, referred to as “composition for lower layer”) composed of a radiation-curable composition described below is applied to the surface of the substrate 12. Then, the lower cladding layer 13 is formed by drying or pre-baking to form a lower layer thin film, and curing the lower layer thin film by irradiating it with radiation.

Next, on this lower cladding layer 13, FIG.
As shown in (c), a core-forming composition (hereinafter, referred to as “core composition”) composed of a radiation-curable composition described below is applied and dried or further prebaked to form a core thin film 14. . Thereafter, as shown in FIG. 2D, the upper surface of the core thin film 14 is irradiated with radiation according to a predetermined pattern, for example, via a photomask 18 having mask holes of a predetermined pattern. As a result, the portion irradiated with the radiation hardens, and by removing the other uncured portions, as shown in FIG. Is formed.

On the surface of the lower cladding layer 13 on which such a core portion 15 is formed, a composition for forming an upper cladding layer (hereinafter referred to as "upper layer composition") composed of a radiation-curable composition described later is applied. Then, drying or pre-baking is performed to form an upper layer thin film, and the upper layer thin film is irradiated with radiation and cured to form an upper clad layer 17 as shown in FIG. 10 are manufactured.

In the optical waveguide obtained as described above, the thicknesses of the lower cladding layer 13, the upper cladding layer 17 and the core portion 15 are not particularly limited, but the thickness of the lower cladding layer 13 is 3 to 50 μm. Core part 15
Is 3 to 20 μm, and the thickness of the upper cladding layer 17 is 3 μm.
It is preferably from 50 to 50 μm. The width of the core portion 15 is not particularly limited, but is, for example, in the range of 1 to 50 μm. The refractive index of the core portion 15 needs to be larger than the refractive index of any of the lower cladding layer 13 and the upper cladding layer 17. 1.450 to 1.650, lower cladding layer 13
The refractive index of the upper cladding layer 17 is 1.400 to 1.
648 is preferable, and the refractive index of the core portion is preferably larger than the refractive index of both cladding layers in the range of 0.002 to 0.5.

In a specific embodiment of the present invention, the lower clad layer, the core portion and the upper clad layer are each composed of a radiation-curable composition for forming those layers,
That is, the step of applying the composition for the lower layer, the composition for the core and the composition for the upper layer, drying the formed coating film, or pre-baking as needed to form a thin film, and curing the thin film by irradiation with radiation. It is preferable to form them after passing through.

In the present invention, the composition for the lower layer, the composition for the core and the composition for the upper layer include the following (A) to (C)
A radiation-curable composition containing the components is preferably used. (A) at least one compound selected from the group consisting of a hydrolyzable silane compound represented by the general formula (1), a hydrolyzate thereof and a condensate thereof; a general formula (1) (R ¹ ) _p Si (X) _{4 -p} [wherein, R ¹ is a non-hydrolyzable organic group having 1 to 12 carbon atoms, X is a hydrolyzable group, and p is an integer of 0 to 3. (B) Photoacid generator (C) Dehydrating agent

Hereinafter, the radiation-curable composition will be described. (1) Component (A) The component (A) is a main component of the radiation-curable composition, and comprises a hydrolyzable silane compound represented by the general formula (1), a hydrolyzate thereof, and a condensate thereof. At least one compound selected from the group consisting of:

Here, the hydrolyzable group represented by X is usually from room temperature (25 ° C.) to 10
It refers to a group that can be hydrolyzed to generate a silanol group by heating within a temperature range of 0 ° C., or a group that can form a siloxane condensate. Further, the subscript p in the general formula (1) is an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 1. However, in the hydrolyzate of the hydrolyzable silane compound represented by the general formula (1), a part of the hydrolyzable group that has not been hydrolyzed may remain. It becomes a mixture with an object. Further, the term "hydrolyzate of a hydrolyzable silane compound" means not only a compound in which an alkoxy group is changed to a silanol group by a hydrolysis reaction but also a partial condensate in which some silanol groups are condensed. . Furthermore, the hydrolyzable silane compound does not necessarily need to be hydrolyzed at the time of blending the radiation-curable composition, and at least a part of the hydrolyzable group is hydrolyzed at the stage of irradiation with radiation. Just fine. That is, in the case where the hydrolyzable silane compound is used without being hydrolyzed in advance in the radiation-curable composition, water is added in advance to hydrolyze the hydrolyzable group and generate a silanol group. Thereby, the radiation-curable composition can be radiation-cured.

[0020] [Organic radicals R ^1] The organic group R ¹ in the general formula (1) may be selected from the monovalent organic group is non-hydrolyzable. As such a non-hydrolyzable organic group, a non-polymerizable organic group and a polymerizable organic group or any one of the organic groups can be selected. Note that the non-hydrolysable in the organic group R ^1, in the conditions hydrolyzable group X is hydrolyzed, which means that the property of existing as stable.

Here, as the non-polymerizable organic group R ¹ ,
Examples include an alkyl group, an aryl group, and an aralkyl group. These may be linear, branched, cyclic, or a combination thereof. Further, more specific alkyl groups include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, an octyl group, and a deuterated alkyl group or a halogenated alkyl group. Among these alkyl groups, a methyl group is more preferred.

Specific examples of the aryl group in the non-polymerizable organic group R ¹ include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a biphenyl group, and a deuterated aryl group or a halogenated aryl group. Can be
Of these, a phenyl group is more preferred. Further, specific aralkyl groups in the non-polymerizable organic group R ¹ include a benzyl group and a phenylethyl group. Of these, a benzyl group is more preferred.

Further, the non-polymerizable organic group R ¹ is preferably a structural unit containing a hetero atom. Examples of such a structural unit include ether, ester, sulfide and the like. When the compound contains a hetero atom, it is preferably non-basic.

The polymerizable organic group R ¹ is preferably an organic group having a radically polymerizable functional group and a cationically polymerizable functional group or one of the functional groups in the molecule. By introducing such a functional group,
The radiation-curable composition can be more effectively cured by using radical polymerization or cationic polymerization in combination.

Of the radically polymerizable functional groups and cationically polymerizable functional groups in the polymerizable organic group R ¹ , more preferred are cationically polymerizable functional groups.
This is because the photoacid generator can cause not only a curing reaction at the silanol group but also a curing reaction at the cationically polymerizable functional group at the same time.

Organic group R having a radical polymerizable functional group
Examples of ¹ include an organic group having an olefin group, an organic group having (meth) acryloxy, an organic group having a styryl group, and an organic group having a vinyl ether. And more specific olefin groups include a vinyl group, a propenyl group and a butadienyl group. Of these, a vinyl group is more preferred. Also, (meta)
Examples of the organic group having acryloxy include (meth) acryloxymethyl and (meth) acryloxypropyl. Examples of the organic group having a styryl group include styryl, styrylethyl, and styrylpropyl. Further, examples of the organic group having a vinyl ether include vinyloxyethyl, vinyloxypropyl, vinyloxybutyl, vinyloxyoctyl, vinyloxycyclohexyl, and vinyloxyphenyl.

The organic group R ¹ having a cationically polymerizable functional group includes an organic group having a cyclic ether structure,
An organic group having a vinyl ether is exemplified. And more preferably, it is an organic group having a cyclic ether structure. As such a cyclic ether group, a 3- to 6-membered cyclic ether structure having a linear or cyclic structure, more specifically, an epoxy group, an oxetane group, a tetrahydrofuran,
And a structure containing a pyran unit. Further, among these cyclic ether groups, more preferred are those having a 4-membered or less cyclic ether structure such as an epoxy group and an oxetane group.

Further, specific examples of the organic group having a cyclic ether structure include glycidylpropyl, epoxidized cyclohexylethyl, methyloxetanylmethoxypropyl, and ethyloxetanylmethoxypropyl. Examples of the organic group having a vinyl ether include vinyloxyethyl, vinyloxypropyl, vinyloxybutyl, vinyloxyoctyl, vinyloxycyclohexyl, and vinyloxyphenyl.

[Hydrolysable group X] Examples of the hydrolyzable group X in the general formula (1) include a hydrogen atom, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, an amino group and an acyloxy group. Here, the preferred number of carbon atoms is 1 to 1
Specific examples of the alkoxy group 2 include methoxy, ethoxy, propoxy, butoxy, phenoxybenzyloxy, methoxyethoxy, acetoxyethoxy, 2- (meth) acryloxyethoxy, and 3- (meta). ) Acryloxypropoxy group, 4- (meth) acryloxybutoxy group, or epoxy group-containing alkoxy group such as glycidyloxy group, epoxidized cyclohexylethoxy group, etc., oxetane group-containing alkoxy group such as methyloxetanemethoxy, ethyloxetanemethoxy, oxa Examples thereof include an alkoxy group having a 6-membered ring ether group such as cyclohexyloxy. Further, among the above-mentioned alkoxy groups having 1 to 12 carbon atoms, a methoxy group and an ethoxy group are more preferable. These alkoxy groups are easily hydrolyzed to generate silanol groups, so that a radiation curing reaction can be stably caused.

Preferred examples of the halogen atom include fluorine, chlorine, bromine and iodine. However, when using a hydrolyzable silane compound containing a halogen atom as the hydrolyzable group, care must be taken so as not to lower the storage stability of the radiation-curable composition. That is, depending on the amount of hydrogen halide generated by hydrolysis, such hydrogen halide is neutralized,
It is preferable that the radiation-curable composition is removed by an operation such as distillation so as not to affect the storage stability.

Preferred examples of the amino group include an amino group, a dimethylamino group, a diethylamino group, a butylamino group, a dibutylamino group, a phenylamino group and a diphenylamino group. However, when an amino group is used as the hydrolyzable group, amines are generated by hydrolysis. Therefore, it is preferable to remove such by-product amines before finally preparing the radiation-curable composition so as not to affect the storage stability of the radiation-curable composition.

Preferred acyloxy groups include:
Examples include an acetoxy group and a butyroyloxy group.

[Specific Examples of Hydrolyzable Silane Compound] Next, specific examples of the hydrolyzable silane compound represented by the formula (1) (may be simply referred to as a silane compound) will be described. First, silane compounds having a non-polymerizable organic group R ¹ include tetrachlorosilane, tetraaminosilane, tetraacetoxysilane, tetramethoxysilane,
Examples thereof include silane compounds substituted with four hydrolyzable groups such as tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenzyloxysilane, trimethoxysilane, and triethoxysilane.

Similarly, methyltrichlorosilane,
Methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, pentafluorophenyltrimethoxysilane, phenyltrimethoxysilane, d ₃ Silane compounds substituted with three hydrolyzable groups, such as -methyltrimethoxysilane, nonafluorobutylethyltrimethoxysilane, and trifluoromethyltrimethoxysilane.

Similarly, dimethyldichlorosilane,
Dimethyldiaminosilane, dimethyldiacetoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, silane compounds substituted with two hydrolyzable groups such as dibutyldimethoxysilane, and trimethylchlorosilane, hexamethyldisilazane, trimethylsilane,
Examples thereof include silane compounds substituted with one hydrolyzable group such as tributylsilane, trimethylmethoxysilane, and tributylethoxysilane.

Among these, more preferred examples of the hydrolyzable silane compound include methylalkoxysilanes such as methyltrimethoxysilane and methyltriethoxysilane, and tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane. is there.

Examples of the silane compound having a polymerizable organic group R ¹ include a silane compound containing a polymerizable organic group R ¹ as a non-hydrolyzable organic group in X, and a silane compound containing a polymerizable organic group R ¹ in X. Any of the silane compounds having a polymerizable organic group R ¹ can be used.

Here, silane compounds containing a polymerizable organic group R ¹ in the non-hydrolyzable organic group X include (meth) acryloxypropyltrimethoxysilane, (meth) acryloxypropyltriethoxysilane, ( (Meth) acryloxypropylmethyldimethoxysilane,
(Meth) acryloxysilane compounds such as (meth) acryloxypropyltrichlorosilane, bis (methacryloxypropyl) dimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, etc. Epoxy such as vinylsilane compound, glycidyloxytrimethoxysilane, bis (glycidyloxy) dimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane Oxetanesilane compounds such as silane compounds, 3- (3-methyl-3-oxetanemethoxy) propyltrimethoxysilane, and 3- (3-ethyl-3-oxetanemethoxy) propyltriethoxysilane And silane compounds having a 6-membered ring ether structure such as oxacyclohexyltrimethoxysilane and oxacyclohexyltriethoxysilane. These can be used alone or in combination of two or more.

Examples of the silane compound containing a polymerizable organic group R ¹ as a hydrolyzable organic group in X include tetra (meth) acryloxysilane, tetrakis [2-
((Meth) acryloxyethoxy) silane, tetraglycidyloxysilane, tetrakis (2-vinyloxyethoxy) silane, tetrakis (2-vinyloxybutoxy) silane, tetrakis (3-methyl-3-oxetanemethoxy) silane, methyltri ( (Meth) acryloxysilane,
Methyl [2- (meth) acryloxyethoxy] silane,
Methyl-triglycidyloxysilane, methyl tris (3
-Methyl-3-oxetanemethoxy) silane. These can be used alone or in combination of two or more.

Further, among the silane compound having a polymerizable organic group R ^1, more preferably a silane compound containing an organic group R ¹ in the polymerizable to a non-hydrolyzable organic group, more preferably, the cationic It is a silane compound having a polymerizable organic group. Such specific examples include glycidyloxypropyltrimethoxysilane, glycidyloxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4
-Epoxycyclohexyl) ethyltriethoxysilane, 3- (3-methyl-3-oxetanemethoxy) propyltrimethoxysilane, 3- (3-ethyl-3-oxetanemethoxy) propyltrimethoxysilane, 3-
(3-methyl-3-oxetanemethoxy) propyltriethoxysilane, 3- (3-ethyl-3-oxetanemethoxy) propyltrimethoxysilane, and the like.

[Example of obtaining hydrolyzable silane compound] The hydrolyzable silane compound described above can be synthesized by a known method. For example, Pure Appl.
Chem. , A34 (11), 2335, 1997.
Year, Eur. Polym. J. Vol. 33, N
o. 7, page 1021, 1997, a compound having an olefin group is subjected to hydrosilylation of a trialkoxysilane with a transition metal complex or a radical generator as a catalyst to obtain an alkoxy compound having various functional groups. Silanes can be produced.

Some of these hydrolyzable silane compounds are commercially available and can be easily obtained. For example, A-15 manufactured by Nippon Unicar Co., Ltd.
1, A-171, A-172, A-174, Y-993
6, AZ-6167, AZ-6134, A-186, A
-187, MAC-2101, MAC-2301, FZ
-3704, AZ-6200, A-162, A-16
3, AZ-6171, A-137, A-153, A-1
230, for example, SZ-6030, SH-6040, SZ-6 manufactured by Dow Corning Toray Silicone Co., Ltd.
070, SZ-6072, SZ-6075, SZ-60
79, SZ-6300, PRX11, PRX19, PR
X24, AY43-154M and the like.

[Hydrolysis Conditions of Hydrolyzable Silane Compound] The conditions for hydrolyzing or condensing the above-mentioned silane compound are not particularly limited. It is preferably carried out by a process.

1) The hydrolyzable silane compound represented by the general formula (1) and a predetermined amount of water are accommodated in a vessel equipped with a stirrer. 2) Next, while adjusting the viscosity of the solution, the organic solvent is further accommodated in the container to form a mixed solution. 3) The obtained mixed solution is heated and stirred in an air atmosphere at 0 ° C. to a temperature not higher than the boiling point of the organic solvent or the hydrolyzable silane compound for 1 to 24 hours. During the heating and stirring, if necessary, the mixed solution is concentrated by distillation,
Alternatively, it is also preferable to replace the solvent.

(2) Photoacid generator [Definition] The photoacid generator of the component (B) in the radiation-curable composition emits the hydrolyzable silane compound as the component (A) upon irradiation with radiation. It is defined as a compound capable of releasing a curable (crosslinkable) acidic active substance.

The radiation for decomposing the photoacid generator to generate cations includes visible light, ultraviolet light, infrared light,
X-rays, α-rays, β-rays, γ-rays and the like can be mentioned, but they have the advantage that they have a constant energy level, can obtain a large curing rate, and the irradiation device can be relatively inexpensive and small. For this reason, ultraviolet rays are preferred.

It is also preferable to use a radical generator described below together with the photoacid generator. Radicals, which are neutral active substances, do not promote the condensation reaction of silanol groups, but when the component (A) has a radical polymerizable functional group, it can promote the polymerization of such a functional group. it can. Therefore, the radiation-curable composition can be more efficiently cured.

[Types of photoacid generator] As the photoacid generator, an onium salt (compound of the first group) having a structure represented by the general formula (2) or a structure represented by the general formula (3) (A second group of compounds).

Formula (2) [R ² _a R ³ _b R ⁴ _c R ⁵ _d W] ^{+ m} [MZ _{m + n} ] ^-m [wherein the cation is an onium ion, and W is S, S
e, Te, P, As, Sb, Bi, O, I, Br, Cl
Or -N≡N, R ² , R ³ , R ⁴ and R ⁵ are the same or different organic groups, and a, b, c and d are each an integer of 0 to 3; The value is equal to the valence of W. M is a halide complex
A metal or metalloid constituting the central atom of [MZ _{m + n} ], for example, B, P, As, Sb, Fe, Sn, B
i, Al, Ca, In, Ti, Zn, Sc, V, Cr,
Mn and Co. Z is, for example, a halogen atom or an aryl group such as F, Cl, or Br; m is the net charge of the halide complex ion; and n is the valence of M. ]

General formula (3): Q _S- [S (ＯO) ₂ -R ⁶ ] _t [wherein Q is a monovalent or divalent organic group, and R ⁶ is a monovalent monovalent having 1 to 12 carbon atoms. The organic group, the subscript s is 0 or 1, and the subscript t is 1 or 2. ]

First, onium salts, which are a first group of compounds, are compounds that can release an acidic active substance upon receiving light. Here, specific examples of the anion [MZ _{m + n} ] in the general formula (2) include tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), and hexafluoroantimonate (SbF
₆ ^-), hexafluoroarsenate (AsF ₆ ^-),
Hexachloroantimonate (SbCl ₆ ⁻ ), tetraphenylborate, tetrakis (trifluoromethylphenyl) borate, tetrakis (pentafluoromethylphenyl) borate and the like can be mentioned.

The anion [M] in the general formula (2)
Z_{m + n}] Instead of the general formula [MZ _nOH^-]
It is also preferred to use anions. In addition, perchlorine
Acid ion (ClO_Four ^-), Trifluoromethanesulfo
Acid ion (CF_ThreeSO_Three ^-), Fluorosulfonic acid
Ion (FSO_Three ^-), Toluenesulfonate ion,
Trinitrobenzenesulfonate anion, trinitro
Has other anions such as toluenesulfonate anion
Onium salts can also be used.

Examples of commercially available products of the first group of compounds are as follows: San Aid SI-60, SI-80, SI-10
0, SI-60L, SI-80L, SI-100L, S
I-L145, SI-L150, SI-L160, SI
-L110, SI-L147 (manufactured by Sanshin Chemical Industry Co., Ltd.), UVI-6950, UVI-6970, U
VI-6974, UVI-6990 (all manufactured by Union Carbide), Adeka Optomer SP-150, SP
-151, SP-170, SP-171 (all manufactured by Asahi Denka Kogyo KK), Irgacure 261 (made by Ciba Specialty Chemicals KK), CI-2481, C
I-2624, CI-2639, CI-2064 (all manufactured by Nippon Soda Co., Ltd.), CD-1010, CD-10
11, CD-1012 (all made by Sartomer), DS
-100, DS-101, DAM-101, DAM-1
02, DAM-105, DAM-201, DSM-30
1, NAI-100, NAI-101, NAI-10
5, NAI-106, SI-100, SI-101, S
I-105, SI-106, PI-105, NDI-1
05, Benzoin Tosylate, MBZ-1
01, MBZ-301, PYR-100, PYR-20
0, DNB-101, NB-101, NB-201, B
BI-101, BBI-102, BBI-103, BB
I-109 (all manufactured by Midori Kagaku Co., Ltd.), PCI-0
61T, PCI-062T, PCI-020T, PCI
-022T (Nippon Kayaku Co., Ltd.), IBPF, I
BCF (manufactured by Sanwa Chemical Co., Ltd.) and the like can be mentioned.

Of the above-mentioned compounds of the first group, more effective onium salts are aromatic onium salts, particularly preferably diaryliodonium salts represented by the following general formula (4). General formula (4) [R ⁷ -Ar ¹ -I ⁺ -Ar ² -R ⁸ ] [Y ⁻ ] wherein R ⁷ and R ⁸ are each a monovalent organic group, and And at least one of R ⁷ and R ⁸ has an alkyl group having 4 or more carbon atoms, Ar ¹ and Ar ² are each an aromatic group, which may be the same or different, and Y ⁻ is A monovalent anion, a fluoride anion of group 3 or 5 of the periodic table, or
An anion selected from ClO ₄ ⁻ and CF ₃ —SO ₃ ^— . ]

Specific examples of such diaryliodonium salts include (4-n-decyloxyphenyl) phenyliodonium hexafluoroantimonate,
[4- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium hexafluoroantimonate, [4- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium trifluorosulfonate, [4- (2 -Hydroxy-n-tetradecyloxy) phenyl] phenyliodonium hexafluorophosphate, [4- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium tetrakis (pentafluorophenyl) borate, bis (4
-T-butylphenyl) iodonium hexafluoroantimonate, bis (4-t-butylphenyl) iodonium hexafluorophosphate, bis (4-
t-butylphenyl) iodonium trifluorosulfonate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) One or a combination of two or more of iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium trifluoromethylsulfonate and the like can be mentioned.

Commercially available diaryliodonium salts include, for example, CD1012 manufactured by Sartomer, IBPF and IBCF manufactured by Sanwa Chemical Co., Ltd., and BBI-101, BBI-102 and BBI manufactured by Midori Chemical Co., Ltd. −
103, BBI-109 and the like.

Further, the method for producing the diaryliodonium salt represented by the general formula (4) is not particularly limited. For example, J. Polymer Science: Part A: polyme
r Chemistry, Vol. 31, 1473-1482 (1993), J. Polymer Sc
ience: Part A: polymer Chemistry, Vol.31, 1483-1491 (1
It can be produced by the method described in 993).

Next, the second group of compounds will be described.
Examples of the sulfonic acid derivative represented by the general formula (3) include disulfones, disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzoylmethanes, imidosulfonates, benzoin sulfonates, 1-
Examples thereof include sulfonates of oxy-2-hydroxy-3-propyl alcohol, pyrogallol trisulfonates, and benzyl sulfonates. Further, in the general formula (3), imide sulfonates are more preferable, and trifluoromethyl sulfonate derivatives are more preferable among imido sulfonates.

Specific examples of such sulfonates include diphenyldisulfone, ditosyldisulfone, bis (phenylsulfonyl) diazomethane, bis (chlorophenylsulfonyl) diazomethane, bis (xylylsulfonyl) diazomethane, and phenylsulfonylbenzoyl. Diazomethane, bis (cyclohexylsulfonyl) methane, 1,8-naphthalenedicarboxylic acid imide methylsulfonate, 1,8-naphthalenedicarboxylic acid imide tosylsulfonate, 1,8-naphthalenedicarboxylic acid imide trifluoromethylsulfonate,
1,8-naphthalenedicarboxylic acid imide camphorsulfonate, succinimide phenylsulfonate,
Succinimide tosyl sulfonate, succinimide trifluoromethylsulfonate, succinimide
Camphorsulfonate, phthalimide trifluorosulfonate, cis-5-norbornene-endo-
2,3-dicarboxylic imide trifluoromethylsulfonate, benzoin tosylate, 1,2-diphenyl-2-hydroxypropyl tosylate, 1,2-di (4-methylmercaptophenyl) -2-hydroxypropyl tosylate, pyrogallol methylsulfonate , Pyrogallol ethylsulfonate, 2,6-dinitrophenylmethyl tosylate, ortho-nitrophenylmethyl tosylate and para-nitrophenyl tosylate.

[Amount of Photoacid Generator] The content of the photoacid generator in the radiation-curable composition is not particularly limited, but is usually 0.1 to 100 parts by weight of the component (A). It is preferred that the value be in the range of 1 to 15 parts by weight.
If the amount of the photoacid generator is less than 0.1 parts by weight, the radiation curability tends to decrease, and a sufficient curing speed tends not to be obtained. On the other hand, if the amount of the photoacid generator exceeds 15 parts by weight, the cured product obtained tends to have reduced weather resistance and heat resistance. Therefore, from the viewpoint of better balance between the radiation curability and the weather resistance of the obtained cured product, the addition amount of the photoacid generator is 1 to 10 parts by weight based on 100 parts by weight of the component (A).
More preferably, the value is in the range of parts by weight.

(3) Dehydrating agent [Definition] The dehydrating agent in the radiation-curable composition affects the radiation-curing property and the storage stability by a compound that converts to a substance other than water by a chemical reaction, or by physical adsorption or inclusion. It is defined as a compound that is not given. That is, by containing such a dehydrating agent, conflicting properties such as storage stability and radiation curability can be improved without impairing the weather resistance and heat resistance of the radiation-curable composition.
Although the reason for this is not necessarily clear, the storage stability of the radiation-curable composition is improved because the dehydrating agent effectively absorbs water entering from the outside.On the other hand, in the condensation reaction, which is a radiation curing reaction, It is considered that the radiation curability of the radiation curable composition is improved because the generated water is successively and effectively absorbed by the dehydrating agent.

[Type of Dehydrating Agent] The type of the dehydrating agent is not particularly limited, but is selected from the group consisting of carboxylic esters, acetals (including ketals), and carboxylic anhydrides as organic compounds. Preferably, at least one compound is used. It is also preferable to use a ceramic powder having a dehydration function as the inorganic compound. These dehydrating agents exhibit an excellent dehydrating effect, and can efficiently exhibit the function of the dehydrating agent with a small amount of addition.

The carboxylic acid ester as the dehydrating agent is selected from among carboxylic acid orthoesters and carboxylic acid silyl esters. Here, preferred carboxylic acid orthoesters include methyl orthoformate, ethyl orthoformate, propyl orthoformate, butyl orthoformate, methyl orthoacetate, ethyl orthoacetate, propyl orthoacetate, butyl orthoacetate, methyl orthopropionate, methyl orthopropionate and orthopropion Ethyl acid and the like. In addition, among these carboxylic acid orthoesters, orthoformate is particularly preferred as a dehydrating agent, from the viewpoint of exhibiting a more excellent dehydration effect and further improving storage stability and radiation curability. Preferred examples of the silyl carboxylate include trimethylsilyl acetate, tributylsilyl acetate, trimethylsilyl formate, and trimethylsilyl oxalate.

It is more preferable to use carboxylic acid orthoester among the carboxylic acid esters. The carboxylic acid orthoester can efficiently absorb water and hydrolyze on its own. Further, the compound formed by hydrolysis of the carboxylic acid orthoester is neutral.
Therefore, the carboxylic acid orthoester exhibits an excellent dehydration effect, and can further improve storage stability and radiation curability.

Preferred acetals include, for example, dimethyl acetal which is a reaction product of a ketone such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone, acetaldehyde, propionaldehyde, benzaldehyde and a monohydric alcohol; Examples thereof include diethyl acetal and dipropyl acetal, and ketene silyl acetals produced by a silylation reaction of an acetal composed of a dihydric alcohol such as ethylene glycol and a ketone and a carboxylic acid ester.

Among these acetals, acetone dimethyl acetal, acetone diethyl acetal, methyl ethyl ketone dimethyl acetal, methyl ethyl ketone diethyl acetal, cyclohexanone dimethyl acetal, and cyclohexanone diethyl acetal exhibit particularly excellent dehydration effects, and have excellent storage stability and radiation stability. It is preferable for use as a dehydrating agent in the present invention from the viewpoint that the curability can be further improved.

Preferred carboxylic anhydrides include, for example, formic anhydride, acetic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, benzoic anhydride and the like. In particular, acetic anhydride and succinic anhydride are particularly excellent in the dehydration effect and are preferred.

Examples of the ceramic powder having a preferable dehydration function include silica gel particles, alumina particles, silica alumina particles, activated clay, zeolite and the like. These ceramic powders have a strong affinity for water and can exhibit an excellent dewatering effect.

[Properties of Dehydrating Agent] Next, the properties of the dehydrating agent will be described. First, the dehydrating agent is a solid or liquid at normal temperature and normal pressure, and is selected from compounds that exhibit a dehydrating effect by being dissolved or dispersed in the radiation-curable composition. Also, when the dehydrating agent is selected from organic compounds,
The boiling point (under normal pressure) is preferably set to a value within the range of 40 to 200 ° C. If the boiling point is within such a range, the solvent can be volatilized efficiently under drying conditions at room temperature (25 ° C.) to 200 ° C. Therefore, it is easy to remove the dehydrating agent. On the other hand, when the dehydrating agent is selected from inorganic compounds, it is uniformly dispersed and used so as not to impair the applicability and transparency of the radiation-curable resin composition.

[Amount of Dehydrating Agent] The content of the dehydrating agent in the radiation-curable composition is not particularly limited, but is usually 0.1 to 10 parts by weight based on 100 parts by weight of the component (A).
Preferably, the value is within the range of 100 parts by weight. When the amount of the dehydrating agent is less than 0.1 part by weight, the effect of the addition tends to be poor, and the effect of improving storage stability and radiation curability tends to be low. On the other hand, if the addition amount of the dehydrating agent exceeds 100 parts by weight, the effect of improving storage stability and radiation curability tends to be saturated. Therefore, more preferably, the addition amount of the dehydrating agent is a value in the range of 0.5 to 50 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the component (A). Value.

(4) Additives The radiation-curable composition used in the present invention contains a radical photopolymerization initiator, a photosensitizer, and a reactive diluent as long as the objects and effects of the present invention are not impaired. Agents, silica particles, additives such as organic solvents, and the like.

[Radical Photopolymerization Initiator] In the radiation-curable composition used in the present invention, a radical photopolymerization initiator (radical generator) may be added in combination with the photoacid generator. The radical generator is a compound that is decomposed by receiving radiation such as ultraviolet rays to generate a radical, and the radical polymerizable group is polymerized by the radical.

Examples of such a radical generator include acetophenone, acetophenone benzyl ketal,
Anthraquinone, 1- (4-isopropylphenyl)-
2-hydroxy-2-methylpropan-1-one, carbazole, xanthone, 4-chlorobenzophenone,
4,4'-diaminobenzophenone, 1,1-dimethoxydeoxybenzoin, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthones, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -Propan-2-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, triphenylamine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide,
Bis (2,6-dimethoxybenzoyl) -2,4,4-
Tri-methylpentylphosphine oxide, benzyldimethylketal, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, fluorenone, fluorene,
Benzaldehyde, benzoin ethyl ether, benzoin propyl ether, benzophenone, benzophenone derivatives, Michler's ketone, 3-methylacetophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone (BTTB) and the like. In addition, such a radical generator can be used alone or in combination of two or more.

[Photosensitizer] The radiation-curable composition used in the present invention may contain a photosensitizer in combination with a photoacid generator. A photosensitizer is a compound that absorbs energy rays such as light and improves the sensitivity of a photoacid generator.

Such photosensitizers include thioxanthone, diethylthioxanthone and thioxanthone derivatives; anthraquinone, bromoanthraquinone and anthraquinone derivatives; anthracene, bromoanthracene and anthracene derivatives; perylene and perylene derivatives; xanthene, thioxanthene and Derivatives of thioxanthene; coumarin and ketocoumarin; Further, among these photosensitizers, more preferable compounds are diethylthioxanthone and bromoanthracene.

[Reactive Diluent] By adding (blending) a reactive diluent to the radiation-curable composition used in the present invention, the curing shrinkage of the resulting cured film can be reduced, and Mechanical strength can be controlled. Further, when a radically polymerizable reactive diluent is used, the photoreactivity of the radiation-curable composition can be adjusted by further adding a radical generator. When a cationically polymerizable reactive diluent is used, photoreactivity and mechanical properties can be adjusted.

[Type of Reactive Diluent] As the reactive diluent, it is preferable to blend a cationically polymerizable monomer and an ethylenically unsaturated monomer, or one of them. Here, the cationic polymerizable monomer that is a reactive diluent is defined as an organic compound that causes a polymerization reaction or a cross-linking reaction when irradiated with light in the presence of a photoacid generator. Thus, for example, epoxy compounds, oxetane compounds, oxolane compounds, cyclic acetal compounds,
Cyclic lactone compounds, thiirane compounds, thiethane compounds, vinyl ether compounds, spiroorthoester compounds which are reaction products of epoxy compounds and lactones, ethylenically unsaturated compounds, cyclic ether compounds, cyclic thioether compounds, vinyl compounds and the like. it can. One of these cationically polymerizable monomers can be used alone, or two or more of them can be used in combination.

The epoxy compounds as the above-mentioned cationic polymerizable monomers include, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, and brominated bisphenol F diglycidyl. Ether, brominated bisphenol S diglycidyl ether, epoxy novolak resin,
Hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 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, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylene bis (3
4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether Trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers; by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin Polyglycidyl ethers of the resulting polyether polyol;
Diglycidyl esters of aliphatic long-chain dibasic acids; monoglycidyl ethers of higher aliphatic alcohols; monoglycidyl ethers of phenol, cresol, butylphenol or polyether alcohols obtained by adding alkylene oxide to them; higher fatty acids Glycidyl esters; epoxidized soybean oil; butyl epoxystearate; octyl epoxystearate; epoxidized linseed oil; epoxidized polybutadiene, and the like.

Other cationically polymerizable monomers include trimethylene oxide, 3,3-dimethyloxetane, 3,3-dichloromethyloxetane, 3-ethyl-
3-phenoxymethyloxetane, bis (3-ethyl-
Oxetanes such as 3-methyloxy) butane; oxolanes such as tetrahydrofuran and 2,3-dimethyltetrahydrofuran; trioxane, 1,3-dioxolan;
Cyclic acetals such as 1,3,6-trioxanecyclooctane; cyclic lactones such as β-propiolactone and ε-caprolactone; thiirane such as ethylene sulfide, 1,2-propylene sulfide and thioepichlorohydrin; Thiethanes such as 3,3-dimethylthiethane; vinyl ethers such as ethylene glycol divinyl ether, triethylene glycol divinyl ether, and trimethylolpropane trivinyl ether; spiro ortho esters obtained by reacting an epoxy compound with a lactone; vinylcyclohexane And ethylenically unsaturated compounds such as isobutylene and polybutadiene; and derivatives of the above compounds.

Among the above cationically polymerizable monomers, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, (3,4-epoxycyclohexylmethyl) adipate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether,
Polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether are preferred.

Particularly preferred cationically polymerizable monomers are 3,4-epoxycyclohexylmethyl-3 ′,
An epoxy compound having two or more alicyclic epoxy groups in one molecule, such as 4'-epoxycyclohexanecarboxylate and bis (3,4-epoxycyclohexylmethyl) adipate.

The above-mentioned cationic polymerizable monomers include UVR-6100, UVR-6105, and UVR-6105.
110, UVR-6128, UVR-6200, UVR
-6216 (all manufactured by Union Carbide Co.), Celloxide 2021, Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 20
85, celoxide 2000, celoxide 3000,
Glycidol, AOEX24, Cyclomer A200,
Cyclomer M100, EPOLID GT-300, EPOLID GT-301, EPOLID GT-302, EPOLID GT-400, EPOLID 401, EPOLID 40
3 (Daicel Chemical Industries, Ltd.), Epicoat 8
28, Epicoat 812, Epicoat 1031, Epicoat 872, Epicoat CT508 (all manufactured by Yuka Shell Co., Ltd.), KRM-2100, KRM-2110, K
RM-2199, KRM-2400, KRM-241
0, KRM-2408, KRM-2490, KRM-2
200, KRM-2720, KRM-2750 (or more,
Asahi Denka Kogyo Co., Ltd.), Rapi-Cure DVE-
3, CHVE, PEPC (above, manufactured by ISP), VEC
TOMER 2010, 2020, 4010, 4020
(All manufactured by Allied Signal Co., Ltd.).

Next, an ethylenically unsaturated monomer as a reactive diluent will be described. Here, the ethylenically unsaturated monomer is a compound having an ethylenically unsaturated bond (C = C) in a molecule, a monofunctional monomer having one ethylenically unsaturated bond in one molecule, and one molecule. It can be defined as a polyfunctional monomer having two or more ethylenically unsaturated bonds therein.

Therefore, examples of the monofunctional monomer which is an ethylenically unsaturated monomer include (meth) acryloylmorpholine, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide, Bornyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate, t-octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) Acrylate, diethylaminoethyl (meth) acrylate, lauryl (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, diacrylate Clopentenyl (meth) acrylate, N, N-dimethyl (meth) acrylamide tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrabromophenyl (meth) acrylate, 2-tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxyethyl (meth) acrylate, tribromophenyl (meth) acrylate, 2-tribromophenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2 -Hydroxypropyl (meth) acrylate, vinyl caprolactam, N-vinylpyrrolidone, phenoxyethyl (meth) acrylate,
Butoxyethyl (meth) acrylate, pentachlorophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, bornyl (meth) acrylate, methyltriethylenediglycol ( (Meth) acrylates.

Among these acrylates, acrylates containing no amide or amine structure are preferable from the viewpoint of not deteriorating radiation curability, and acrylates containing no aromatic ring are preferable for the purpose of securing weather resistance. Examples of these acrylates include isobornyl (meth) acrylate, lauryl (meth) acrylate, butoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, bornyl (meth) acrylate, and methyltriethylene diglycol (meth) acrylate Can be mentioned.

The monofunctional monomers which are ethylenically unsaturated monomers include, for example, Aronix M-101, M-102, M-111, M-113, M-113
-117, M-152, TO-1210 (all manufactured by Toagosei Co., Ltd.), Kayarad TC-110S, R-56
4, R-128H (Nippon Kayaku Co., Ltd.), Biscoat 192, Biscoat 220, Biscoat 2311H
P, Viscoat 2000, Viscoat 2100, Viscoat 2150, Viscoat 8F, Viscoat 17F (all manufactured by Osaka Organic Chemical Industry Co., Ltd.) and the like can be easily obtained.

The polyfunctional monomers which are ethylenically unsaturated monomers include, for example, ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth)
Acrylate, triethylene glycol diacrylate, tetraethylene glycol di (meth) acrylate, tricyclodecanediyl dimethylene di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) Isocyanurate tri (meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide (hereinafter referred to as “EO”) modified trimethylolpropane tri (meth) A) acrylate, propylene oxide (hereinafter referred to as “PO”) modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate , Neopentyl glycol di (meth) acrylate, both-terminal (meth) acrylic acid adduct of bisphenol A diglycidyl ether, 1,4
-Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, polyethylene glycol di (meth)
Acrylate, dipentaerythritol hexa (meth)
Acrylate, dipentaerythritol penta (meth)
Acrylate, dipentaerythritol tetra (meth)
Acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate,
Ditrimethylolpropane tetra (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, PO-modified bisphenol A di (meth) acrylate, EO-modified hydrogenated bisphenol A di (meth) acrylate, PO-modified hydrogenated bisphenol A di (meth) ) Acrylate, EO-modified bisphenol F di (meth) acrylate, (meth) acrylate of phenol novolak polyglycidyl ether, and the like.

Among these acrylates and the like, acrylates containing no amide or amine structure are preferable from the viewpoint of not deteriorating radiation curability, and acrylates containing no aromatic ring are preferable for the purpose of securing weather resistance.
Thus, for example, ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate, tetraethylene glycol di (meth) acrylate, tricyclodecanediyl dimethylene di (meth) acrylate, trimethylolpropane Examples thereof include tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol tetra (meth) acrylate.

Examples of these polyfunctional monomers which are ethylenically unsaturated monomers include SA1002 (manufactured by Mitsubishi Chemical Corporation), Biscoat 195, Biscoat 230, Biscoat 260, Biscoat 215 and Biscoat 31.
0, Biscoat 214HP, Biscoat 295, Biscoat 300, Biscoat 360, Biscoat GPT, Biscoat 400, Biscoat 700, Biscoat 54
0, Viscoat 3000, Viscoat 3700 (or more,
Osaka Organic Chemical Industry Co., Ltd.), Kayarad R-526,
HDDA, NPGDA, TPGDA, MANDA, R-
551, R-712, R-604, R-684, PET
-30, GPO-303, TMPTA, THE-33
0, DPHA, DPHA-2H, DPHA-2C, DP
HA-2I, D-310, D-330, DPCA-2
0, DPCA-30, DPCA-60, DPCA-12
0, DN-0075, DN-2475, T-1420,
T-2020, T-2040, TPA-320, TPA
-330, RP-1040, RP-2040, R-01
1, R-300, R-205 (Nippon Kayaku Co., Ltd.)
Alonix M-210, M-220, M-23
3, M-240, M-215, M-305, M-30
9, M-310, M-315, M-325, M-40
0, M-6200, M-6400 (all manufactured by Toagosei Co., Ltd.), light acrylate BP-4EA, BP-
4PA, BP-2EA, BP-2PA, DCP-A (all manufactured by Kyoeisha Chemical Co., Ltd.), New Frontier BPE
-4, BR-42M, GX-8345 (above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), ASF-400 (above, manufactured by Nippon Steel Chemical Co., Ltd.), Lipoxy SP-1506, SP-150
7, SP-1509, VR-77, SP-4010, S
P-4060 (all, manufactured by Showa Polymer Co., Ltd.), NK ester A-BPE-4 (all, manufactured by Shin-Nakamura Chemical Co., Ltd.)
Etc., and can be easily obtained as a commercial product.

The monofunctional monomer and the polyfunctional monomer, which are ethylenically unsaturated monomers, may be used alone or in combination of two or more. Alternatively, at least one monofunctional monomer and at least one polyfunctional monomer may be used. Are preferably combined. Examples of such a polyfunctional monomer having a polymerizable group having three or more functional groups include the tri (meth) acrylate compounds, tetra (meth) acrylate compounds, penta (meth) acrylate compounds, and hexa (meth) acrylate compounds exemplified above. You can choose from. Among them, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate Is particularly preferred.

[Silica Particles] By adding (blending) silica particles to the radiation-curable composition used in the present invention, curing shrinkage of the obtained cured film can be reduced. Here, the addition amount of the silica particles is not particularly limited, but is preferably, for example, in the range of 10 to 250 parts by weight, particularly 20 to 200 parts by weight, per 100 parts by weight of the component (A). And more preferably 30 to 150 parts by weight.

Types of Silica Particles The silica particles to be used may be particles containing silica as a main component, and may contain components other than silica.
Such components other than silica include alkali metal oxides, alkaline earth oxides, and Ti, Zr, Al,
Oxides such as B, Sn, and P can be given. Also,
The average particle diameter of the silica particles is preferably set to a value in the range of 0.001 to 20 μm, but in particular, from the viewpoint of forming a transparent cured film, the average particle diameter is preferably in the range of 0.001 to 0.2 μm. , And more preferably 0.0
The value is in the range of 01 to 0.01 μm.

The refractive index of the silica particles (at a temperature of 25 ° C.,
It is preferable to select the silica particles so that the difference between the Na-D line (hereinafter the same) and the refractive index of the radiation-curable composition is 0.02 (-) or less. By setting the refractive index difference to such a value, the transparency of the cured film can be further increased. Further, the specific surface area of the silica particles, 0.1
Preferably, the value is in the range of ３3000 m ² / g.
More preferably, the value is in the range of 10 to 1500 m ² / g. Furthermore, the shape of the silica particles is not particularly limited, but is preferably at least one shape selected from the group consisting of spherical, hollow, porous, rod-like, plate-like, fibrous and irregular shapes. However, from the viewpoint of better dispersibility, it is more preferable to use spherical silica particles. The method of using the silica particles is not particularly limited. For example, the silica particles can be used in a dry state, or can be used in a state of being dispersed in water or an organic solvent.

Further, a dispersion liquid of fine silica particles known in the industry as colloidal silica can also be used directly. And since a particularly high transparency is obtained, use of colloidal silica is preferred. Here, when the dispersing solvent of the colloidal silica is water, the hydrogen ion concentration is preferably a value within a range of 2 to 13 as a pH value, and more preferably a value within a range of 3 to 7. When the dispersion solvent of colloidal silica is an organic solvent, methanol, isopropyl alcohol, ethylene glycol, butanol, ethylene glycol monopropyl ether, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, dimethylformamide, etc. may be used as the organic solvent. It may be used, or may be used as a mixture with an organic solvent or water compatible with these. Preferred dispersion solvents include methanol, isopropyl alcohol, methyl ethyl ketone, xylene and the like.

Commercially available silica particles include, for example, colloidal silica such as methanol silica sol, IPA-ST, MEK-ST, and NBA-S.
T, XBA-ST, DMAC-ST, ST-UP, ST
-OUP, ST-20, ST-40, ST-C, ST-
N, ST-O, ST-50, ST-OL (all manufactured by Nissan Chemical Industries, Ltd.) and the like. As powdered silica, AEROSIL130, AEROSIL
300, AEROSIL380, AEROSILTT6
00, AEROSILOX50 (all manufactured by Nippon Aerosil Co., Ltd.), Sildex H31, H32, H51, H
52, H121, H122 (all manufactured by Asahi Glass Co., Ltd.),
E220A, E220 (Nippon Silica Industry Co., Ltd.)
SYLYSIA470 (Fuji Silysia Ltd.)
And SG flakes (manufactured by Nippon Sheet Glass Co., Ltd.).

[Organic Solvent] The radiation-curable composition used in the present invention may optionally contain an organic solvent. Such an organic solvent may be added when producing a hydrolyzate or condensate of the hydrolyzable silane compound as the component (A), or may be added when the components (A) to (C) are blended. Is also good.

Such an organic solvent can be selected within a range that does not impair the objects and effects of the present invention. Usually, an organic compound having a boiling point at atmospheric pressure within a range of 50 to 200 ° C. And an organic compound that uniformly dissolves each component is preferable. Preferred organic solvents include alcohols such as methanol, ethanol, propanol and butanol, dibutyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, propylene glycol methyl ether acetate,
Ethers such as propylene glycol ethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, tetrahydrofuran, and dioxane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and methyl amyl ketone; ethyl acetate; butyl acetate; Amyl acetate, ethyl lactate, ethyl 2-hydroxypropionate,
Esters such as γ-butyrolactone, and aromatic hydrocarbons such as benzene, toluene and xylene. These can be used alone or in combination of two or more. Among these, more preferable organic solvents include alcohols, ethers, and ketones. More preferred are alcohols and ketones.

In the present invention, in particular, it is preferable to use a spin coating method for applying the radiation-curable composition. Glycol ethers such as ethyl ether and propylene glycol monomethyl ether; ethyl cellosolve acetate, propylene glycol methyl ether acetate;
Ethylene glycol alkyl ether acetates such as propylene glycol ethyl ether acetate; esters such as ethyl lactate and ethyl 2-hydroxypropionate; diethylene glycol monomethyl ether;
It is preferable to use diethylene glycols such as diethylene glycol dimethyl ether and diethylene glycol ethyl methyl ether; ketones such as methyl isobutyl ketone, 2-heptanone, cyclohexanone, and methyl amyl ketone, and in particular, ethyl cellosolve acetate, propylene glycol methyl ether acetate,
Ethyl lactate, methyl isobutyl ketone and methyl amyl ketone are preferred.

[Others] The radiation-curable composition used in the present invention may further contain various additives as necessary. Examples of such additives include epoxy resin, acrylic resin, polyamide resin, polyamideimide resin, polyurethane resin, polybutadiene resin, polychloroprene resin, polyether resin, polyester resin, styrene-butadiene block copolymer, petroleum resin, xylene Organic resins (polymers) or oligomers such as resins, ketone resins, cellulose resins, fluoropolymers, silicone polymers, and polysulfide polymers, or compounds in which these organic resins or oligomers are substituted with hydrolyzable silyl groups. . Further, as other additives, phenothiazine, 2,6-
Polymerization inhibitors such as di-t-butyl-4-methylphenol; polymerization initiation aids; leveling agents; wettability improvers; surfactants; plasticizers; ultraviolet absorbers; antioxidants; Ring agents; inorganic fillers and the like can also be mentioned.

[Preparation and Properties of Radiation-Curable Composition]
The radiation-curable composition for forming the lower clad layer, the core portion and the upper clad layer constituting the optical waveguide, that is, the lower layer composition, the core composition and the upper layer composition are respectively the above-described hydrolyzable It can be produced by mixing and stirring a silane compound, a dehydrating agent and the like according to a conventional method. The lower layer composition, the core composition, and the upper layer composition each have a different radiation index so that the refractive index relationship of each part finally obtained satisfies the condition required for the optical waveguide. Although a curable composition can be used, the composition for the lower layer and the composition for the upper layer may be the same radiation curable composition, and it is generally preferable that the composition be the same from various points. .

The above-mentioned radiation-curable composition comprises the (A)
By selecting the type of the hydrolyzable silane compound and / or the hydrolyzate thereof as a component, a cured film having a different refractive index is formed. Therefore, two or three types of radiation-curable compositions having a difference in refractive index of an appropriate size are used, and a radiation-curable composition that gives a cured film having the highest refractive index is used as a core composition. May be used as the lower layer composition and the upper layer composition.

Each radiation-curable composition has a viscosity of 5 to 10
It is preferable that the value be in the range of 000 cps (25 ° C.). If the viscosity exceeds these ranges, it tends to be difficult to form a uniform coating film. In addition, the viscosity of the radiation-curable composition can be appropriately adjusted depending on the amount of the reactive diluent or the organic solvent.

As described above, in the present invention, by forming a lower cladding layer on a substrate, forming a core portion thereon, and further forming an upper cladding layer, a desired optical waveguide is formed. The cladding layer and the core portion are formed in common, in that a thin film is formed by applying and drying a radiation-curable composition, and curing is performed by irradiating the thin film with radiation. However, the formation of the core portion is different in that irradiation of radiation to the thin film is performed according to a predetermined pattern, and an operation of removing an uncured portion is performed.

Means for applying the radiation-curable composition include spin coating, dipping, spraying, bar coating, roll coating, curtain coating, gravure printing, silk screen printing, and ink jet printing. A method can be used. Of these, spin coating is particularly preferred. Further, in order to make the rheological properties of the radiation-curable composition suitable for actual application means, various leveling agents, thixotroping agents, fillers,
An organic solvent, a surfactant and the like can be blended as required.

The coating film formed by applying the radiation-curable composition is dried at a temperature of 50 to 90 ° C. or, if necessary, further heated to a temperature of 60 to 120 ° C. to form a thin film. Is done. The heating conditions for the prebaking vary depending on the type of each component of the radiation-curable composition to be used, the mixing ratio, and the like, but are usually 60 to 60%.
It is about 10 to 600 seconds at 120 ° C.

The formed thin film is cured by irradiating it with radiation. In forming the lower cladding layer and the upper cladding layer, the entire surface of the thin film is irradiated with radiation, and the whole is cured. Here, as radiation
Visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, γ-rays and the like can be used, but as described above, ultraviolet rays are particularly preferable. The means for irradiating ultraviolet rays is not particularly limited, and various means can be used. For example, as a light source, an ultraviolet light source lamp such as a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, and an excimer lamp can be used. The radiation applied to the thin film has a wavelength of 200 to 390 nm and an illuminance of 1 to 1.
It is preferable to irradiate 500 mW / cm ² for a predetermined time so that the irradiation amount is 10 to 5000 mJ / cm ² .

Irradiation of radiation to the core thin film for forming the core portion is performed according to a predetermined pattern.
Thereafter, by developing with a developer, uncured unnecessary portions are removed, thereby forming a core portion. The method of irradiating radiation according to a predetermined pattern is not limited to a method using a photomask having a mask hole of a predetermined pattern. A method of using a means for electro-optically forming a mask image composed of a radiation opaque region, using a light guide member formed by bundling a large number of optical fibers, and using an optical fiber corresponding to a predetermined pattern in the light guide member A method of irradiating a radiation or a method of irradiating a radiation-curable composition while scanning convergent radiation obtained by a laser beam or a converging optical system such as a lens or a mirror can also be used.

The thin film selectively cured according to the predetermined pattern in this manner is developed with an appropriate organic solvent or alkali developing solution by utilizing the difference in solubility between the cured portion and the uncured portion. By the treatment, the uncured portion can be removed and the cured portion can be left, thereby forming the core portion.

Here, as the developing solution, the organic solvents described above as those used for preparing the radiation-curable composition,
Or sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, N-methylpyrrolidone, dimethylethanol Amine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3. 0] -5
An alkaline aqueous solution composed of alkalis such as nonane can be used. The concentration of the alkali water-soluble is usually 0.1 to 2.5% by weight, preferably 0.2 to 0.5% by weight. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like to the alkaline aqueous solution can also be used as the developer.

The development time is usually from 30 to 180 seconds, and the development method may be any of a puddle method and a dipping method. When an organic solvent is used as a developing solution, the water on the surface is dried by air drying. By removing, a patterned film is formed. Subsequently, by a heating device such as a hot plate or an oven, at a predetermined temperature, for example, 150 to 250 ° C., for a predetermined time, for example, 5 to 30 minutes on a hot plate, and 30 minutes in an oven.
By performing the heat treatment for 90 minutes, a core portion composed of a patterned crosslinked film is formed.

The cured film obtained by irradiation with radiation can be further heated, if necessary. The heating in this case may be performed at a temperature from room temperature to a temperature not higher than the decomposition start temperature of the substrate or the thin film, for example, for 5 minutes to 72 hours. As described above, by further heating after radiation curing, a core portion excellent in hardness and heat resistance can be obtained. Thereafter, the heating can be performed also in the formation of the lower clad layer and the upper clad layer. As described above, the finely patterned core portion is formed in a state of being embedded in the lower clad layer and the upper clad layer stacked thereon, whereby an optical waveguide is obtained.

According to the present invention, since a radiation-curable composition containing a specific hydrolyzable silane compound and / or a hydrolyzate thereof is used to form a core portion, The core can be formed very easily and in a short time by irradiating radiation according to the pattern described above, and the obtained core has high transparency because it is mainly composed of polysiloxane. Thus, the obtained optical waveguide has small waveguide loss and high heat resistance.

Further, the lower cladding layer and the upper cladding layer can also be formed of a radiation-curable composition having the same composition as the composition for the above-mentioned core portion, in which case it is required. Since the operation is only application of the radiation-curable composition and irradiation of radiation,
As a coating device, a radiation irradiating device, and other processing devices, those used for forming the core portion can be used as they are, and as a result, as a whole, the target light guide can be formed very simply and at very low cost. Waveguides can be manufactured.

[0114]

(Preparation of polysiloxane solution)

Polysiloxane solution 1 In a container equipped with a stirrer, phenyltrimethoxysilane (2
3.3 g (0.12 mol), methyltrimethoxysilane (61.6 g, 0.43 mol) and an electric conductivity of 8 ×
10 ⁻⁵ S · cm ⁻¹ ion-exchanged water (15.7 g, 0.8
7 mol), and heated and stirred at a temperature of 60 ° C. for 6 hours to hydrolyze phenyltrimethoxysilane and methyltrimethoxysilane. Next, methanol by-produced by hydrolysis was removed by distillation while methyl isobutyl ketone (MIBK) was added dropwise. Then, finally, a methyl isobutyl ketone solution containing polysiloxane whose solid content was adjusted to 40% by weight was obtained. This is designated as “polysiloxane solution 1”.

Polysiloxane solution 2 In a vessel equipped with a stirrer, methyltrimethoxysilane (8
0.0g, 0.558 mol) and an electric conductivity of 8 × 10
^-5 S · cm ⁻¹ ion-exchanged water (16.0 g, 0.889)
), And the mixture was heated and stirred at a temperature of 60 ° C for 6 hours to hydrolyze methyltrimethoxysilane. While dropping MIBK, methanol by-produced by hydrolysis was removed by distillation. Then, finally, a methyl isobutyl ketone solution containing polysiloxane whose solid content was adjusted to 40% by weight was obtained. This is designated as “polysiloxane solution 2”.

[Preparation of Radiation-Curable Composition] Radiation-curable composition A (composition for core) 100 parts by weight of polysiloxane solution 1 (solid content and solvent) were mixed with a photoacid generator (CD101, manufactured by Sartomer Co., Ltd.).
2) and 3.0 parts by weight of methyl orthoformate as a dehydrating agent were added, and the mixture was uniformly mixed to obtain a radiation-curable composition A. Radiation-curable composition B (composition for lower layer and composition for upper layer) To 100 parts by weight of polysiloxane solution 2 (solid content and solvent), a photoacid generator (CD101, manufactured by Sartomer Co., Ltd.)
2) was added, and 3.0 parts by weight of methyl orthoformate were added as dehydrating agents, respectively, and uniformly mixed to obtain a radiation-curable composition B.

Example 1 The radiation-curable composition B was applied on the surface of a silicon substrate by a spin coater and heated at 70 ° C. for 1 hour.
After drying for 0 minutes, wavelength 365nm, illuminance 200mW
/ Cm ² for 5 seconds.
A lower cladding layer of 0 μm was formed. The refractive index of light having a wavelength of 1550 nm of the lower cladding layer was 1.423. Next, the radiation-curable composition A was applied on the lower clad layer by a spin coater, dried at 70 ° C. for 10 minutes, and then, using a photomask engraved with an optical waveguide pattern having a width of 4 to 20 μm, using a photomask having a wavelength of 365 nm. , Illuminance 200mW / c
Exposure was performed by irradiating ultraviolet rays of m ² for 5 seconds. Thereafter, the substrate was immersed in a developing solution composed of ethanol to dissolve the unexposed portions, thereby forming a 7 μm thick core portion. The refractive index of light having a wavelength of 1550 nm in the core portion was 1.452. Further, the radiation curable composition B is applied to the upper surface of the lower clad layer having the core portion by a spin coater, dried at 70 ° C. for 10 minutes, and then irradiated with ultraviolet rays having a wavelength of 365 nm and an illuminance of 200 mW / cm ² for 5 seconds. As a result, an upper cladding layer having a thickness of 15 μm was formed, and thus, an optical waveguide was manufactured. The refractive index of light having a wavelength of 1550 nm of the formed upper cladding layer was 1.423.

For the optical waveguide thus obtained, the amount of light emitted from one end of the waveguide when light having a wavelength of 1300 nm is incident from one end of the waveguide is measured.
When the waveguide loss was determined, it was 0.1 dB / cm or less. Further, after the obtained optical waveguide was heated at 150 ° C. for 5000 hours, the waveguide loss was measured in the same manner as described above. As a result, it was 0.1 dB / cm or less. It was confirmed to have.

[0119]

As described above, according to the present invention, an optical waveguide having a low waveguide loss for light in the visible region to the infrared region and having excellent heat resistance can be manufactured in a short time and with a simple process. The present invention provides an optical waveguide manufactured by the method and suitable for an optical communication system or the like.

[Brief description of the drawings]

FIG. 1 is an explanatory sectional view showing a basic configuration of an optical waveguide manufactured by a method of the present invention.

FIGS. 2A to 2E are cross-sectional views illustrating an example of a method for manufacturing an optical waveguide of the present invention in the order of steps.

DESCRIPTION OF SYMBOLS 10 Optical waveguide 12 Substrate 13 Lower cladding layer 15 Core part 14 Core thin film 17 Upper cladding layer 18 Photomask

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Hozumi Sato 2--11-24 Tsukiji, Chuo-ku, Tokyo JSR Co., Ltd. F-term (reference) 2H047 KA04 PA02 PA13 PA21 PA22 PA24 PA28 QA05 TA35 TA36 TA43 4J035 BA01 BA11 CA13N CA131 CA14N CA141 EA01 EB02 LA03 LB17 4J038 DL051 DL071 DL081 HA216 HA446 HA556 JA29 JA31 JA33 JA42 JA56 JA59 JB15 JC01 JC19 JC20 JC37 JC38 KA02 KA04 KA11 KA20 NA17 PA17 PB08 PB09 PB11

Claims (6)

[Claims] A substrate, a lower cladding layer formed on the substrate, a core portion formed on the lower cladding layer, and an upper cladding layer formed on the core portion and the lower cladding layer. A method of manufacturing an optical waveguide, comprising forming at least one of a lower clad layer, a core portion, and an upper clad layer by means including applying a radiation-curable composition and curing the composition by irradiation with radiation. A method for manufacturing an optical waveguide. 2. A thin film obtained by applying a radiation-curable composition for forming a core portion is irradiated with radiation in accordance with a predetermined pattern, and then the unexposed portion is removed to form the core portion. The method for manufacturing an optical waveguide according to claim 1, wherein: 3. The radiation-curable composition for forming a core portion has a refractive index of a core portion formed thereby.
The method according to claim 1 or 2, wherein the radiation-curable composition is a radiation-curable composition having a refractive index higher than that of the lower clad layer and the upper clad layer. 4. The radiation curable composition for forming the lower clad layer, the core portion and the upper clad layer contains the following components (A) to (C). A method for manufacturing the optical waveguide according to any one of the above. (A) at least one compound selected from the group consisting of a hydrolyzable silane compound represented by the general formula (1), a hydrolyzate thereof and a condensate thereof; a general formula (1) (R ¹ ) _p Si (X) _{4 -p} [wherein, R ¹ is a non-hydrolyzable organic group having 1 to 12 carbon atoms, X is a hydrolyzable group, and p is an integer of 0 to 3. (B) Photoacid generator (C) Dehydrating agent 5. The method according to claim 4, wherein R ¹ in the general formula (1) has a radical polymerizable group or a cationic polymerizable group. 6. An optical waveguide manufactured by the method according to claim 1. Description: