JP4810956B2 - Resin composition for optical material, resin film for optical material, and optical waveguide using the same - Google Patents

Description

  The present invention relates to a resin composition for an optical material, a resin film for an optical material excellent in transparency, heat resistance and productivity, and an optical waveguide using these.

In order to cope with the increase in information capacity accompanying the spread of the Internet and LAN (Local Area Network), not only for communication fields such as trunk lines and access systems, but also for short-distance signal transmission between boards in routers and server devices or within boards. Development of optical interconnection technology using optical signals is in progress. Specifically, in order to use light for short-distance signal transmission between boards in a router or a server device or in a board, an opto-electric hybrid board in which an optical transmission line is combined with an optical transmission path has been developed.
As an optical transmission line in this case, it is desirable to use an optical waveguide that has a higher degree of freedom of wiring and can be densified than an optical fiber, and among them, a polymer material that is excellent in workability and economy is used. Optical waveguides are promising. Since the polymer optical waveguide has a structure that coexists with the electrical wiring board as described above, the polymer optical waveguide is required to have high transparency (low propagation loss) and high heat resistance. Fluorinated polyimide (for example, Non-Patent Document 1) and epoxy resin (for example, Non-Patent Document 2) have been proposed.

When a fluorinated polyimide waveguide material is used, the resin itself has a high heat resistance of about 300 ° C. and a high transparency of 0.3 dB / cm at a wavelength of 850 nm. However, since heating for several tens of minutes to several hours is necessary, film formation on an electric wiring board was difficult. Further, since fluorinated polyimide has no photosensitivity, the optical waveguide production method by photosensitivity / development cannot be applied, and the productivity and the area increase are inferior.
On the other hand, it is reported that the epoxy resin can form a core pattern by a photosensitivity / development method by adding a photopolymerization initiator and has a high transparency of 0.1 dB / cm. The heat resistance of the epoxy resin is generally 200 to 280 ° C., and there are some which can be applied to the above-described opto-electric hybrid board. However, in order to obtain high reliability, higher heat resistance is required.
As described above, an optical waveguide having (1) high transparency, (2) high heat resistance, and (3) high productivity has not been developed.

Journal of Japan Institute of Electronics Packaging, Vol. 7, No. 3, pp. 213-218, 2004 Optics, Vol.31, No.2, pp.81-83, 2002

  In view of the above problems, the present invention provides a resin composition for optical materials, a resin film for optical materials, and an optical waveguide using these having high transparency and high heat resistance and high productivity. Objective.

（Ｘは下記式（II）で表されるものであり、Ｙは水素又はメチル基、ｍ及びｎはそれぞれ１〜２０の整数である。）

（Ｒ１〜Ｒ１６は、それぞれ独立に水素、炭素数１〜１２のアルキル基、炭素数１〜６のアルコキシ基、総炭素数２〜７のアルコキシカルボニル基、炭素数６〜１０のアリール基、または炭素数７〜９のアラルキル基である。）
（２）（Ａ）成分と（Ｂ）成分の総量に対して、（Ａ）成分の含有量が９０．０〜９９．９質量％であり、（Ｂ）成分の含有量が０．１〜１０．０質量％である上記（１）に記載の光導波路材料用樹脂組成物、
（３）（Ａ）成分と（Ｃ）成分の総量に対して、（Ａ）成分の含有量が２０〜９０質量％であり、（Ｃ）成分の含有量が１０〜８０質量％であり、かつ（Ａ）成分と（Ｃ）成分の総量１００質量部に対して（Ｂ）成分の含有量が０．１〜５質量部である上記（１）又は（２）に記載の光導波路材料用樹脂組成物、
（４）（Ｃ）ベースポリマーの数平均分子量が１０，０００以上である上記（１）〜（３）のいずれかに記載の光導波路材料用樹脂組成物、 As a result of intensive studies, the present inventors have solved the above-mentioned problems with a resin composition for an optical waveguide material, which includes full orange (meth) acrylate, a photopolymerization initiator, and a base polymer, and an optical waveguide resin film. Found to get. The present invention has been completed based on this finding.
That is, the present invention
(1) (A) fluorene (meth) acrylate represented by the following formula (I), a (B) a photopolymerization initiator, and (C) including a base polymer, an optical waveguide material for the resin composition (C) The resin composition for optical waveguide material, wherein the base polymer is a phenoxy resin having a number average molecular weight of 5,000 or more,

(X is represented by the following formula (II), Y is hydrogen or a methyl group, and m and n are each an integer of 1 to 20.)

(R1 to R16 are each independently hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms in total, an aryl group having 6 to 10 carbon atoms, or (It is an aralkyl group having 7 to 9 carbon atoms.)
(2) The content of the component (A) is 90.0 to 99.9% by mass relative to the total amount of the components (A) and (B), and the content of the component (B) is 0.1 to 9%. The resin composition for an optical waveguide material according to the above (1), which is 10.0% by mass,
(3) The total content of the (A) component and the (C) component, the content of the (A) component is 20 to 90% by mass, the content of the (C) component is 10 to 80% by mass, And the content of (B) component is 0.1-5 mass parts with respect to 100 mass parts of total amounts of (A) component and (C) component, For optical waveguide materials as described in said (1) or (2) Resin composition,
(4) The resin composition for an optical waveguide material according to any one of (1) to (3), wherein the number average molecular weight of the (C) base polymer is 10,000 or more ,

( 5 ) A resin film for an optical waveguide material comprising the resin composition for an optical waveguide material according to any one of (1) to ( 4 ).
( 6 ) The resin composition for an optical waveguide material according to any one of (1) to ( 4 ) or the resin film for an optical waveguide material according to ( 5 ) above, a lower clad of an optical waveguide, a core, and An optical waveguide used for at least one of the upper claddings,
Is to provide.

  The optical waveguide produced using the resin composition for an optical material of the present invention has high transparency and high heat resistance. Furthermore, according to the resin film of the present invention, these highly transparent and high heat resistant optical waveguides are It can be manufactured with extremely high productivity.

  The resin composition for an optical optical material of the present invention is characterized by containing (A) a full orange (meth) acrylate represented by the following general formula (I). Here, (meth) acrylate refers to acrylate or methacrylate.

  Here, X is represented by the following formula (II), and Y is hydrogen or a methyl group. M and n are each an integer of 1 to 20, preferably an integer of 1 to 10.

Here, R1 to R16 are each independently hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 7 total carbon atoms, or an aryl group having 6 to 10 carbon atoms. Or an aralkyl group having 7 to 9 carbon atoms. R9 to R16 may be located at any position on the benzene ring, and bonded to oxygen in the skeleton of the formula (I) in these non-substituent parts (marked with “*” in the formula (II)). is doing.
In general formulas (I) and (II), those in which Y is hydrogen, R1 to R16 are hydrogen, m is 1, and n is 1 are commercially available (Shin Nakamura Chemical Co., Ltd.) Product name "A-BPEF").

Next, (B) the photopolymerization initiator is not particularly limited, and various types can be used. For example, benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2- Hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1,2-methyl Aromatic ketones such as -1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one; 2-ethylan Laquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methyl Quinones such as anthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl 1,4-naphthoquinone, 2,3-dimethylanthraquinone; benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, etc. Benzoin ether compounds; benzoin compounds such as benzoin, methylbenzoin and ethylbenzoin; benzyl derivatives such as benzyldimethyl ketal; 2- (o-chlorophenyl) -4,5-diphenyl Midazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o -Methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer such as 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer; 2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. Phosphine oxides; 9-phenylacridine, 1,7-bis (9,9′-acridinyl) Examples include acridine derivatives such as pentane; N-phenylglycine; N-phenylglycine derivatives; coumarin compounds. In addition, in the 2,4,5-triarylimidazole dimer, the aryl group substituents of two 2,4,5-triarylimidazoles may give the same and symmetric compounds, or differently asymmetric Such compounds may be provided. Moreover, you may combine a thioxanthone type compound and a tertiary amine compound like the combination of diethyl thioxanthone and dimethylaminobenzoic acid.
(B) The photoinitiator illustrated above can be used individually or in combination of 2 or more types.

  (B) The content of the photopolymerization initiator is preferably in the range of 0.1 to 10% by mass with respect to the total mass of the component (A) and the component (B). On the other hand, the content of the component (A) is preferably in the range of 90 to 99.9% by mass. When the content of the component (B) is 0.1% by mass or more, the photosensitivity is sufficient. On the other hand, when the content is 10% by mass or less, only the surface of the optical waveguide is selectively cured, and the curing is insufficient. It is preferable that the propagation loss does not increase due to absorption of the polymerization initiator itself. From the above viewpoint, the content of the (B) photopolymerization initiator is more preferably 0.2 to 5% by mass.

Further, the resin composition of the present invention can further contain (C) a base polymer. (C) By containing a base polymer, it can be set as the film-form resin composition for optical materials, and is preferable.
That is, (A) a resin for an optical material comprising a resin composition for an optical material comprising a full orange (meth) acrylate represented by the above general formula (I), (B) a photopolymerization initiator, and (C) a base polymer. Films are also encompassed by the present invention. By making it into a film, film thickness control, which is complicated in liquid form, becomes easy, and productivity is greatly improved.
The base polymer of the component (C) is for forming a film and ensuring the strength of the film, and is not particularly limited as long as the object can be achieved. Phenoxy resin, (meth) acrylic resin , Polycarbonate resin, polyetherimide, polyethersulfone, epoxy resin and the like. These base polymers may be used alone or in combination of two or more.
Of the base polymers exemplified above, from the viewpoint of high heat resistance, the main chain preferably has an aromatic skeleton, and particularly preferably a phenoxy resin. Further, from the viewpoint of compatibility with (A) full orange (meth) acrylate, and improvement of photosensitivity / development characteristics, an epoxy resin, particularly an epoxy resin that is solid at room temperature can be preferably used.

  A phenoxy resin is an amorphous polymer generally obtained from diphenols and epihalohydrin, and has a repeating unit represented by the following general formula (III).

Here, n ′ is an integer of 1 or more, m ′ is 0 or 1, —R ₀ — is a group represented by the following general formulas (IV), (V), (VI), or —O—. .

Here, an organic group such as R ₁ to R ₁₀ each is H or CH _3, CF _3.
In particular, among the phenoxy resins represented by the general formula (III), a linear polymer of a bisphenol A type epoxy resin having a repeating unit represented by the following formula (VII) has high heat resistance. It is preferable.

The linear polymer phenoxy resin is generally produced by a one-stage method in which bisphenol A and epichlorohydrin are polycondensed, or a two-stage method in which a bifunctional epoxy resin and bisphenol A are polyaddition-reacted. Specific examples include “YP-50 (trade name)” manufactured by Toto Kasei Co., Ltd., Japanese Patent Laid-Open No. 4-120124, Japanese Patent Laid-Open No. 4-122714, and Japanese Patent Laid-Open No. 4-339852. There are things.
In addition to the phenoxy resin represented by the general formula (III), a high molecular weight product obtained by polyaddition reaction of various bifunctional epoxy resins and bisphenols, for example, brominated phenoxy resin (Japanese Patent Laid-Open No. 63-191826). Gazette, Japanese Patent Publication No. 8-26119), bisphenol A / bisphenol F copolymerization type phenoxy resin (Japanese Patent No. 2917884, Japanese Patent No. 2799401), phosphorus-containing phenoxy resin (Japanese Patent Laid-Open No. 2001-310939), fluorene High heat-resistant phenoxy resins into which a skeleton is introduced (Japanese Patent Laid-Open Nos. 11-269264 and 11-302373) are also known as phenoxy resins.

  In the resin composition of the present invention, as the epoxy resin solid at room temperature used as the component (A), for example, “Epototo YD-7020, Epototo YD-7019, Epototo 7017 (trade name)” manufactured by Toto Kasei Co., Ltd. Bisphenol A type epoxy resins such as “Epicoat 1010, Epicoat 1009, Epicoat 1008 (trade name)” manufactured by Japan Epoxy Resins Co., Ltd., and the like.

Next, the content of the (C) base polymer is preferably 10 to 80% by mass of the (C) component with respect to the total amount of the (A) component and the (C) component. On the other hand, the content of the component (A) is preferably 20 to 90% by mass. When the content of the component (C) is 10% by mass or more, a film having a thickness of about 50 μm can be easily produced, and when it is 80% by mass or less, the photocuring reaction proceeds sufficiently. From the above viewpoint, the content of the (C) base polymer is more preferably in the range of 20 to 70% by mass.
(C) Regarding the molecular weight of the base polymer, it is possible to form a film with a thickness of 50 μm or more required for the optical signal transmission optical waveguide between the boards in the router or server device. Is preferably 5,000 or more, more preferably 10,000 or more, and particularly preferably 30,000 or more. Although there is no restriction | limiting in particular about the upper limit of a number average molecular weight, From a compatible viewpoint with (A) component, it is preferable that it is 1,000,000 or less, Furthermore, 500,000 or less, Especially 200,000. The following is preferable. The number average molecular weight in the present invention is a value measured by gel permeation chromatography (GPC) and converted to standard polystyrene.

  The resin composition for an optical material of the present invention is obtained by dissolving the components (A) and (B) in a solvent. The solvent used here is not particularly limited as long as it can dissolve the resin composition. For example, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, cyclohexanone, methyl ethyl ketone, methyl Isobutyl ketone, γ-butyrolactone, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, acetone, toluene, or a mixed solvent thereof can be used. The resin concentration in the resin solution is usually preferably 30 to 80% by mass.

The resin for an optical material of the present invention is preferably used for at least one of a lower clad, a core and an upper clad of an optical waveguide.
Hereinafter, a method for producing an optical waveguide using the resin composition of the present invention will be described. As the method, for example, the resin composition is applied onto a substrate using a method such as a spin coating method, a dipping method, a spray method, a curtain coating method, a silk screen method, or a roll coating method, and then heated or dried under reduced pressure. After the solvent is removed by drying, etc., the resin is cured by irradiation with actinic rays or heating. This resin layer constitutes the cladding layer.
Next, a resin composition having a higher refractive index than that of the previously formed optical waveguide layer is applied by the same application method, and this is used as the core layer. Subsequently, actinic rays are irradiated through a negative or positive mask pattern, and after exposure, unexposed portions are removed and developed by wet development, dry development, or the like to produce a core pattern. Here, if necessary, the optical waveguide pattern may be further cured by heating at about 60 to 250 ° C. or exposure at about 0.1 to 1000 mJ / cm ² .
Thereafter, a resin having a refractive index lower than that of the core layer is applied and formed by the same method to produce an optical waveguide.

Below, the preparation methods of the resin film for optical materials of this invention and the preparation methods of an optical waveguide using the same are demonstrated.
The resin film for an optical material of the present invention can be easily produced by dissolving a resin composition containing the components (A) to (C) in a solvent, applying it to a substrate, and removing the solvent. The solvent used here is not particularly limited as long as it can dissolve the resin composition, and those listed as solvents for dissolving the components (A) and (B) described above can be used. Moreover, it is preferable that the resin content density | concentration in a resin solution is 30-80 mass% normally.

  When the resin film for optical materials of the present invention is used as a film for forming an optical waveguide, the thickness is not particularly limited, but is usually 10 to 100 μm after drying. When it is 10 μm or more, there is an advantage that the alignment tolerance can be increased in the coupling with the light emitting / receiving element or the optical fiber after the optical waveguide is formed, and when it is 100 μm or less, the coupling with the light emitting / receiving element or the optical fiber after the optical waveguide is formed. There is an advantage that the coupling efficiency is improved. From the above viewpoint, the thickness of the film is preferably in the range of 30 to 70 μm.

The substrate used in the production process of the resin film for optical material of the present invention is a support for supporting the resin film for optical material, and the material is not particularly limited, but the resin film for optical material is peeled later. From the viewpoint of being easy and having heat resistance and solvent resistance, polyesters such as polyethylene terephthalate, polypropylene, polyethylene and the like are preferable.
The thickness of the substrate is preferably 5 to 50 μm. When it is 5 μm or more, there is an advantage that the strength as a support is easily obtained, and when it is 50 μm or less, there is an advantage that a gap with the mask at the time of pattern formation becomes small and a finer pattern can be formed. From the above viewpoint, the thickness of the base material is preferably 10 to 40 μm, and more preferably 20 to 30 μm.
The resin film for an optical material provided on the substrate thus obtained can be easily stored, for example, by winding it into a roll. Moreover, a protective film can also be provided on the resin film for optical materials as needed. In addition, in order to make peeling of the resin film for optical materials easy later, the base material and the protective film may be subjected to antistatic treatment or the like.

The resin film for optical material of the present invention is preferably used for at least one of a lower clad, a core and an upper clad of an optical waveguide.
Hereafter, the manufacturing method for forming an optical waveguide using the resin film for optical materials of this invention is explained in full detail. As the method, for example, in the case where a protective film is present, a method of laminating the lower clad film on the substrate by thermocompression after the protective film is peeled off can be mentioned. Here, it is preferable to laminate | stack under reduced pressure from the viewpoint of adhesiveness and followable | trackability. The heating temperature of the film is preferably 50 to 130 ° C., and the pressing pressure is preferably 0.1 to 1.0 MPa (about 1 to 10 kgf / cm ² ), but these conditions are particularly limited. There is no.
Next, the lower clad film is cured by light or heating, and a core film having a refractive index higher than that of the lower clad film is laminated by the same method. After laminating in this way, actinic rays are irradiated in an image form through a negative or positive mask pattern. Examples of the active light source include known light sources that effectively emit ultraviolet rays, such as carbon arc lamps, mercury vapor arc lamps, ultrahigh pressure mercury lamps, high pressure mercury lamps, and xenon lamps. In addition, those that effectively emit visible light, such as a photographic flood bulb and a solar lamp, can be used.

Next, the unexposed portion is removed and developed by wet development or the like to form a waveguide pattern. In the case of wet development, development is performed by a known method such as spraying, rocking immersion, brushing, and scraping using a developer such as an organic solvent suitable for the composition of the film.
Examples of organic solvent developers include N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, γ-butyrolactone, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl Examples include ether. These organic solvents preferably add water in the range of 1 to 20 parts by mass in order to prevent ignition. Moreover, you may use together 2 or more types of image development methods as needed. Examples of the development method include a dip method, a battle method, a spray method such as a high-pressure spray method, brushing, and scraping. The high-pressure spray method is most suitable for improving the resolution.
As the treatment after development, the optical waveguide pattern may be further cured and used by heating at about 60 to 250 ° C. or exposure at about 0.1 to 1000 mJ / cm ² as necessary.
Thereafter, an upper clad film having a refractive index lower than that of the core film is laminated by the same method to produce an optical waveguide.

Hereinafter, the present invention will be described in more detail with reference to examples relating to optical waveguides, but the present invention is not limited to these examples. In the following Examples, the optical material resin composition of the present invention is referred to as an optical waveguide forming resin composition, and the optical material resin film is referred to as an optical waveguide forming resin film.
Example 1
Full orange acrylate (trade name “A-BPEF” manufactured by Shin-Nakamura Chemical Co., Ltd.) and photopolymerization initiator (“2,2-bis (2-chlorophenyl) -4,4 ′ manufactured by Tokyo Chemical Industry Co., Ltd.) , 5,5'-tetraphenyl 1,2'-biimidazole ","4,4'-bis (diethylamino) benzophenone "made by the company, and" 2-mercaptobenzimidazole "made by the company 2 mass%), and 30 parts by mass of N, N-dimethylacetamide as a solvent is added to 100 parts by mass of the total amount of full orange acrylate and photoinitiator to prepare a resin composition for forming an optical waveguide. did. Next, a resin layer is formed on a silicon wafer (thickness 1 mm) with a thermal oxide film (thickness 1 μm) by spin coating, and a solvent is added at 80 ° C. for 10 minutes and then at 100 ° C. for 10 minutes. Removed dry. Subsequently, the resin layer was irradiated with 1 mJ / cm ² of ultraviolet light from a high-pressure mercury lamp, the resin was photocured, and further post-baked at 160 ° C. for 1 hour to form a slab optical waveguide (core thickness 10 μm). Obtained. The refractive index of the slab optical waveguide (core) at this time was 1.613 when measured using a prism coupler (Model 2020) manufactured by Metricon (measurement wavelength: 830 nm). Moreover, the thermal decomposition temperature of this slab optical waveguide measured by ULGD and TGD-7000 was about 300 degreeC, and it turned out that it has high heat resistance.
The slab optical waveguide was passed through a solder reflow furnace (Furukawa Electric Co., Ltd., “Salamanda”) three times under the conditions of a maximum ultimate temperature of 265 ° C. (a holding time of 260 ° C. or higher, 15 to 20 seconds) and a nitrogen atmosphere. I let it pass. Results of measurement of propagation loss before and after reflow using a prism coupler type optical characteristic measuring device (SAIRON TECHNOLOGY, SPA-4000) (measurement wavelength: 830 nm, using matching oil of nD = 1.62), propagation loss before and after reflow Were 0.1 dB / cm and 0.1 dB / cm, respectively. It can be seen that the resin composition for forming an optical waveguide of the present invention has high heat resistance and low loss. In this embodiment, the thermal oxide film serves as a lower clad and air serves as an upper clad.

Example 2
Full orange acrylate (made by Shin-Nakamura Chemical Co., Ltd., trade name “A-BPEF”) and phenoxy resin (made by Toto Kasei Co., Ltd., trade name “Phenotote YP-50”) as a base polymer are used. In addition to 80% by mass of acrylate and 20% by mass of phenoxy resin, photoinitiator (manufactured by Tokyo Chemical Industry Co., Ltd., 2,2-bis (2-chlorophenyl)- Generation of ternary photoradicals consisting of 4,4 ', 5,5'-tetraphenyl 1,2'-biimidazole, the company's 4,4'-bis (diethylamino) benzophenone, and the company's 2-mercaptobenzimidazole 2 parts by mass of (agent) was added, and 40 parts by mass of methyl ethyl ketone as a solvent was added thereto to prepare a resin composition for forming an optical waveguide. This was applied on a PET film (Toyobo Co., Ltd., trade name “A-4100”) using an applicator (Yoshimi Seiki Co., Ltd., “YBA-4”), 80 ° C., 10 minutes, and then 100 ° C. The solvent was removed by drying in 10 minutes to obtain a resin film for forming an optical waveguide, and the thickness of the resin film for forming an optical waveguide was adjusted to 5 to 100 μm by adjusting the gap between the applicators. In this embodiment, the thickness can be adjusted to 12 μm.
The resin film for forming an optical waveguide is placed on a silicon wafer (thickness 1 mm) with a thermal oxide film (thickness 1 μm) using a vacuum pressurizing laminator (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd.) with a pressure of 0. .4 MPa, laminated at 60 ° C., and “EXM-7172-B-00” manufactured by Oak Manufacturing Co., Ltd., was irradiated with ultraviolet rays at 1 J / cm ² to photocur the resin. Post-baking was performed for 1 hour to obtain a slab optical waveguide (core thickness: 12 μm). The refractive index of the slab optical waveguide (core) at this time was 1.607 at a measurement wavelength of 830 nm. Next, this was passed through a solder reflow furnace (Furukawa Electric Co., Ltd., “Salamanda”) three times under the conditions of maximum temperature 265 ° C. (holding time 15 to 20 seconds above 260 ° C.) and nitrogen atmosphere. It was.
Results of measurement of propagation loss before and after reflow using a prism coupler type optical characteristic measuring device (SAIRON TECHNOLOGY, SPA-4000) (measurement wavelength: 830 nm, using matching oil of nD = 1.62), propagation loss before and after reflow Were 0.2 dB / cm and 0.2 dB / cm, respectively. It can be seen that the resin film for forming an optical waveguide of the present invention has high heat resistance and low loss.

Example 3
In Example 2, instead of the phenoxy resin, a slab was obtained in the same manner as in Example 2 except that a solid epoxy resin (trade name “Epototo YD-7020” manufactured by Toto Kasei Co., Ltd.) was used at room temperature. An optical waveguide was obtained. The refractive index of the slab optical waveguide (core) at this time was 1.604 at a measurement wavelength of 830 nm. Next, this was passed through a solder reflow furnace (Furukawa Electric Co., Ltd., “Salamanda”) three times under the conditions of maximum temperature 265 ° C. (holding time 15 to 20 seconds above 260 ° C.) and nitrogen atmosphere. It was. Results of measurement of propagation loss before and after reflow using a prism coupler type optical characteristic measuring device (SAIRON TECHNOLOGY, SPA-4000) (measurement wavelength: 830 nm, using matching oil of nD = 1.62), propagation loss before and after reflow Were 0.2 dB / cm and 0.2 dB / cm, respectively. It can be seen that the resin film for forming an optical waveguide of the present invention has high heat resistance and low loss.

Example 4
A resin composition having the same composition as the resin composition for forming an optical waveguide described in Example 1 was prepared, and 40 parts by mass of methyl ethyl ketone was added as a solvent to the total amount to prepare a resin varnish. This was applied onto a PET film (product name “A-4100” manufactured by Toyobo Co., Ltd.) using an applicator (“YBA-4” manufactured by Yoshimitsu Seiki Co., Ltd.), and then at 80 ° C. for 10 minutes. The solvent was dried at 100 ° C. for 10 minutes to obtain a resin film for an optical material. The thickness of the resin film for optical material at this time can be arbitrarily adjusted between 5 and 100 μm by adjusting the gap of the applicator. In this embodiment, the thickness after curing is 10 μm. Adjusted.
Using a vacuum pressurizing laminator (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd.), the resin film for optical material was placed on a silicon substrate under the conditions of pressure 0.5 MPa, temperature 50 ° C., pressurization time 30 seconds. Laminated.
The refractive index and birefringence of the resin film were measured using a prism coupler (Model 12020) manufactured by Metricon (measurement wavelength: 830 nm). The results are shown in Table 1.
Further, a resin film for optical material was obtained in the same manner as described above except that the thickness was set to 70 μm, the optical material resin film was laminated on a silicon substrate, and a spectrophotometer (model U-3410) manufactured by Hitachi, Ltd. was obtained. ) Was used to measure the light transmittance. A transmittance of 90% or more was exhibited in the visible region of 400 to 800 nm.
As described above, the optical material is an optical material having a high refractive index but low birefringence and excellent transparency.

Example 5
A resin film for an optical material was obtained using a resin composition having the same composition as the optical waveguide forming resin composition described in Example 2, and the refractive index and birefringence were measured in the same manner as in Example 4. The results are shown in Table 1. Further, when the light transmittance was measured in the same manner as in Example 4, it showed a transmittance of 90% or more in the visible region of 400 to 800 nm. It can be seen that the optical material has a high refractive index but low birefringence and excellent transparency.

Example 6
A resin film for an optical material was obtained using a resin composition having the same composition as the resin composition for forming an optical waveguide described in Example 3, and the refractive index and birefringence were measured in the same manner as in Example 4. The results are shown in Table 1. Further, when the light transmittance was measured in the same manner as in Example 4, it showed a transmittance of 90% or more in the visible region of 400 to 800 nm. It can be seen that the optical material has a high refractive index but low birefringence and excellent transparency.

  The resin composition for optical material of the present invention and the resin film for optical material comprising the resin composition are excellent in transparency and heat resistance. For example, optical waveguide, lens, optical sealing material, optical adhesive, light guide plate In particular, it can be used as a diffraction grating, and can be suitably used as a resin composition for an optical waveguide and a resin film for an optical waveguide. It can also be used for other coating materials, resists and the like. By using the resin composition of the present invention for at least one of the core, lower clad, or upper clad of the optical waveguide, an optical waveguide with excellent performance can be obtained. Further, by using the resin film for optical material of the present invention, it is possible to produce an optical waveguide with high productivity.

Claims (6)

(A) fluorene (meth) acrylate represented by the following formula (I), a (B) a photopolymerization initiator, and (C) including a base polymer, an optical waveguide material for the resin composition, (C ) A resin composition for an optical waveguide material, wherein the base polymer is a phenoxy resin having a number average molecular weight of 5,000 or more.

(X is represented by the following formula (II), Y is hydrogen or a methyl group, and m and n are each an integer of 1 to 20.)

(R1 to R16 are each independently hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms in total, an aryl group having 6 to 10 carbon atoms, or (It is an aralkyl group having 7 to 9 carbon atoms.)   The content of the component (A) is 90.0 to 99.9% by mass relative to the total amount of the component (A) and the component (B), and the content of the component (B) is 0.1 to 10.0. The resin composition for an optical waveguide material according to claim 1, wherein the resin composition is in mass%.   The content of the component (A) is 20 to 90% by mass, the content of the component (C) is 10 to 80% by mass with respect to the total amount of the component (A) and the component (C), and (A The resin composition for an optical waveguide material according to claim 1 or 2, wherein the content of the component (B) is 0.1 to 5 parts by mass relative to 100 parts by mass of the total amount of the component (C) and the component (C). (C) The number average molecular weight of a base polymer is 10,000 or more, The resin composition for optical waveguide materials in any one of Claims 1-3. The resin film for optical waveguide materials which consists of a resin composition for optical waveguide materials in any one of Claims 1-4 . The resin composition for an optical waveguide material according to any one of claims 1 to 4 or the resin film for an optical waveguide material according to claim 5 is applied to at least one of a lower clad, a core, and an upper clad of the optical waveguide. The optical waveguide used.