JP2003185863A - Photocuring composition for formation of optical waveguide, method for forming optical waveguide and optical waveguide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a photocuring composition for the formation of an optical waveguide which contains polysiloxane having a photo-sensitizing group and a photoacid generating agent, which has high sensitivity for an all-purpose light source and favorable storage stability and with which a pattern with high accuracy can be formed and an optical waveguide having favorable optical characteristics can be formed, to obtain a method for manufacturing an optical waveguide by using the above composition, and to obtain the optical waveguide. <P>SOLUTION: The photocuring composition for the formation of an optical waveguide contains (A) polysiloxane having a photo-sensitizing group and (B) a photoacid generating agent. <P>COPYRIGHT: (C)2003,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photocurable composition for forming an optical waveguide, an optical waveguide using the same, and a method for forming an optical waveguide. More specifically, storage stability that can form a highly accurate pattern with high sensitivity to a general-purpose light source containing a polysiloxane containing a photosensitizing group and a photoacid generator, and has good optical characteristics, and storage stability. The present invention relates to a photocurable composition for forming an optical waveguide, which has a good value, a method for producing an optical waveguide using the same, and an optical waveguide.

[0002]

2. Description of the Related Art In the era of multimedia, optical waveguides have attracted attention as optical transmission media due to demands for large-capacity and high-speed information processing in optical communication systems and computers. Optical waveguides used for such purposes are:
In addition to good optical characteristics such as transmission loss, its performance is stable for a long time without affecting the external environment.
It is desired that the optical waveguide having a fine and complicated shape be manufactured with a low energy, a short time, and a small number of steps without causing environmental pollution. A typical example of such an optical waveguide is a silica-based waveguide, which is generally manufactured by the following steps. A lower cladding layer made of a glass film is formed on a silicon substrate by a technique such as a flame deposition method (FHD) or a CVD method. An inorganic thin film having a different refractive index from the lower clad layer is formed on the lower clad layer, and the thin film is patterned by using a reactive ion etching (RIE) to form a core portion. Further, an upper clad layer is formed by a flame deposition method.

However, such a method of manufacturing a silica-based waveguide is said to have good optical characteristics and durability, but requires special equipment for the manufacture, and requires many complicated steps. Problems such as a long manufacturing time and a low yield were observed. A technique using a photosensitive optical waveguide material has been disclosed for the purpose of shortening the manufacturing time of the optical waveguide, reducing the number of steps, and improving the yield. For example, in JP-A-10-254140, a condensate of a hydrolyzable silane, a photocurable composition comprising a photoacid generator and a dehydrating agent, and in JP2000-180643, a silane compound containing an epoxy group, an organic oligomer , A photosensitive composition comprising a polymerization initiator, JP-A-2001-288364 discloses a radiation-curable composition comprising a condensate of a hydrolyzable silane, a photoacid generator, and a basic acid diffusion controller. . These technologies disclose that the use of a photosensitive composition enhances the productivity of optical waveguides and enables high-precision pattern formation. However, it is not sufficient to meet the demand for increasing the productivity by increasing the sensitivity to general-purpose light sources that emit light having a wavelength of 360 nm or more at high illuminance.
In other words, a photoacid generator with high sensitivity to such a general-purpose light source is easily decomposed by exposure to light such as sunlight or fluorescent light at the same time, so it is difficult to handle, and is added when the pattern accuracy of an acid diffusion control agent or the like is increased. However, there is a problem that it is thermally unstable in the coexistence of the basic substance. The use of a photoacid generator in combination with a sensitizer in order to achieve both sensitivity, stability and ease of handling is disclosed, for example, in Examples of JP-A-2001-288364. However, the condensed aromatic compound used as a photosensitizer has low solubility in general-purpose organic solvents such as alcohols. Therefore, when the amount of addition is increased, the condensed aromatic compound precipitates in the composition and deteriorates the optical characteristics of the optical waveguide. . Further, there is a problem that the sensitivity is low with a small amount of addition. That is, at present, the improvement of sensitivity by adding a photosensitizer is limited.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has been disclosed in the prior art, and includes hydrolyzable silane condensate, photoacid generator, and acid diffusion control. A photocurable composition for forming an optical waveguide composed of a photosensitizer and a photosensitizer, using a photoacid generator that is easy to handle, has high sensitivity to general-purpose light sources, and has high pattern accuracy, optical characteristics, and storage. An object is to provide a photocurable composition for forming an optical waveguide having good stability, an optical waveguide using the same, and a method for producing the same.

[0005]

Means for Solving the Problems A photocurable composition for forming an optical waveguide, an optical waveguide using the same and an optical waveguide using the same, shown in the present invention, which have been studied diligently to solve the above-mentioned problems of the prior art. Invented a method.

The components and embodiments of the present invention will be specifically described below with reference to the drawings as needed. (A) of the present invention
A photocurable composition for forming an optical waveguide, comprising a polysiloxane having a photosensitizing group and (B) a photoacid generator. The photosensitizing group in the polysiloxane containing the photosensitizing group of the component (A) has the function of expanding the wavelength range of light that induces the photodecomposition reaction of the photoacid generator and increasing the decomposition efficiency. Is a multivalent organic compound, and is characterized by being bonded to polysiloxane by a covalent bond. The structure of the photosensitizing group is not particularly limited as long as it meets this purpose, but when a photoacid generator having a light absorption maximum at a wavelength of 300 nm or less is used, photodecomposition to light having a wavelength of 300 nm or more is performed. Since the efficiency is reduced, it is selected from organic groups having absorption at a wavelength of 300 nm or more. An example of the structural characteristics of an organic group having an absorption at a wavelength of 300 nm or more is a condensed aromatic group. The condensed aromatic group may have a hetero atom such as oxygen, sulfur, nitrogen, phosphorus, and halogen (fluorine, chlorine, bromine, iodine). The absorbance of the photosensitizing group at a wavelength of 300 nm or more can be defined by the molar extinction coefficient when the sample concentration is measured at mol / liter and the cell length is 1 cm, and the preferred molar extinction coefficient is 100. If it is less than 10, the molar extinction coefficient of the photosensitizing group is preferably 1,000 or more, more preferably 10,000 or more, because the sensitizing effect is small.
The content of the photosensitizing group is 0.00 with respect to 100 parts by weight of the component (A).
01 to 1 part by weight, preferably 0.001 to 0.1 part. The photosensitizing group can be selected from the following monovalent organic groups excluding the hydrogen atom of the parent compound having absorption at a wavelength of 300 nm or more.

Specific examples of the parent compound having absorption at a wavelength of 300 nm or more include anthracene, cyanoanthracene, bromoanthracene, chloranthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, and vinyl anthracene. Anthracenes, anthraquinone, 2-hydroxymethylanthraquinone, ethylanthraquinone, vinylanthraquinone, anthraquinones such as thioxanthone, chlorothioxanthone, diethylthioxanthone, isopropylthioxanthone, thioxanthone, hydroxymethylthioxanthone, vinylthioxanthone, thioxanthones such as benzophenone, Methyl orthobenzoyl benzoate, [4- (methylphenylthio) phenyl] phenylmethane, 4, 4 Benzophenones such as' -bisdiethylaminobenzophenone, 4-benzoylbiphenyl, 1,4-dibenzoylbenzene, etc .; naphthalenes such as benzyl, naphthalene, hydroxymethylnaphthalene, benzoylnaphthalene, vinylnaphthalene, etc., and 10-butyl-2-chloroacrylic Don, acridone, acridones such as hydroxymethylacridone, biphenyl, terphenyl, hydroxymethylbiphenyl, polyphenylenes such as vinylbiphenyl, perylene, hydroxymethylperylene, methylperylene,
Coumarins such as perylenes, 6-methylcoumarin, diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin, coumarin, etc., ethyl dimethylaminobenzoate, isoamyl dimethylaminobenzoate,
Aminobenzoic acid esters such as acridine, 1,7
Acridines such as -diacridylheptane, 9-hydroxy-4-methoxyacridine, N-octyl-bis (α-morphonyldimethylacetyl) carbazole,
Examples thereof include carbazoles such as ethyl carbazole, methyl carbazole, hydroxymethyl carbazole, and vinyl carbazole. Among these, preferred compounds are anthracenes, thioxanthones, benzophenones, and carbazoles.

The method of chemically bonding the photosensitizing group to the polysiloxane is not particularly limited, but specific examples include the following methods 1) to 4). 1) A method in which a hydroxy-substituted photosensitizer and a hydrolyzable silane compound as a raw material of a polysiloxane are mixed, then hydrolyzed and condensed. 2) A method in which a hydroxy-substituted photosensitizer is added to a polysiloxane having an alkoxy group or a hydroxyl group, followed by heating. 3) A method of mixing a photosensitizer having a hydrolyzable silyl group in a molecule with a hydrolyzable silane compound which is a raw material of polysiloxane, followed by hydrolysis and co-condensation. 4) a photosensitizer containing a vinyl group with respect to a polysiloxane having a hydrosilane (Si-H) bond in the molecule;
A method in which a hydrosilylation catalyst is mixed and produced by heating.

The production method of 1) is a method in which a hydroxy-substituted photosensitizer is present at the time of hydrolysis and condensation of a hydrolyzable silane compound to bond to a silicon atom as an alkoxy group. This is a production method characterized by substituting a hydroxyl group or an alkoxy group in the produced polysiloxane. In this production method, as in 1), the photosensitizing group is bonded to a silicon atom in the polysiloxane as an alkoxy group. Therefore, particularly in the production method 2), it is preferable to increase the reaction efficiency of the photosensitizing group by adding a catalyst effective as a transesterification catalyst. At that time, the reaction temperature is usually 20 to 200 ° C. under normal pressure, and then water and alcohols are removed by reduced pressure treatment, whereby the substitution of the photosensitizing group is carried out efficiently. As an example of the esterification catalyst, the same catalyst as the hydrolysis and condensation catalyst of a hydrolyzable silane compound described later can be used, but preferably, a metal alkoxide such as tetrabutoxyzirconium, tetrabutoxytitanium, or tributoxyaluminum is used. And organic metals such as dibutyltin dilaurate and butyltin oxide, and sulfonates such as sodium p-toluenesulfonate and sodium methanesulfonate.

Specific examples of the hydroxy-substituted photosensitizer used in the production methods 1) and 2) include 9-
Examples thereof include hydroxymethylanthracene, 2-hydroxymethylanthraquinone, hydroxymethylthioxanthone, hydroxymethylnaphthalene, hydroxymethylbiphenyl, 7-hydroxy-4-methylcoumarin, 9-hydroxy-4-methoxyacridine, and hydroxymethylcarbazole. Specific examples of the photosensitizer having a hydrolyzable silyl group in the molecule used in the production method 3) include 2-trimethoxysilylethylnaphthalene, 2-triethoxysilylethylnaphthalene, and 2-trimethoxysilylethylnaphthalene.
Trimethoxysilylethylbiphenyl, 2-trimethoxysilylethylanthracene, 2-triethoxysilylethylanthracene, 2-trimethoxysilylethylthioxanthone, 2-trimethoxysilylethylcarbazole, 2-triethoxysilylethylcarbazole, 2
-Trichlorosilylethylcarbazole and the like. These silane compounds can be produced by a hydrosilylation reaction of a corresponding vinyl compound with an alkoxysilane or chlorosilane having a Si—H group. Examples of the photosensitizer having a vinyl group used in 4) include vinyl anthracene, vinyl anthraquinone, vinyl thioxanthone, vinyl biphenyl, vinyl naphthalene, and vinyl carbazole.

The polysiloxane containing a photosensitizing group as the component (A) contains any one of the following structural units (1) to (3) as a component other than the photosensitizing group, and is bonded to a silicon atom. Selected from polysiloxanes containing hydroxyl and / or alkoxy groups.

(1)

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(2)

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(3)

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In the structural units (1) to (3), R ¹ , R ² , R
³ is a monovalent organic group, which may be the same or different and is selected from non-hydrolyzable cyclic, branched and straight-chain alkyl, aryl and aralkyl groups having 1 to 12 carbon atoms. Part or all of the hydrogen atoms on R ¹ , R ² and R ³ may be substituted with deuterium, fluorine or chlorine. R ¹ , R ² , R ³
Illustrative examples of the alkyl group include methyl, ethyl, propyl, butyl, octyl, dodecyl, and their deuterium substitutes, and the aryl group is phenyl, biphenyl, naphthyl, and their deuterium, fluorine,
Chloride aralkyl groups include tolyl, xylyl, mesityl, and the deuterium, fluorine, and chlorides thereof. Preferred alkyl groups are methyl group, 3,3,3-trifluoropropyl and trideuteriomethyl, preferred aryl groups are phenyl, pentafluorophenyl and pentadeuteriophenyl, and preferred aralkyl groups are trifluoromethylphenyl , Bis (trifluoromethyl) phenyl.

The structural unit (1) in the component (A),
The ratio of (2) to (3) is 0 to 100 for the structural unit (1) and 0 for the structural unit (3) when the structural unit (2) is 100 mol.
~ 50 is selected.

The hydroxyl group and the alkoxy group bonded to the silicon atom have a structure in which part or all of the oxygen atom terminals in the structural units (1) to (3) are bonded by a hydrogen atom or an alkyl group, an aryl group or an aralkyl group. (A) It is contained in the component. The content of the hydroxyl group is 0 to 7 in 100 parts by weight of the component (A).
0 parts by weight, preferably 0.1 to 40 parts by weight, more preferably 1 to 10 parts by weight. The content of the alkoxy group,
It is 0 to 90 parts by weight, 0.1 to 30 parts by weight, more preferably 1 to 15 parts by weight based on 100 parts by weight of the component (A).

The polysiloxane containing a photosensitizing group has a weight average molecular weight in terms of polystyrene determined by gel permeation chromatography (hereinafter abbreviated as GPC) of 50.
It is 0 to 50,000, preferably 1,000 to 10,000. If the weight average molecular weight is less than 500, the optical properties of the optical waveguide will decrease, and if it exceeds 50,000, the storage stability of the photocurable composition will decrease, which is not preferable.

Specific examples of the silane compound constituting the structural unit (1) in the component (A) include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetra (2-methacryloxyethoxy) silane, tetra ( 2-
Acryloxyethoxy) silane, tetrachlorosilane,
Preferred specific examples of tetraacetoxysilane, tetraaminosilane, and the main constituent component include tetramethoxysilane, tetraethoxysilane, and tetraacetoxysilane. Specific examples of the silane compound constituting the structural unit (2) in the component (A) include methyltrimethoxysilane, methyltrichlorosilane, methyldichlorosilane,
Methyldimethoxysilane, methyltriacetoxysilane, trideuteriomethyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane,
3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, benzyltrimethoxysilane, phenyltrimethoxysilane, phenylsilane, phenyltriacetoxysilane, phenyltriaminosilane, phenyltrimethoxysilane Chlorosilane, phenyltriethoxysilane, pentafluorophenyltrimethoxysilane, pentafluorophenyltrichlorosilane, pentadeuteriophenyltrimethoxysilane, pentadeuteriophenyltriacetoxysilane, pentadeuteriophenyltrichlorosilane, pentadeuteriophenyltriethoxysilane Silane, xylyltrimethoxysilane, trifluoromethylphenyltothimethoxysilane, biphenyltrimethoxysilane, biphenyl Trichlorosilane, aminopropyltriethoxysilane, N- aminoethyl trimethoxy silane, glycidyl Giro trimethoxy silane,
There are methacryloxypropyltrimethoxysilane and the like, and preferable specific examples of the main components include methyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, and phenyltrimethoxysilane.

Specific examples of the silane compound constituting the structural unit (3) in the component (A) include bis (trideuteriomethyl) dimethoxysilane, dimethyldimethoxysilane, dimethyldichlorosilane, diphenyldimethoxysilane, and diphenyldimethoxysilane. Chlorosilane, and the like, and specific examples preferable as a main component are:
Examples thereof include dimethyldimethoxysilane and diphenyldimethoxysilane.

Other examples of the hydrolyzable silane that can constitute the component (A) include, for example, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-aminoethylpropyltrimethoxysilane,
3- (N-allylamino) propyltrimethoxysilane, 4-aminobutyltriethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N
-(2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (6-aminohexyl) aminopropyltrimethoxysilane, 3- (m-aminophenoxy) propyltrimethoxysilane, m-aminophenyltrimethoxysilane , P-aminophenyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane,
Bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, 3-dimethylaminopropyldiethoxymethylsilane, (N, N-dimethylaminopropyl)
Hydrogen in which an amino group such as trimethoxysilane, 3-morpholinopropyltrimethoxysilane, 2- (trimethoxysilylethyl) pyridine, (3-trimethoxysilylpropyl) diethylenetriamine is bonded to a silicon atom via an alkylene Degradable silane compounds, bis (diethylamino) dimethylsilane, bis (dimethylamino) diethylsilane, bis (dimethylamino) dimethylsilane, bis (dimethylamino) diphenylsilane,
Bis (dimethylamino) methylsilane, bis (dimethylamino) vinylethylsilane, bis (dimethylamino)
Vinylmethylsilane, bis (ethylamino) dimethylsilane, bis (ethylmethylketoxime) methylisopropoxysilane, methyltris (methylethylketoxime) silane, tetrakis (diethylamino) silane, tetrakis (dimethylamino) silane, tris (dimethylamino) methylsilane , A hydrolyzable silane compound in which an amino group such as tris (dimethylamino) phenylsilane is directly bonded to a silicon atom, an acrylic-substituted silane such as methacryloxypropyltrimethoxysilane, glycidyloxypropyltrimethoxysilane, 2- Epoxy-functional silane compounds such as trimethoxysilylethylcyclohexene oxide can be mentioned.

The conditions for hydrolyzing and condensing the hydrolyzable silane compound as the component (A) are as follows. When the hydrolyzable group is an alkoxy group, an alcohol is by-produced by hydrolysis. It can be implemented without. On the other hand, when the hydrolyzable group is a halogen group or the like, since a by-product serving as a diluting solvent is not generated and an acid serving as a catalyst is produced as a by-product, the hydrolysis is performed in a state where an organic solvent is previously added and diluted. It is desirable to carry out a condensation reaction. In that case, when a photocurable composition for forming an optical waveguide is prepared in a state where a large amount of acid is left, storage stability is reduced,
For example, it is preferable to form a stable photocurable composition by adding a step of washing or removing a generated salt by adding an ion exchange resin after neutralization with a basic substance.

The hydrolysis and condensation steps of a silane compound when the hydrolyzable group is an alkoxy group will be described below as an example. That is, it is performed by the following steps 1) to 4). 1) The hydrolyzable silane compound is contained in a container. 2) Next, a predetermined amount of water and a catalyst are added dropwise with stirring. 3) Then, the mixture is heated and stirred at a predetermined temperature for a predetermined time. 4) Dilute by adding a predetermined solvent.

The temperature in the above step 1) is usually 0 ° C to 5 ° C.
The test is performed at 0 ° C. in a dry atmosphere. The step 2) is a step of starting hydrolysis of the hydrolyzable silane, and is performed at the same temperature as the step 1) under a dry atmosphere. When the amount of water to be added is P moles and the number of moles of the total hydrolyzable groups in the hydrolyzable silane compound is Q, if the P / Q ratio is too small, the yield and molecular weight of the hydrolysis and condensate decrease. As a result, the durability of the formed optical waveguide decreases. On the other hand, if the P / Q ratio is too large, the storage stability of the photocurable composition will decrease due to the molecular weight exceeding the appropriate range. For this reason, usually, 0.1 <P / Q <7, preferably 0.3 <P / Q <4,
More preferably, it is performed in the range of 0.3 <P / Q <2. The water to be added is usually ion-exchanged water or distilled water, but a catalyst may be added for the purpose of accelerating the reaction. The amount of the catalyst added is 0.00 0.00 parts by weight of the hydrolyzable silane (A).
The amount is from 01 to 10 parts by weight, preferably from 0.001 to 1 part by weight.

The method of adding the catalyst is not particularly limited, but it is preferably added as an aqueous solution. Catalysts include formic acid, acetic acid,
Oxalic acid, lactic acid, malonic acid, citric acid, tartaric acid, malic acid,
Succinic acid, fumaric acid, phthalic acid, pyromellitic acid, p-
1 such as toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, etc.
, Divalent, trivalent organic acids, inorganic acids such as hydrochloric acid, phosphoric acid, nitric acid, hydrofluoric acid, bromic acid, chloric acid, perchloric acid, and hydroxides of alkali metals and alkaline earths in the periodic table Hydroxides and carbonates of quaternary alkylammoniums; alkalis such as primary to tertiary amines; acidic salts such as ammonium chloride, tetramethylammonium chloride, tetrabutylammonium bromide and tetrabutylammonium sulfonate; Sodium acid, basic salts, tin, zirconium, titanium, aluminum, metal alkoxides other than silicon such as boron and their chelate complexes, etc., have a reaction promoting effect, but organic acids, inorganic acids, metal alkoxides, metal alkoxides Acid catalysts such as chelate compounds are preferred, and organic acids are particularly preferred.

The above step 3) is a step of carrying out hydrolysis and condensation of the hydrolyzable silane. The reaction is carried out at a temperature not higher than the boiling points of the silane compound, water and the alcohol by-produced by the hydrolysis. ℃ ~ 150 ℃, preferably 20 ℃ ~
It is performed at 100 ° C. in a dry atmosphere. The reaction time is usually 1 hour to 12 hours. In the above step 4), dilution or replacement with a predetermined solvent is performed, but it is preferable to perform replacement with a diluting solvent suitable for forming an optical waveguide at this stage. The diluting solvent is 10 to 10 parts by weight of the component (A).
1000 parts by weight, preferably 40 to 250 parts by weight are used. The method of solvent replacement is not particularly limited, and examples thereof include a method of performing distillation replacement under normal pressure and a method of performing distillation under reduced pressure. The diluting solvent can be selected from organic solvents capable of uniformly dissolving each component and forming a good optical waveguide.

As the type of the photoacid generator of the component (B), an onium salt (a first group of compounds) having a structure represented by the general formula (1) or a structure represented by the general formula (5) (A second group of compounds). Particularly effective compounds are the aromatic onium salts. For example, JP-A-50-151996 and JP-A-50-15
Aromatic halonium salts described in JP-A-8680 and JP-A-50-151997, JP-A-52-30899
JP, JP-A-56-55420, JP-A-55-55420
Group VIA aromatic onium salts described in JP-A-125105, and V-group aromatic onium salts described in JP-A-50-158699.
Group A aromatic onium salt, JP-A-56-8428,
JP-A-56-149402, JP-A-57-192
Oxosulfoxonium salts described in, for example, US Pat.
Preferred are aromatic diazonium salts described in JP-A-49-17040 and the like, and thiobrillium salts described in U.S. Pat. No. 4,139,655. Further, an iron / allene complex, an aluminum complex / photolytic silicon compound-based initiator and the like can also be mentioned.

[R ⁴ _a R ⁵ _b R ⁶ _c R ⁷ dW] ^{+ m} [MZ _{m + n} ] ^−m (4) [In the general formula (4), the cation is an onium ion;
W is S, Se, Te, P, As, Sb, Bi, O, I, Br, Cl or a ^{-N≡N,, R 4, R 5} , R 6, R 7 are the same or different organic groups A, b, c, and d are each an integer of 0 to 3, and (a + b + c + d) is equal to the valence of W. Also, M
Is a metal or metalloid constituting the central atom of the halide complex [MZ _{m + n} ], for example, B, P, As, Sb,
Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co
It is. Z is, for example, a halogen atom or an aryl group such as F, Cl, Br, etc., m is the net charge of the halide complex ion, and n is the valence of M]

Q _S- [S (= O) ₂ -R ⁸ ] _t (5) [In the general formula (5), Q is a monovalent or divalent organic group, R ⁸
Is a monovalent organic group having 1 to 12 carbon atoms, the subscript s is 0 or 1, and the subscript t is 1 or 2.]

First, onium salts, which are the first group of compounds, are compounds that can release an acidic active substance upon receiving light. Here, [MZ in the general formula (5)
_{m + n} ] as tetrafluoroborate (B
F ₄ ^over), hexafluorophosphate (PF ₆ ^{chromatography),} hexafluoroantimonate (Sb ₆ ^{chromatography),} hexafluoroarsenate (AsF ₆ ^{chromatography),} among such onium salts,
Component (B) and then hexachloroantimonate (SbCl ₆ ^over),
Tetraphenylborate (BPh ₄ ^over), tetrakis (trifluoromethylphenyl) borate [B (CF3-P
h) ₄ ^over, and the like pentakis (pentafluorophenyl) borate (B (C6 F5) ₄ ^over). Further, instead of the anion [MZ _{m + n} ] used in the general formula (4),
The anion represented by the general formula (MZ _n OH ^{chromatography)} may be used. Furthermore, valent chlorate ion (ClO ₄ ―), trifluoromethane sulfonate ion (CF ₃ SO ₃ ^ー ), fluorosulfonic acid (FSO ₃ ^ー ), toluene sulfonate ion, trinitrobenzene sulfonate ion, trinitrotoluene sulfonate ion Onium salts having other anions such as, for example, can also be used. Next, the second group of compounds will be described. Examples of the sulfonic acid derivative represented by the general formula (5) include disulfonic acids,
Disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzoylmethanes, imidosulfonates, benzoinsulfonates, sulfonates of 1-oxy-2-hydroxy-3-propyl alcohol, pyrogrol trisulfonates, Benzyl sulfonates can be mentioned. Further, among the sulfonic acid derivatives represented by the general formula (5), imide sulfonates are more preferable, and trifluoromethane sulfonate derivatives are more preferable.

Commercially available compounds which can be suitably used as a photoacid generator include UVI-6950 and UVI-697.
0, UVI-6974, UVI-6990 (all manufactured by Union Carbide), Adeka Optomer SP-15
0, SP-151, SP-170, SP-171, SP
-172 (manufactured by Asahi Denka Kogyo KK), Irgaccu
re 261 (all manufactured by Ciba Specialty Chemicals Co., Ltd.), CI-2481, CI-2624, C
I-2639, CI-2064 (Nippon Soda Co., Ltd.
Manufactured), CD-1010, CD-1011, CD-101
2, KI85 (all manufactured by Sartomer), DS-10
0, DS-101, DAM-101, DAM-10
2. DAM-105, DAM-201, DSM-30
1, DTS-103, NAI-100, NAI-10
1, NAI-105, NAI-106, PAI-101,
SI-100, SI-101, SI-105, SI-1
06, PI-105, NDI-105, BENZOIN TOSYLAT
E, MBZ-101, MBZ-301, PYR-10
0, PYR-200, DNB-101, NB-101, N
B-201, NDS-103, NAT-103, NAT-
105, NDS-103, NDS-105, NDS-
155, NDS-165, CMS-105, TPS-
102, TPS-103, TPS-105, MDS-1
03, MDS-105, MDS-205, MDS-30
5, DTS-103, MPI-103, BBI-10
1, BBI-102, BBI-103, BBI-105,
BBI-106, BBI-109, BBI-201, D
PI-105, DPI-109, DPI-201, MPI
-103, MPI-105, MPI-106, MPI-
109 (all manufactured by Midori Kagaku Co., Ltd.), PCI-061
T, PCI-062T, PCI-020T, PCI-0
22T (all manufactured by Nippon Kayaku Co., Ltd.), IBPF and IBCF (all manufactured by Sanwa Chemical Co., Ltd.). Of these, more preferred photoacid generators include those having a wavelength of 20
An onium salt photoacid generator, which is a first group of compounds having an absorption maximum of 0 nm or more at 360 nm or less, may be mentioned. The photoacid generator is added in an amount of 0.01 to 100 parts by weight of the component (A).
To 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.1 to 1 part. If the amount is less than 0.01 part by weight, the photocurability becomes insufficient, and if the amount exceeds 10 parts by weight, the optical characteristics as an optical waveguide deteriorate.

The photocurable composition for forming an optical waveguide of the present invention may contain the following components (C) to (I) in addition to the above components (A) and (B). Hereinafter, these will be described. (C) Acid Diffusion Control Agent The acid diffusion control agent of the component (C) controls the diffusion of the acidic active substance generated from the photoacid generator by light irradiation in the coating, and suppresses the curing reaction in the non-irradiated area. Is defined as a compound having However, in order to distinguish it from the photoacid generator by definition, the acid diffusion controller of the component (C) is a compound having no acid generating function. By adding such an acid diffusion controlling agent, the photocurable composition can be effectively cured, and the pattern accuracy can be improved.

(1) As the acid diffusion controlling agent of the type (C), a nitrogen-containing organic compound whose basicity is not changed by exposure or heat treatment during the formation step is preferable. As such nitrogen-containing organic compounds,
For example, a compound represented by the following general formula (6) (hereinafter, referred to as “nitrogen-containing compound (I)”) may be mentioned. NR ⁹ R ¹⁰ R ¹¹ (6) [In the general formula (6), R 9, R 10 and R 11 are mutually independent and represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or Represents a substituted or unsubstituted aralkyl group. ]

Examples of the other nitrogen-containing organic compound include a diamino compound having two nitrogen atoms in the same molecule (hereinafter referred to as "nitrogen-containing compound (II)") and a diamino compound having three or more nitrogen atoms. Examples thereof include polymers (hereinafter, referred to as “nitrogen-containing compound (III)”), amide group-containing compounds, urea compounds, and nitrogen-containing heterocyclic compounds. Here, as the nitrogen-containing compound (I), n-
Monoalkylamines such as hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine; di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n Dialkylamines such as heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine;
Triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-nonylamine Trialkylamines such as -n-decylamine; aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine , Aromatic amines such as 1-naphthylamine; ethanolamine, diethanolamine,
Alkanolamines such as triethanolamine and the like can be mentioned.

Examples of the nitrogen-containing compound (II) include, for example, ethylenediamine, N, N, N ', N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, N, N, N', N'- Tetrakis (2-hydroxyethyl) ethylenediamine, N, N,
N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 4,4'
-Diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2'-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4- Aminophenyl)-
2- (3-hydroxyphenyl) propane, 2- (4-
Aminophenyl) -2- (4-hydroxyphenyl) propane, 1,4-bis [1- (4-aminophenyl)-
1-methylethyl] benzene, 1,3-bis [1- (4
-Aminophenyl) -1-methylethyl] benzene and the like.

Examples of the nitrogen-containing compound (III) include polymers of polyethyleneimine, polyallylamine, and dimethylaminoethylacrylamide. Further, as the amide group-containing compound, for example,
Formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone and the like can be mentioned. Examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, and tributylthiourea. Can be mentioned.

Examples of the nitrogen-containing heterocyclic compound include, for example, imidazole, benzimidazole, 2-methylimidazole, 4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, and 4-methylimidazole.
Imidazoles such as 2-phenylimidazole; pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, Pyridines such as nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, acridine; pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, morpholine,
4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane and the like can be mentioned. Among these nitrogen-containing organic compounds, a nitrogen-containing compound (I), a nitrogen-containing heterocyclic compound and the like are preferable. Further, among the nitrogen-containing compounds (I), trialkylamines are particularly preferable, and among the nitrogen-containing heterocyclic compounds, pyridines are particularly preferable. The acid diffusion controller can be used alone or as a mixture of two or more.

(5) Addition Amount of the acid diffusion controller is preferably in the range of 0.001 to 15 parts by weight based on 100 parts by weight of component (A). The reason for this is that if the amount of the acid diffusion controller is less than 0.001 part by weight, the pattern shape and dimensional reproducibility of the optical waveguide may be reduced depending on the process conditions. If the amount of the control agent exceeds 15 parts by weight, the photocurability of the component (A) may decrease. Therefore, the addition amount of the acid diffusion controller is based on 100 parts by weight of the component (A).
The value is more preferably in the range of 0.001 to 10 parts by weight, and even more preferably in the range of 0.005 to 5 parts by weight.

(D) Surface tension-reducing agent The surface tension-reducing agent of the component (D) is used for the step of coating the photocurable composition of the present invention for repelling, unevenness,
It is added for the purpose of improving coating performance due to surface tension incompatibility such as undulation, and is selected from compounds having a function of reducing surface tension by adding a small amount. Such surface tension reducing agents can be selected from commercially available surfactants, leveling agents, defoamers, defoamers, foam stabilizers, and paint additives. The surface tension reducing agent is basically a compound containing both a polar group and a hydrophobic group. Structurally, silicone-based, organic-based, and fluorine-based products are commercially available, and these are classified into anionic, nonionic, cationic, and amphoteric, respectively, depending on the ionicity of the polar group. The surface tension-lowering agent can be selected from the compounds described above, but it has high compatibility with the polysiloxane containing a photosensitizing group, which is a main component of the present invention, and an effect can be obtained in a small amount. For this reason, silicone-based or fluorine-based surface tension reducing agents are preferred.

The silicone-based surface tension reducing agent is selected from polyether-modified silicones, polyester silicones, alkyl-modified silicones, acryl silicones, and the like. Silicone surface tension reducing agents are selected. In addition, the fluorine type is selected from fluoroalkyl silicones, fluoroalkyl carboxylic acids, fluoroalkyl alcohols, fluoroalkyl ethers, and fluoroalkyl quaternary ammonium salts. These may be used alone or in combination of two or more. The amount of the surface tension reducing agent is 0.1 to 0.00 parts by weight based on 100 parts by weight of the composition for forming an optical waveguide.
01 parts, preferably 0.1 to 0.001 part. Further, based on 100 parts by weight of the solid content after drying in the composition, 1 to 0.001 part,
Preferably it is 1 to 0.01 part. When the addition amount of the surface tension reducing agent is less than 0.0001, the homogeneity and the smoothness of the optical waveguide of the present invention may be reduced. On the other hand, when it exceeds 0.1, the durability of the optical waveguide is reduced.

The surface tension reducing agent may be added at any stage during the production of the composition of the present invention. It is preferably added after the production of the polysiloxane. The method of addition is not limited as long as the surface tension reducing agent is uniformly dissolved in the composition. However, the method of adding the compound after dilution with an organic solvent in advance is preferable because the time until uniformization can be shortened.

Examples of commercially available products include:
Dow Corning Silicone Co., Ltd.'s silicon-based product, SH20, which has been commercialized as a silicone paint additive
0, DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, S
H30PA, ST80PA, ST83PA, ST86PA, ST90PA, ST94PA, ST9
6PA, ST97PA, ST101PA, ST102PA, ST103PA, ST105PA, S
T110PA, SH550, SH710, etc., as well as SH200, FS1265, SH203, SD559 which have been commercialized as silicone defoamers
1, SH7PA, commercialized as silicone for cosmetics
SH3746, SH3771C, SH3772C, SH3773C, SH3775C, SH374
8, SH3749, and the like. In addition, BYK-300, BYK-301, BYK-335, and BYK-3, which are commercialized as silicone-based surface conditioners manufactured by BYK Japan KK
02, BYK-331, BYK-306, BYK-330, BYK-341, BYK-344, B
YK-307, BYK-332, BYK-333, BYK-310, BYK-077, BYK-315, which have been commercialized as silicone-based leveling agents
BYK-370, BYK-325, BYK-322, BYK-323, etc.BYK-370, B commercialized as reactive silicone surface conditioners
BYK-UV3500, BYK-UV3510, which have been commercialized as UV curable surface conditioners such as YK-371, BYK-373, and BYK-375
BYK-UV3530, and BYK-051 and BYK-0, which are commercialized as non-silicone defoamers for solvent-based and solvent-free paints
52, BYK-053, BYK-055, BYK-057, and the like. An example of a product that has been commercialized as a fluorine-based paint additive is Floren manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.
AC-300, Floren AC-900, Floren AO-3, Floren AKS, Flonon SB-110N, Flonon SB-210, Flonon SB-510, Flonon SB-551, EF-3 manufactured by Shin-Akita Chemical Co., Ltd.
05, EF-306A, etc., and those commercialized as surfactants include, for example, Kao Corporation's Emal 0, Emal AD-25R, Emal TD, Emal E-27C, Emal N
C-35, Reodol MS-50, Reodol SP-L10, Reodol AO-10, Reodol TW-L120, Reodol TW-O120, Reodol Super TW-S120, Reodol 430, Neoperex F-25, Neoperex No.25, Emanon 1112, emmanone 4110 EMANO-NN3299, emazol L-10H, emazol P-120, emazol O-120, etc., Kao Atlas Co., Ltd.Emulgen 105, Emulgen 108, Emulgen 147, Emulgen 210, Emulgen 320P, Emulgen 404, Emulgen 430 , Emulgen 903, Emulgen 906, Emulgen 92
0, Emulgen 950, Emulgen 705, Emulgen PP-15
0, Emulgen PP-230, Emulgen PP-250, Emulgen P
P-290, Amit 105, Amit 308, Amit 320, Cotamine 24P, Cotamine D-86P, Amphitol 24B, Amphitol 86B and the like. Among these surfactants, nonionic surfactants are particularly preferable.

(E) Organic solvent The propylene ether unit of the component (E), α- or β-
An organic solvent containing a hydroxycarbonyl structural unit,
It can be suitably used as a diluting solvent when producing the polysiloxane containing the photosensitizing group of the component (A), and at the same time, is a preferred solvent as a solvent component of the photocurable composition for forming an optical waveguide of the present invention. One of them is an organic compound having a propylene ether unit, and more preferably an ether-containing alcohol having a propylene ether unit as a constituent unit. The other is an organic compound containing an α- or β-hydroxycarbonyl structural unit, specifically, α-hydroxyesters and β-hydroxyketones. These solvents are preferably used because they have no mutagenicity, have good solubility for the component (A), and have the characteristics of being able to form good optical waveguides.

Specific examples of ether-containing alcohols include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether,
And dipropylene glycol monobutyl ether. Specific examples of the α-hydroxy esters include methyl lactate, ethyl lactate, propyl lactate, butyl lactate, amyl lactate, and octyl lactate. Specific examples of β-hydroxy ketones include 4-hydroxy-4-methyl-2-pentanone, 4-hydroxy-2-pentanone,
-Hydroxy-5-methyl-3-heptanone, and the like. These may be used alone or in combination of two or more.

(F) Metal alkoxide As the component (F), a metal alkoxide can be added for the purpose of controlling the refractive index of the optical waveguide of the present invention. Illustrative of such metal alkoxides are Ge, Sn, B, A
l, Ga, In, Sb, Ti and Zr, and the alkoxy group is selected from linear, branched and cyclic alkoxy groups having 1 to 12 carbon atoms. To show specific examples, tetramethoxygermanium, tetraethoxygermanium, tetrabutoxygermanium, methyltriethoxygermanium, phenyltrimethoxygermanium, tetrabutoxytin,
Tetrabutoxy tin, methyl tributoxy tin, trimethoxy borane, triethoxy borane, tributoxy borane, tributoxy aluminum, tris (ethyl acetoacetonato) aluminum, dibutoxy (acetyl acetonato) aluminum, triisopropoxy gallium,
Tributoxy gallium, triisopropoxy indium, tributoxy indium, triisopropoxy antimony, tributoxy antimony, tetraisopropoxy titanium, tetrabutoxy titanium, diacetylacetonato (dibutoxy) titanium, tetrakis (ethyl acetoacetonato) titanium, tetraiso Propoxy zirconium, tetrabutoxy zirconium, tetrakis (ethylacetoacetonato) zirconium and the like can be mentioned. The amount of the metal alkoxide to be added is 50 to 0.01 parts based on 100 parts by weight of the component (A). When it is added before the production, it is preferable to mix and hydrolyze and co-condense the hydrolyzable silane compound at the time of producing the polysiloxane.

(G) Inorganic Fine Particles As the component (G), inorganic fine particles can be added for the purpose of increasing the strength of the optical waveguide of the present invention. The element constituting the inorganic fine particles is not particularly limited, but is preferably an oxide or a nitride. Examples of the oxide include silicon oxide, aluminum oxide, boron oxide, titanium oxide, zirconium oxide, zinc oxide, cerium oxide, and nitride. Examples of the material include silicon nitride and boron nitride. The average particle diameter of these inorganic fine particles is 1 to 100
A material having a particle diameter of less than 1 nm is not stably present, while a particle diameter of more than 100 nm deteriorates the smoothness of the optical waveguide, thereby deteriorating the optical characteristics. The amount of addition can be 1 to 200 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the aminopolysiloxane (A). If the amount is less than 1 part by weight, the effect of improving the strength is low, while if it exceeds 200 parts by weight, the strength is undesirably reduced.

The inorganic fine particles are obtained as a powder or a solvent-dispersed colloidal liquid, but a solvent-dispersed colloidal liquid is more preferable because of its good dispersibility in the composition. In addition, in order not to impair optical transmission loss due to light scattering in the optical waveguide,
The difference in refractive index between the inorganic fine particles and the polysiloxane containing the photosensitizing group of the component (A) is preferably 0.03 or less, more preferably 0.003 or less. Among the examples of commercially available inorganic fine particles, examples of colloidal silica include Nissan Chemical Industries, Ltd.Snowtex O, Snowtex N, methanol silica sol, IPA-ST, MEK-ST, NBA-ST, DMAC-S
T, and the like.

(H) Dehydrating Agent The dehydrating agent of the component (H) can be added for the purpose of enhancing the storage stability and curability of the photocurable composition for forming an optical waveguide of the present invention. When a large amount of water is contained in the composition, it is presumed that unhydrolyzed groups contained in the polysiloxane containing a photosensitizing group are decomposed during storage and a gel is formed by crosslinking. Further, it is known that water serves as a chain transfer agent in a polymerization reaction by an acidic active substance such as cationic polymerization. Therefore, in order to form a photocured product having a high crosslinking density, it is preferable that the amount of water at the time of light irradiation is small. For these reasons, a dehydrating agent can be added for the purpose of enhancing the storage stability and photocurability of the composition of the present invention. In addition, such a dehydrating agent is selected from organic compounds which can be removed by evaporation under the drying conditions at the time of forming the optical waveguide and have a dehydrating property. Specific examples of such organic compounds include, for example, methyl orthoformate, ethyl orthoformate, methyl orthoacetate, orthoesters such as ethyl acetate, dimethyl acetal of acetone, diethyl acetal of acetone, dimethyl acetal of cyclohexane, Acetals of ketones such as diethyl acetal of cyclohexane can be mentioned. These orthoesters and ketone acetals react with water to form highly volatile esters / alcohols,
It is preferable because it decomposes into ketone / alcohol. The amount of the dehydrating agent to be added is 0.1 to 100 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the component (A). If it is less than 0.1 part by weight, there is no effect of improving storage stability and curability, while if it exceeds 100 parts by weight, the effect is saturated and it is not economical.

(I) Crosslinkable Compound As the component (I), a crosslinkable compound other than the component (A) can be added to the composition of the present invention. Examples of such a crosslinkable compound include the following. As a first example, when a hydrolyzable silane compound or a condensate thereof which is polymerized and cross-linked by an acidic active substance other than the component (A) is exemplified, for example, glycidyloxypropyl trisilane which is commercially available as a silane coupling agent Methoxysilane, glycidyloxypropyltriethoxysilane,
Glycidyloxypropylmethyldimethoxysilane, glycidyloxypropyldimethylmethoxysilane, and 2-
Trimethoxysilylethylcyclohexene oxide, 2
-Triethoxysilylethyl cyclohexene oxide,
Such as epoxy-substituted alkoxysilanes such as methacryloxypropyltrimethoxysilane and acryloxytrimethoxysilane; mercapto-substituted alkoxysilanes such as mercaptopropyltrimethoxysilane and mercaptopropylmethyldimethoxysilane; Ethoxysilane, N-
Examples include amino-substituted alkoxysilanes such as aminoethylaminopropyltrimethoxysilane, and one or more compounds selected from the group consisting of hydrolysis and condensation products thereof.

As a second example, epoxy compounds containing one or more epoxy groups in the molecule, for example, 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, 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, ethylenebis (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; one or more of aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin; Polyglycidyl ethers of polyether polyols obtained by adding two or more alkylene oxides; diglycidyl esters of aliphatic long-chain dibasic acids; monoglycidyl ethers of aliphatic higher alcohols; phenol, cresol, butylphenol or Monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxide thereto; glycidyl of higher fatty acids Ester ethers; epoxidized soybean oil; butyl epoxy stearate, epoxy stearic octyl, epoxidized linseed oil; epoxidized polybutadiene can be exemplified.

As a third example, oxetane compounds containing one or more oxentane groups in the molecule include, for example, 3,3-dimethyloxetane, 3,3-dichloromethyloxetane, 3-ethyl-3-phenoxy Oxetanes such as methyloxetane and bis (3-ethyl-3-methyloxy) butane can be mentioned.

As a fourth example, as a vinyl ether compound containing one or more vinyl ether groups in the molecule,
Examples thereof include vinyl ethers such as ethylene glycol divinyl ether, triethylene glycol divinyl ether, and trimethylolpropane trivinyl ether.

A fifth example is a vinyl polymer containing one or more groups selected from the group consisting of one or more epoxy, oxetane, vinyl ether and hydrolyzable silyl groups in the molecule. it can. These groups may be contained in the molecule in an amount of 0.1 to 50% by weight, preferably 1 to 30% by weight. The copolymerization of these functional groups can be carried out by radically copolymerizing (meth) acrylic esters containing these functional groups with a vinyl monomer as a main constituent, or by vinylic acid containing a carboxylic acid, epoxy group or hydroxy group. It is produced by a method of being introduced into a system polymer by a polymer reaction.

For example, in the production of a hydrolyzable silyl group-containing vinyl polymer, a carboxylic acid-containing vinyl polymer and glycidyloxypropyl trimethoxy are added to the method of radically copolymerizing methacryloxypropyltrimethoxysilane. It is produced by a method of reacting a silane, a method of reacting a hydroxy-containing vinyl polymer with trimethoxysilylpropyl isocyanate, a method of reacting an epoxy group-containing vinyl polymer with aminopropyltriethoxysilane, and the like. The weight average molecular weight by GPC of the vinyl polymer containing these crosslinkable groups is 500 to 100,000,
Preferably, 1000 to 50,000, more preferably 3000 to 100
00.

Examples of the vinyl monomer which is a main component of the vinyl polymer include aromatic unsaturated ethylene-containing compounds such as styrene and α-methylstyrene, and methyl (meth).
Acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, phenyl (meth) acrylate, methyl (meth) acrylate, isobornyl (meth) acrylate, lauryl (meth) acrylate, naphthyl (meth) acrylate, biphenyl (meth) acrylate, etc. (Meth) acrylates such as alkyl (meth) acrylates, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate, and (meth) acrylic acids such as acrylic acid and methacrylic acid N-vinyllactams such as N-vinylpyrrolidone and N-vinylcaprolactam; unsaturated amides such as (meth) acryloylmorpholine and N, N-dimethyl (meth) acrylamide It can be mentioned. The production of these vinyl polymers is known in the art of heating and stirring a mixed solution of a diazo-based thermal radical polymerization initiator such as bisazovaleronitrile, a vinyl monomer, and an organic solvent in a range of 50 ° C to 150 ° C for 1 to 10 hours. It is manufactured by a method.

Component (I) can be added to and mixed with a mixture containing at least one of components (A) to (H). A vinyl polymer containing a hydrolyzable silyl group is used. When blending the union as the component (I), after mixing the mixture of the raw material hydrolyzable silane and the hydrolyzable silyl group-containing vinyl polymer when producing the aminopolysiloxane of the component (A), It is preferable to mix by hydrolysis and condensation. In the present invention, components other than the above-mentioned components (C) to (I) can be blended as long as the effects of the present invention are not impaired.

In the present invention, the production of the optical waveguide includes the steps of forming the lower clad layer, the core portion, and the upper clad layer, and at least one of the steps is described in the first embodiment (A). And a step of applying a photocurable composition for forming an optical waveguide comprising the component (B) and then curing the composition with radiation.

1. Preparation of Photocurable Composition for Forming Optical Waveguide Photocurable Composition for Forming Optical Waveguide for Forming Lower Cladding Layer, Core Portion and Upper Cladding Layer Constituting Optical Waveguide, That is, Composition for Lower Layer, Composition for Core The product and the composition for the upper layer can be prepared by mixing and stirring the aminopolysiloxane, the photoacid generator, and the like described in the first embodiment in a conventional manner. Further, as the prepared lower layer composition, core composition and upper layer composition, respectively, the relationship between the refractive indices of each part finally obtained, so as to satisfy the conditions required for the optical waveguide, It is preferable to use different photocurable compositions for forming an optical waveguide.

Therefore, by appropriately selecting the type of the hydrolyzable silane compound as the component (A), a photocurable composition for forming an optical waveguide can be obtained from which cured films having different refractive indices can be obtained. Then, by using two or three kinds of photocurable compositions for forming an optical waveguide such that the difference in refractive index becomes an appropriate size, a photocurable composition for forming an optical waveguide that gives a cured film having the highest refractive index is used. As a core composition,
It is preferable to use another composition as the lower layer composition and the upper layer composition. However, the composition for the lower layer and the composition for the upper layer may be the same photocurable composition for forming an optical waveguide, and usually the same composition is economically advantageous, It is more preferable since the above-mentioned process can be easily performed. Further, when preparing each photocurable composition for forming an optical waveguide, its viscosity is adjusted to 1 to 10,000 cps (25 ° C.).
Is preferably in the range of 5 to 8,000 c
The value is more preferably in the range of ps (25 ° C.), and even more preferably in the range of 10 to 5,000 cps (25 ° C.). The reason for this is that if the viscosity of each optical waveguide forming photocurable composition is a value outside these ranges, it may be difficult to handle, or it may be difficult to form a uniform coating film. is there. In addition, the viscosity of the photocurable composition for forming an optical waveguide can be appropriately adjusted depending on the amount of the reactive diluent or the organic solvent.

2. Forming Method In the present invention, the optical waveguide 10 is formed through steps as shown in FIG. That is, the lower clad layer 13, the core portion 15, and the upper clad layer (not shown) are all coated with a photocurable composition for forming an optical waveguide for forming those layers, and then photocured. It is preferable to form by carrying out. In the following formation examples, the lower clad layer, the core portion and the upper clad layer are each a light-curable composition for forming an optical waveguide from which a cured product having a different refractive index after curing is obtained. The description will be made on the assumption that the composition is formed from the composition for the upper layer and the composition for the upper layer.

Preparation of Substrate First, as shown in FIG. 2A, a substrate 12 having a flat surface is prepared. Although the type of the substrate 12 is not particularly limited, for example, a silicon substrate, a glass substrate, or the like can be used. Step of Forming Lower Cladding Layer This is a step of forming a lower cladding layer 13 on the surface of the prepared substrate 12. Specifically, as shown in FIG. 2B, a lower layer composition is applied to the surface of the substrate 12 and dried or pre-baked to form a lower layer thin film. And
The lower cladding layer 13 can be formed by curing the lower thin film by irradiating light. The light used for forming the core layer and the cladding layer is not particularly limited, but is usually light in the ultraviolet to visible region of 200 to 450 nm, preferably light containing ultraviolet light having a wavelength of 365 nm. Illuminance at 200~450nm the 1~1000mW / cm ^2, irradiation amount 0.
01~5000mJ / cm ^2, preferably by irradiation so as 0.1~1000mJ / cm ^2, is exposed. Here, the type of light to be irradiated includes visible light, ultraviolet light, infrared light, X-ray, α-ray, β
Although rays, γ rays and the like can be used, a wavelength including ultraviolet rays, particularly preferably 200 to 400 nm, particularly preferably 365 nm, is preferable from the industrial versatility of the light source. And
As the irradiation device, for example, a lamp light source that simultaneously irradiates a large area such as a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, an excimer lamp, a pulse, a laser light source of continuous light emission, and a mirror light source from either of the two light sources. Convergent light can be used using a lens, an optical fiber, or the like. When an optical waveguide is formed using convergent light, exposure can be performed to the shape of the optical waveguide by moving the convergent light or the irradiation target. Among these light sources, a light source having a high ultraviolet intensity of 365 nm is preferable. For example, a high-pressure mercury lamp is preferable as a lamp light source, and an argon laser is preferable as a laser light source. In the step of forming the lower cladding layer 13, light is irradiated on the entire surface of the thin film,
Preferably, the whole is cured. Here, as a method of applying the composition for the lower layer, a method such as a spin coating method, a dipping method, a spray method, a bar coating method, a roll coating method, a curtain coating method, a gravure printing method, a silk screen method, or an inkjet method. Can be used. Among them, it is more preferable to adopt the spin coating method, since a lower layer thin film having a particularly uniform thickness can be obtained.

Further, in order to appropriately adjust the rheological properties of the composition for the lower layer to the coating method, additives other than the surface tension reducing agent can be blended as required. Further, the lower layer thin film composed of the lower layer composition is preferably pre-baked at 50 to 200 ° C. after application.
In addition, the coating method in the formation process of the lower clad layer,
The improvement of the rheological properties and the like also applies to the step of forming the core portion and the step of forming the upper clad layer described later. After the exposure, it is preferable to further perform a heat treatment (hereinafter, referred to as “post bake”) so that the entire surface of the coating film is sufficiently cured. This heating condition varies depending on the composition of the photocurable composition for forming an optical waveguide, the type of additive, and the like, but is usually 30 to 400 ° C., preferably 50 to 300 ° C., for example, 5 minutes to 72 hours. It should be a condition. The irradiation amount, type, irradiation device, and the like of the light in the lower clad layer forming step are the same as those in the core part forming step and the upper clad layer forming step described later.

Next, as shown in FIG. 2C, a core composition is applied onto the lower clad layer 13 and dried or further prebaked to form a core thin film 14. Then, FIG.
As shown in (d), with respect to the upper surface of the core thin film 14,
According to a predetermined pattern, it is preferable to irradiate the radiation 16 via a photomask 19 having a predetermined line pattern, for example. As a result, only the light-irradiated portions are cured, and the remaining uncured portions are removed by development, as shown in FIG. The core portion 15 made of a film can be formed. Also, core part 1
Irradiation of the light 16 to the core thin film 14 for forming 5 is performed according to a photomask 19 having a predetermined pattern, and then the unexposed portion is developed with a developer so that an uncured unnecessary portion is removed. Removed, thereby forming the core portion 15. The method of irradiating light in accordance with the predetermined pattern as described above is not limited to a method using a photomask including a light transmitting portion and a non-transmitting portion, and examples thereof include the following methods a to c. a. A method using a means for electro-optically forming a mask image composed of a light transmitting area and a non-transmitting area according to a predetermined pattern using the same principle as that of a liquid crystal display device. b. Using a light guide member made by bundling many optical fibers,
A method of irradiating light via an optical fiber corresponding to a predetermined pattern on the light guide member. c. A method of irradiating a photocurable composition with laser light or convergent light obtained by a converging optical system such as a lens or a mirror while scanning.

After the exposure, it is preferable to perform a heat treatment (hereinafter, referred to as “PEB”) in order to accelerate the curing of the exposed portion. The heating conditions vary depending on the composition of the photocurable composition for forming an optical waveguide, the types of additives, and the like, but are usually 30 to 200 ° C, preferably 50 to 150 ° C.
It is. On the other hand, before exposure, the coating of the photocurable composition for forming an optical waveguide can be left in a room temperature condition for 1 to 10 hours to form the core portion into a semicircular shape.
Therefore, when it is desired to obtain a semi-circular core portion, it is preferable to leave the core portion at room temperature for several hours before exposure. In this manner, the thin film that has been subjected to pattern exposure according to a predetermined pattern and selectively cured can be subjected to development processing by utilizing the difference in solubility between the cured part and the uncured part. Therefore, after the pattern exposure, by removing the uncured portion and leaving the cured portion, the core portion can be formed as a result.

Here, the developing solution includes sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, Methyl diethylamine, ethanolamine, N-methylethanolamine,
N, N-dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, choline, pyrrole, piperidine,
Basic substances such as 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonane and water, methanol, ethanol, propyl alcohol, butanol, A solution diluted with a solvent such as octanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, N-methylpyrrolidone, formamide, N, N-dimethylformamide, N, N-dimethylacetamide can be used. The concentration of the basic substance in the developer is usually 0.05 to 25% by weight, preferably 0.1 to 25% by weight.
It is preferable to set the value in the range of 3.0% by weight.

The development time is usually from 30 to 600 seconds, and a known development method such as a puddle method, a dipping method or a shower development method can be employed. When an organic solvent is used as the developing solution, air drying is performed. When an alkaline aqueous solution is used, running water washing is performed, for example, for 30 to 90 seconds, and air drying is performed using compressed air or compressed nitrogen. By removing the water, a patterned film is formed.

Next, in order to further harden the patterning portion, a post-baking process is performed at a temperature of, for example, 30 to 400 ° C. for 5 to 600 minutes by a heating device such as a hot plate or an oven to form a hardened core portion. Will be. In addition, it is preferable to use an aminopolysiloxane having a higher amino group content than the lower layer composition and the upper layer composition for the core composition. With such a configuration, while the pattern accuracy of the core portion can be further improved, the composition for the lower layer and the composition for the upper layer,
Excellent storage stability can be obtained, and curing can be sufficiently performed with a relatively small radiation dose.

Formation of Upper Cladding Layer Next, the lower cladding layer 13 on which the core portion 15 is formed
An upper layer composition is applied to the surface of the substrate and dried or prebaked to form an upper layer thin film. The upper cladding layer 17 can be formed as shown in FIG. 1 by irradiating the upper thin film with light to cure it. In addition, the upper cladding layer obtained by irradiation of radiation,
It is preferable to perform the above-mentioned post-baking as needed. By post-baking, an upper clad layer having excellent hardness and heat resistance can be obtained.

[0069]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. [Production of Photosensitizing Group-Containing Polysiloxane Solution 1 (PS1)] In a vessel equipped with a stirrer, phenyltrimethoxysilane (7
6.9 g, 0.39 mol), methyltrimethoxysilane (101.7 g, 0.75 mol), 9-hydroxymethylanthracene (0.27 g, 1.3 mmol),
(Oxalic acid (0.1 g, 1.1 x mmol), heated and stirred at 80 ° C for 3 hours, then cooled, and ion-exchanged water (45 .9 g,
2.55 mol), and the mixture was heated and stirred at 60 ° C. for 6 hours to hydrolyze and condense phenyltrimethoxysilane and methyltrimethoxysilane. Next, propylene glycol monomethyl ether was added into the container, and then methanol produced as a by-product of hydrolysis was removed using an evaporator. Finally, 162 g of a propylene glycol monomethyl ether solution containing polysiloxane whose solid content was adjusted to 55% by weight was obtained. The weight average molecular weight in terms of polystyrene determined by GPC monitored with a differential refractometer was 2,000. Meanwhile, 36
The fluorescence GPC spectrum at 393 nm of the same sample measured while irradiating with 8 nm excitation light showed the same waveform as the GPC spectrum monitored by a differential refractometer, and the raw material 9-hydroxymethylanthracene was distributed in the entire molecular weight region of polysiloxane. This indicated that polysiloxane to which 9-hydroxymethylanthracene was bonded was formed. This is designated as “polysiloxane solution 1 (PS1)”.

[Photosensitizing group-containing polysiloxane solution 2 (PS
2) Production] In a vessel equipped with a stirrer, phenyltrimethoxysilane (103.65 g, 0.52 mol) and methyltrimethoxysilane (136.99 g, 1.00 mol)
And dimethyldimethoxysilane (24.32 g, 0.2
0 mol) and 9-hydroxymethylanthracene (0.
41 g, 2.0 mmol) and tetrabutoxyzirconium (0.15 g, 0.39 mmol).
By stirring at 80 ° C. for 3 hours, tetrakis (anthranylmethoxy) zirconium was prepared. After the solution was cooled to room temperature, ion-exchanged water (90.0 g, 5.0 mol) having an electric conductivity of 8 × 10 −5 S · cm −1 was added, and the mixture was heated and stirred at 60 ° C. for 6 hours to obtain phenyl. Hydrolysis and cocondensation of trimethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane and tetrakis (anthranylmethoxy) zirconium were performed. Next, propylene glycol monomethyl ether was added into the container, and then methanol produced as a by-product of hydrolysis was removed using an evaporator. Finally, 246 g of a propylene glycol monomethyl ether solution containing polysiloxane whose solid content was adjusted to 55% by weight was obtained. GP
The weight average molecular weight determined by C was 1,800. on the other hand,
The fluorescence GPC spectrum at 393 nm of the same sample measured with irradiation of excitation light at 368 nm shows the same waveform as the GPC spectrum monitored by a differential refractometer, and the raw material 9-hydroxymethylanthracene is distributed in the entire molecular weight region of polysiloxane. This indicated that polysiloxane to which 9-hydroxymethylanthracene was bonded was formed.
This is designated as “polysiloxane solution 2 (PS2)”.

[Photosensitizing group-containing polysiloxane solution 3 (PS
3) Production] In a vessel equipped with a stirrer, methyl methacrylate (450 g, 4.50 mol), methacryloxypropyltrimethoxysilane (50 g, 0.20 mol), propylene glycol monomethyl ether (600 g),
Then, after containing 2,2'-azobis- (2.4-dimethylvaleronitrile) (35 g, 0.14 mol), the system is purged with nitrogen. Thereafter, the temperature in the reaction vessel is set at 70 ° C., and the mixture is stirred for 6 hours. Finally, the solid content concentration was adjusted to 45% by weight to obtain a propylene glycol monomethyl ether solution containing an acrylic polymer. The weight average molecular weight determined by GPC was 8,000. In another container equipped with a stirrer, methyltrimethoxysilane (231.36 g,
1.70 mol), phenyltrimethoxysilane (19
3.48 g, 0.97 mol) and tetrabutoxyzirconium (0.15 g, 0.39 mmol) were added.
A solution containing tetrakis (anthranylmethoxy) zirconium was obtained by heating and stirring at 3 ° C. for 3 hours. After cooling, the aforementioned hydrolyzable silane-containing acrylic polymer solution (133.33 g) and an electric conductivity of 8 × 10 −5 S · cm
After containing -1 ion-exchanged water (108.48 g, 6.0 mol), the mixture was heated and stirred at 60 ° C. for 6 hours to obtain phenyltrimethoxysilane, methyltrimethoxysilane, tetrakis (anthranylmethoxy). The zirconium and acrylic polymer solutions were hydrolyzed and co-condensed. Next, propylene glycol monomethyl ether was added into the container, and then methanol produced as a by-product of hydrolysis was removed using an evaporator. And finally, a propylene glycol monomethyl ether solution containing polysiloxane whose solid content was adjusted to 45% by weight was obtained. The weight average molecular weight determined by GPC is 12
000. On the other hand, the fluorescence GPC spectrum at 393 nm of the same sample measured with irradiation of excitation light at 368 nm showed a waveform similar to the GPC spectrum monitored by a differential refractometer, and the raw material 9-hydroxymethylanthracene was shown in the total molecular weight region of polysiloxane. Distributed, indicating that polysiloxane to which 9-hydroxymethylanthracene was bonded was formed. This is designated as “polysiloxane solution 3 (PS3)”.

[Photosensitizing group-containing polysiloxane solution 4 (PS
4) Production] In a vessel equipped with a stirrer, phenyltrimethoxysilane (76.9 g, 0.39 mol), methyltrimethoxysilane (101.7 g, 0.75 mol), 9-
Hydroxymethylanthracene (2.5 g, 12.0 mmol), and tetrabutoxyzirconium (1.0
g, 0.0026 mol), and heated and stirred at 80 ° C. for 3 hours to obtain a solution containing tetrakis (anthranylmethoxy) zirconium. Electric conductivity after cooling is 8
× 10 −5 S · cm −1 of ion-exchanged water (45.9 g;
(55 mol), and the mixture was heated and stirred at 60 ° C. for 6 hours to hydrolyze and condense phenyltrimethoxysilane, methyltrimethoxysilane and tetrakis (anthranylmethoxy) zirconium.
Next, propylene glycol monomethyl ether was added into the container, and then methanol produced as a by-product of hydrolysis was removed using an evaporator. Finally, a propylene glycol monomethyl ether solution 162 containing a polysiloxane whose solid content has been adjusted to 55% by weight.
g was obtained. The weight average molecular weight determined by GPC was 3,000. On the other hand, the fluorescence GPC spectrum at 393 nm of the same sample measured with irradiation of excitation light at 368 nm showed a waveform similar to the GPC spectrum monitored by a differential refractometer, and the raw material 9-hydroxymethylanthracene was shown in the total molecular weight region of polysiloxane. Distributed, indicating that polysiloxane to which 9-hydroxymethylanthracene was bonded was formed. This is called "polysiloxane solution 4 (PS
4) ".

[Production of Comparative Polysiloxane Solution 5 (S1)] In a container equipped with a stirrer, phenyltrimethoxysilane (76.9 g, 0.39 mol) and methyltrimethoxysilane (101.7 g, 0.1 g) were added. 75 mol) and ion-exchanged water (45.9 g,
2.55 mol) and oxalic acid (0.1 g, 1.1 × mmol), and then heated and stirred at 60 ° C. for 6 hours to obtain phenyltrimethoxysilane and methyltrimethoxysilane. Hydrolysis and condensation were performed. Next, propylene glycol monomethyl ether was added into the container, and then methanol produced as a by-product of hydrolysis was removed using an evaporator. Finally, 162 g of a propylene glycol monomethyl ether solution containing polysiloxane whose solid content was adjusted to 55% by weight was obtained. The weight average molecular weight determined by GPC was 2,000. This is designated as “Comparative polysiloxane solution 5 (S1)”.

[Production of Comparative Polysiloxane Solution 6 (S2)]
In a vessel equipped with a stirrer, place phenyltrimethoxysilane (1
03.65 g, 0.52 mol), methyltrimethoxysilane (136.99 g, 1.00 mol), dimethyldimethoxysilane (24.32 g, 0.20 mol),
Tetrabutoxy zirconium (0.15 g, 0.39 mmol) and ion-exchanged water (90.0 g, 5.0 mol) having an electric conductivity of 8 × 10 −5 S · cm −1 were added at 60 ° C.
By heating and stirring for a period of time, hydrolysis and cocondensation of phenyltrimethoxysilane, methyltrimethoxysilane, and dimethyldimethoxysilane were performed. Then
After propylene glycol monomethyl ether was added into the vessel, methanol produced as a by-product of hydrolysis was removed using an evaporator. And finally the solid content is 5
246 g of a propylene glycol monomethyl ether solution containing polysiloxane adjusted to 5% by weight was obtained.
The weight average molecular weight determined by GPC was 1,900. This is designated as “polysiloxane solution 6 (PS2)”.

[Preparation of Cured Composition A for Forming Optical Waveguide] A photoacid generator (TPS-10 manufactured by Midori Kagaku Co., Ltd.) was added to 100 parts by weight of solid content of polysiloxane solution 1 (PS1).
5) 1 part by weight was added, mixed uniformly, and filtered with a 0.5 μm filter to obtain a cured composition A for forming an optical waveguide.

[Preparation of Cured Composition B for Forming Optical Waveguide] A photoacid generator (TPS-10 manufactured by Midori Kagaku Co., Ltd.) was added to 100 parts by weight of solid content of polysiloxane solution 2 (PS2).
5) 1 part by weight was added, mixed uniformly, and filtered with a 0.5 μm filter to obtain a cured composition B for forming an optical waveguide.

[Preparation of Cured Composition C for Forming Optical Waveguide] The above-mentioned polysiloxane solution 1 (PS1) was converted to a solid content of 100.
Add photoacid generator (Sartomer CD-10
12) 1 part by weight, trioctylamine as acid diffusion controller
0.005 parts by weight, respectively, and mixed uniformly.
By filtering through a 5 μm filter, a cured composition C for forming an optical waveguide was obtained. [Preparation of Cured Composition D for Forming Optical Waveguide] 1 part by weight of a photoacid generator (CD-1012 manufactured by Sartomer) is added to 100 parts by weight of the above-mentioned polysiloxane solution 3 (PS3) in terms of solid content. The mixture was added, mixed uniformly, and filtered with a 0.5 μm filter to obtain a cured composition D for forming an optical waveguide. [Preparation of Cured Composition E for Forming Optical Waveguide] With respect to 100 parts by weight of the above-mentioned polysiloxane solution 1 (PS1) in terms of solid content,
Photoacid generator (TPS-105 manufactured by Midori Kagaku Co., Ltd.) 1
Parts by weight, trioctylamine 0.0 as an acid diffusion controller
05 parts by weight, surface tension reducing agent (Dow Corning Toray)
By adding 0.01 part by weight of SH28PA (manufactured by Corporation), mixing uniformly, and filtering through a 0.5 μm filter,
A cured composition E for forming an optical waveguide was obtained. [Preparation of Cured Composition F for Forming Optical Waveguide] A photoacid generator (manufactured by Midori Kagaku Co., Ltd.) was added to 100 parts by weight of the above hydrolyzable silyl group-containing polysiloxane solution 3 (PS3) in terms of solid content. TPS-105) 1 part by weight, surface tension reducing agent (SH28PA, manufactured by Dow Corning Toray Co., Ltd.) 0.01
Parts by weight, add and mix evenly, 0.5μm
By filtering with a filter, a cured composition F for forming an optical waveguide was obtained. Polysiloxane solution 4 (PS
4 parts by weight of photoacid generator (TPS-105 manufactured by Midori Kagaku Co., Ltd.) per 100 parts by weight of solid content of 4), 0.005 parts by weight of trioctylamine as an acid diffusion controller, surface tension reducing agent (SH28P manufactured by Dow Corning Toray)
A) After adding 0.01 part by weight and mixing uniformly,
By filtering through a 0.5 μm filter, a cured composition G for forming an optical waveguide was obtained. [Preparation of Cured Composition H for Forming Optical Waveguide] A photoacid generator (TPS-10 manufactured by Midori Kagaku Co., Ltd.) was added to 100 parts by weight of the above-mentioned polysiloxane solution 4 (PS4) in terms of solid content.
5) 1 part by weight, 0.005 part by weight of trioctylamine as an acid diffusion controlling agent, 0.01 part by weight of a surface tension reducing agent (SH28PA manufactured by Dow Corning Toray Co., Ltd.), and ethyl orthoacetate (3 parts by weight) as a dehydrating agent Was added, and the mixture was uniformly mixed and filtered with a 0.5 μm filter to obtain a cured composition H for forming an optical waveguide. [Preparation of Cured Composition I for Forming Optical Waveguide] A photoacid generator (TPS-10 manufactured by Midori Kagaku Co., Ltd.) was added to 100 parts by weight of the above-mentioned polysiloxane solution 2 (PS2) in terms of solid content.
5) 1 part by weight, surface tension reducing agent (Dow Corning Toray)
SH28PA (manufactured by Nissan Chemical Industry Co., Ltd., IPA-ST, solid content 30%)
(Particle size: 12 nm) 67 parts by weight, and ethyl orthoacetate (3 parts by weight) as a dehydrating agent were added, and mixed uniformly.
The mixture was filtered through a μm filter to obtain a cured composition I for forming an optical waveguide.

[Preparation of Comparative Cured Composition for Forming Optical Waveguide J] To 100 parts by weight of the above-mentioned polysiloxane solution 5 (S1) in terms of solid content, a photoacid generator (TPS-manufactured by Midori Kagaku Co., Ltd.) was used. 105) Add 1 part by weight, mix uniformly,
By filtering through a 0.5 μm filter, a comparative cured composition J for forming an optical waveguide was obtained. [Preparation of Comparative Cured Composition for Forming Optical Waveguide K] To 100 parts by weight of the above-mentioned polysiloxane solution 6 (S2) in terms of solid content, a photoacid generator (TPS-10 manufactured by Midori Kagaku KK) was used.
5) 1 part by weight was added, mixed uniformly, and filtered with a 0.5 μm filter to obtain a comparative cured composition J for forming an optical waveguide. [Preparation of Comparative Cured Composition for Forming Optical Waveguide L] A photoacid generator (TPS-10 manufactured by Midori Kagaku Co., Ltd.) was added to 100 parts by weight of the above-mentioned polysiloxane solution 5 (S1) in terms of solid content.
5) 1 part by weight, 0.3 part by weight of 9-hydroxymethylanthracene as a photosensitizer, and 0.005 part by weight of trioctylamine as an acid diffusion controller are added, and mixed uniformly.
By filtering with a 0.5 μm filter, a comparative cured composition L for forming an optical waveguide was obtained. [Preparation of Comparative Cured Composition for Forming Optical Waveguide M] A photoacid generator (TPS-10 manufactured by Midori Kagaku Co., Ltd.) was added to 100 parts by weight of the above-mentioned polysiloxane solution 6 (S2) in terms of solid content.
5) 1 part by weight, 0.3 part by weight of 9-hydroxymethylanthracene as a photosensitizer were added, and the mixture was uniformly mixed.
By filtering through a 5 μm filter, a comparative cured composition L for forming an optical waveguide was obtained. Tables 1 and 2 show the compositions of the cured compositions (A) to (M) for forming an optical waveguide prepared as described above. Using these compositions, the cores and claddings of the optical waveguides shown in the examples were formed. In addition, Tables 1 and 2 show the results of evaluating the performance of the manufactured photocurable composition for forming an optical waveguide and the performance of the optical waveguide manufactured using the same according to a test method described later.

[Evaluation] [Evaluation of Storage Stability of Photocurable Composition for Forming Optical Waveguide] The prepared photocurable composition for forming an optical waveguide was sealed and sealed at 30 ° C.
After storing in a dark place for 2 weeks, 10μ thick on silicon wafer
m, using an aligner (PLA501F) manufactured by CANON Corporation and a high-pressure mercury lamp (USH-250D) manufactured by USHIO under the atmosphere (illuminance at 356 nm: 7 mW / cm ² ), line / space = 10 μm / 30μ
50 mJ / cm ² through an aligner mask of m
After the irradiation, the unexposed portions were washed with an alkaline aqueous solution. Observing the obtained line pattern with an optical microscope with a magnification of 200,
The line pattern was evaluated. If the line pattern did not change from the initial, it was marked as ○, otherwise it was marked as ×

[Evaluation of Photo-Curability] A 10 μm-thick coated film of the produced photo-curable composition for forming an optical waveguide was coated on a silicon wafer in the atmosphere by an aligner (PLA501F) manufactured by CANON and a product manufactured by USHIO. Using a high pressure mercury lamp (USH-250D) (illuminance at 365 nm is 7 mW / cm ² ), line / space = 10 μm / 30 μm
After irradiating with a light amount of 50 mJ / cm ² through an aligner mask, the unexposed portion was washed with an alkaline aqueous solution. The obtained line pattern was observed with an optical microscope having a magnification of 200, and the photocurability was evaluated based on the presence or absence of the line pattern.ラ イ ン indicates that the line pattern remains, and X indicates that the line pattern disappears.

[Evaluation of Pattern Performance] A coating film coated on a silicon wafer to a thickness of 10 μm was exposed to the atmosphere using an aligner (PLA501F) manufactured by CANON and a high-pressure mercury lamp (USH-250D) manufactured by USHIO (365n).
Illuminance in m is 7 mW / cm ² ), line / space = 10
5 μm through a 30 μm aligner mask
After the irradiation with 0 mJ / cm ² , the unexposed portions were washed with an aqueous alkali solution. The obtained line pattern was observed with an optical microscope having a magnification of 200, and the line pattern was evaluated. When the error from the mask dimension was within ± 0.2 μm, the result was indicated by “○”, and otherwise, ×.

[Evaluation of Transmission Loss of Optical Waveguide] Wavelength 1.31
The optical transmission loss was evaluated by subtracting the connection loss from the transmission loss obtained by the cutback method using the monochromatic light of μm.

[Evaluation Results of Photocurable Composition for Forming Optical Waveguide and Optical Waveguide Using the Same] The results of evaluating the photocurable composition for forming an optical waveguide and the optical waveguide based on the test method described above are shown in Table 3. Shown in As shown in Table 3, the composition comprising the polysiloxane containing a photosensitizing group and the photoacid generator had good photocurability, patterning properties, and optical characteristics of the optical waveguide. The composition comprising the polysiloxane containing no sensitizer and the photoacid generator had low photocurability and could not form an optical waveguide pattern under the test conditions. Further, as shown in Comparative Example-2, a composition comprising a polysiloxane containing no photosensitizer, a photoacid generator, and a photosensitizer has low storage stability, and an optical waveguide formed using the composition has a low storage stability. It is clear that the transmission loss is large. on the other hand,
Under the same conditions, a composition containing an acid diffusion controller, a surface tension reducing agent, a metal alkoxide, an inorganic fine particle, and a crosslinkable compound has similarly good storage stability, photocurability, patterning properties,
And optical properties.

[0084]

[Table 1]

[0085]

[Table 2] b-1: TPS-105 manufactured by Mitupuri Chemical Co., Ltd., b-2: CD-101 manufactured by Sartomer
2, c-1; trioctylamine, d-1; Toray Tow Corning Silicone Co., Ltd.
SH28PA, e-1; propylene glycol monomethyl ether, f-1; tetraethoxysilconium (f-1 is compounded at the time of production of PS4), g-1; h-1; ethyl orthoacetate,
i-1; hydrolyzable silyl group-containing polymethyl methacrylate (i-1 was added at the time of production of PS3), j-1; 9-human peroxymethylanthracene

[0086]

[Table 3]

[0087]

According to the present invention, by using a photocurable composition comprising a polysiloxane containing a photosensitizing group and a photoacid generator, it is highly sensitive to a general-purpose light source and easy to handle. An optical waveguide having good pattern accuracy and good optical characteristics can be formed.

[0088]

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of an optical waveguide of the present invention.

FIGS. 2A to 2E are partial process diagrams of a method for manufacturing an optical waveguide.

[Explanation of symbols]

10 Optical waveguide 12 Substrate 13 Lower cladding layer 14 Core thin film 15 core part 16 Radiation 17 Upper cladding layer 19 Photomask

   ────────────────────────────────────────────────── ─── Continuation of front page    (72) Inventor Hideaki Takase             Jay 11-2-24 Tsukiji, Chuo-ku, Tokyo             SRL Co., Ltd. F term (reference) 2H047 KA04 PA02 PA21 PA24 PA28                       QA05 QA07

Claims (7)

[Claims] 1. A photocurable composition for forming an optical waveguide, comprising (A) a polysiloxane having a photosensitizing group and (B) a photoacid generator. 2. The photocurable composition for forming an optical waveguide according to claim 1, further comprising an acid diffusion controller as the component (C). 3. The photocurable composition for forming an optical waveguide according to claim 1, further comprising a surface tension reducing agent as the component (D). 4. The optical waveguide according to claim 1, wherein the component (E) contains an organic compound containing a propylene ether unit or an α- or β-hydroxycarbonyl structural unit as a solvent. Photocurable composition. 5. The photocurable composition for forming an optical waveguide according to claim 1, wherein the composition contains a metal alkoxide as the component (F). 6. An optical waveguide including a lower cladding layer, a core layer, and an upper cladding layer, wherein at least one layer has the following structure.
A method for producing an optical waveguide, which is a cured product of a photocurable composition containing the component (A) and the component (B). (A) Polysiloxane having photosensitizing group (B) Photoacid generator 7. An optical waveguide manufactured by the method according to claim 6.