JP2005290106A - Photosensitive resin composition for optical waveguide formation, and optical waveguide formed using the same - Google Patents

Abstract

（式中、Ｒ^１〜Ｒ^３は炭素数１〜５のアルキル基であり、Ｒ^４は水素原子又はメチル基であり、ｎは５〜５０の数を表す。）
で示される化合物、
重合性化合物、及び
光重合開始剤
を含有する光導波路形成用感光性樹脂組成物；及びそれを用いた光導波路。
【選択図】 図１
PROBLEM TO BE SOLVED: To provide a photosensitive resin composition for forming an optical waveguide which can form a coating film having excellent coating properties without being subjected to pretreatment and at the same time has excellent adhesion to a substrate.
The following formula (1)
[Chemical 1]

^(Wherein, R 1 to R ³ is an alkyl group of 1 to 5 carbon atoms, ^{R 4} is a hydrogen atom or a methyl radical, n represents a number of 5-50.)
A compound represented by
A photosensitive resin composition for forming an optical waveguide containing a polymerizable compound and a photopolymerization initiator; and an optical waveguide using the same.
[Selection] Figure 1

Description

  The present invention relates to a photosensitive resin composition for forming an optical waveguide for producing an optical circuit used in the fields of optical communication and optical information processing, and an optical waveguide produced using the composition.

  In the multimedia era, in response to demands for large capacity and high speed information processing in optical communication systems and computers, transmission systems using light as a transmission medium are public communication networks, LAN (local area networks), FA (factory automation). ), Being used for interconnects between computers, home wiring, and the like. Among the elements constituting this transmission system, the optical waveguide is, for example, an optical device, an optical integrated circuit (OEIC), an optical integrated circuit (optical IC) and the like. Optical waveguides are intensively studied due to the large amount of demand, and in particular, high performance and low cost products are required.

Conventionally known silica optical waveguides and polymer optical waveguides are known as optical waveguides.
Among these, the quartz-based optical waveguide has an advantage that the transmission loss is low, but has a problem in process such as high processing temperature in the manufacturing process and difficulty in manufacturing a large area.
Also, polymer-based optical waveguides have advantages such as ease of processing and wide material design. Therefore, those using polymer materials such as polymethyl methacrylate and polycarbonate have been studied. However, in general, a polymer-based optical waveguide has a problem that heat resistance is poor. Therefore, recently, fluorinated polyimides having excellent heat resistance and transmission loss have been actively studied.

However, when a polymer material is used, when the core portion in the optical waveguide is manufactured, a dry etching process is required as in the case of the silica-based optical waveguide. is there.
Under such circumstances, in recent years, a photocurable material such as an epoxy-based ultraviolet curable resin imparted with photolithography properties and an optical waveguide using the material have been proposed (for example, see Patent Document 1).

In addition, with conventional materials, depending on the type of substrate material (base material) and the surface condition, “repelling” and “unevenness” of the resin composition may occur during coating, and a uniform coating film may not be obtained. It was. Therefore, it is necessary to pre-treat the substrate (chemical treatment such as primer treatment, physical treatment such as ultraviolet irradiation / plasma treatment / ozone treatment) before applying the material.
Furthermore, even if coating properties such as repellency are good, if the adhesion to the substrate is not good, the resin composition will be peeled off from the substrate and transmission loss will be increased. There was also a problem that reliability was impaired.

JP-A-6-273631 (Claim 1)

  In view of the above problems, the present invention provides a photosensitive resin composition for forming an optical waveguide that can form a coating film excellent in coatability without being subjected to pretreatment, and also has excellent adhesion to a substrate. With the goal.

  In order to achieve the above-mentioned object, the present inventors have eagerly searched for an additive (surfactant) that can suppress the repelling of the resin composition by the substrate, and as a result, have found an additive (surfactant) having a specific structure. By adding it to the material, it was found that a coating film having excellent coating properties such as repelling can be formed without pretreatment, and at the same time, the adhesiveness with the substrate was found to be good, and the present invention was completed.

（式中、Ｒ^１〜Ｒ^３は炭素数１〜５のアルキル基であり、Ｒ^４は水素原子又はメチル基であり、ｎは５〜５０の数を表す。）
で示される化合物、
重合性化合物、及び
光重合開始剤
を含有する光導波路形成用感光性樹脂組成物；
［２］前記式（１）で示される化合物を、重合性化合物１００質量部に対して０．００１〜１０質量部含有する、上記［１］に記載の光導波路形成用感光性樹脂組成物；及び
［３］コア層及びクラッド層とを有する光導波路であって、該コア層及び該クラッド層のいずれか一方又は両方が、上記［１］又は［２］に記載の光導波路形成用感光性樹脂組成物からなる光導波路
を提供する。 That is, the present invention
[1] The following formula (1)

^(Wherein, R 1 to R ³ is an alkyl group of 1 to 5 carbon atoms, ^{R 4} is a hydrogen atom or a methyl radical, n represents a number of 5-50.)
A compound represented by
A photosensitive resin composition for forming an optical waveguide comprising a polymerizable compound and a photopolymerization initiator;
[2] The photosensitive resin composition for forming an optical waveguide according to the above [1], which contains 0.001 to 10 parts by mass of the compound represented by the formula (1) with respect to 100 parts by mass of the polymerizable compound; And [3] an optical waveguide having a core layer and a clad layer, wherein either or both of the core layer and the clad layer are photosensitive for optical waveguide formation according to the above [1] or [2] An optical waveguide comprising a resin composition is provided.

Even if the resin composition for forming an optical waveguide of the present invention is not subjected to the above pretreatment, the repelling is suppressed and a uniform coating film is obtained. Therefore, a waveguide with a large area can be manufactured at a low cost.
Moreover, since the coating film formed from the resin composition of this invention has favorable adhesiveness with a board | substrate, the optical waveguide excellent in long-term reliability can be provided also in the preservation | save on various environmental conditions.

（式中、Ｒ^１〜Ｒ^３は炭素数１〜５のアルキル基であり、Ｒ^４は水素原子又はメチル基であり、ｎは５〜５０の数を表す。）
で示される化合物、
重合性化合物、及び
光重合開始剤
を含有することを特徴とする。 Hereinafter, the present invention will be described in detail.
A. Photosensitive resin composition for forming an optical waveguide The photosensitive resin composition for forming an optical waveguide of the present invention (hereinafter referred to as the resin composition of the present invention) is represented by the following formula (1).

^(Wherein, R 1 to R ³ is an alkyl group of 1 to 5 carbon atoms, ^{R 4} is a hydrogen atom or a methyl radical, n represents a number of 5-50.)
A compound represented by
It contains a polymerizable compound and a photopolymerization initiator.

  In the specification of the present application, the resin composition of the present invention is a liquid composition containing a compound represented by the above formula (1) and a liquid form before curing and a compound represented by the above formula (1). Has a concept including both cured forms.

で示される。
式（１）において、Ｒ^１は、炭素数１〜５のアルキル基であり、好ましくは炭素数１〜３のアルキル基、特に好ましくはエチル基である。
Ｒ２は、炭素数１〜５のアルキル基であり、好ましくは炭素数１〜３のアルキル基、特に好ましくはメチル基である。
Ｒ^３は、炭素数１〜５のアルキル基であり、好ましくは炭素数１〜３のアルキル基、特に好ましくはエチル基である。
Ｒ^４は水素原子又はメチル基であり、好ましくはメチル基である。
ｎは５〜５０の数を表し、好ましくは５〜４５、より好ましくは１５〜４０である。 1. Compound represented by Formula (1) The compound used in the present invention and having an action of suppressing repellency is represented by the following formula (1).

Indicated by
In the formula (1), R ¹ is an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably an ethyl group.
R2 is an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.
R ³ is an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, particularly preferably an ethyl group.
R ⁴ is a hydrogen atom or a methyl group, preferably a methyl group.
n represents the number of 5-50, Preferably it is 5-45, More preferably, it is 15-40.

  The compound represented by the above formula (1) constituting the resin composition of the present invention is a relatively high molecular weight quaternary polyether ammonium salt type cationic surfactant having a polyoxypropylene chain as a lipophilic group. . Such compounds have conventionally been widely used as conditioning ingredients in hair care products such as shampoos and rinses, and have the effect of improving the low-temperature fluidity of the compounding system, and as detergent formulations. It is.

で示される、旭電化工業社製のアデカコールＣＣシリーズを挙げることができる。
アデカコールＣＣ−１５（上記式（２）において、ｎ＝１５）
アデカコールＣＣ−３６（上記式（２）において、ｎ＝２５）
アデカコールＣＣ−４２（上記式（２）において、ｎ＝４０） Commercially available products may be used as the compound represented by the above formula (1), and preferred specific examples thereof include, for example, the following formula (2).

The Adeka Coal CC series manufactured by Asahi Denka Kogyo Co., Ltd. can be mentioned.
ADEKA COAL CC-15 (n = 15 in the above formula (2))
Adeka Coal CC-36 (in the above formula (2), n = 25)
Adeka Coal CC-42 (in the above formula (2), n = 40)

The compounding ratio of the compound represented by the above formula (1) in the resin composition of the present invention should be appropriately selected depending on the type of the resin used and the base material, and is generally 0 with respect to 100 parts by mass of the polymerizable compound. 0.001 to 10 parts by mass, preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass. If the compounding ratio of the compound represented by the formula (1) is too small, the effects of suppressing the desired repellency and good adhesion to the substrate may not be exhibited. May cause problems in reliability.
The compounds represented by the above formula (1) may be used singly or in combination of two or more.

2. Polymerizable compound The polymerizable compound constituting the resin composition of the present invention is not particularly limited, and any conventionally known resin and resin composition may be used as the photosensitive resin used for forming the optical waveguide. Specifically, for example, a polymerizable monomer having an ethylenically unsaturated double bond, an oligomer containing a (meth) acryl group, a (meth) acrylic resin having a polymerizable group, glycidyl ether, cyclohexene oxide, or oxetane. Examples thereof include an epoxy resin.
The polymerizable compound is preferably one or a combination of two or more selected from the following. Here, a (meth) acrylic resin is preferable from the viewpoint of curability and imparting flexibility to a cured product.

  Examples of the polymerizable monomer having an ethylenically unsaturated double bond include a polymerizable monofunctional compound or a polymerizable polyfunctional compound. As such a polymerizable monofunctional compound, vinyl group-containing lactams such as N-vinylpyrrolidone and N-vinylcaprolactam, isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, (Meth) acrylate having an alicyclic structure such as dicyclopentanyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, (meth) acrylate having an aromatic ring structure such as benzyl (meth) acrylate, acryloylmorpholine, Vinylimidazole, vinylpyridine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, pro (Meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, Hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, Undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, tetrahydro Rufuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate , Ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, t- Octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate Acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, N, N-diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2 -Ethylhexyl vinyl ether can be mentioned.

  Examples of the polymerizable polyfunctional compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and polyethylene glycol di (meth). ) Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tris (2 -Hydroxyethyl) isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, bis Di (meth) acrylate of ethylene oxide or propylene oxide adduct diol of enol A, di (meth) acrylate of ethylene oxide or propylene oxide adduct diol of hydrogenated bisphenol A, (meth) acrylate to diglycidyl ether of bisphenol A Added epoxy (meth) acrylate, triethylene glycol divinyl ether, and the like.

  Moreover, as a commercial item, for example, light acrylate 9EG-A and light acrylate 4EG-A (manufactured by Kyoeisha Chemical Co., Ltd.), Iupimer UV SA1002, SA2007 (above, manufactured by Mitsubishi Chemical Corporation); Biscote 700 (Osaka) KAYARAD R-604, DPCA-20, -30, -60, -120, HX-620, D-310, D-330 (above, Nippon Kayaku Co., Ltd.); Aronix M-210, M-215, M-315, M-325 (above, Toagosei Co., Ltd. product) etc. are mentioned.

  These polymerizable monofunctional compounds and polymerizable polyfunctional compounds may be used alone or in combination.

  Examples of the oligomer containing a (meth) acryl group include a urethane (meth) acrylate oligomer.

  Examples of the (meth) acrylic resin having a polymerizable group include methacryloyl group-containing polymethacrylate.

  The compounding ratio of the polymerizable compound in the resin composition of the present invention is usually 90 to 99% by mass, preferably 93 to 99% by mass, and more preferably 94 to 98% by mass with respect to the total amount of the composition. is there. If the resin component is too small, the cured product may contain a large amount of uncured component, which may deteriorate the reliability. Conversely, if the resin component is too large, it can be obtained by adding the compound represented by the above formula (1). The effect is impaired.

3. Photopolymerization initiator The photopolymerization initiator constituting the resin composition of the present invention is not particularly limited, and any conventionally known compound may be used as a photopolymerization initiator used for forming an optical waveguide. Specifically, for example, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2,2-dimethoxy-2 -Phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, Benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl 1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, and the like.
Commercially available photopolymerization initiators include, for example, Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI 11850, CG 24-61, Darocurl 116, 1173 (above, Ciba Specialty Chemicals ( Co., Ltd.), Lucirin LR8728 (manufactured by BASF) and Ubekrill P36 (manufactured by UCB), among which Irgacure 184 is particularly preferred.

  The blending ratio of the component (C) in the resin composition of the present invention is usually 0.01 to 10 parts by weight, preferably 0.5 to 7 parts by weight with respect to 100 parts by weight of the polymerizable compound. By setting the blending ratio to 10 parts by weight or less, curing characteristics, transmission characteristics, patterning properties, handling properties, and the like can be improved. Moreover, by making this compounding ratio 0.01 parts by weight or more, the patterning property, the mechanical properties of the cured product, etc. can be improved, and the decrease in the curing rate can be prevented.

4). Optional addition component In addition to the above components, the optional addition component includes, for example, a photosensitizer, an antioxidant, an ultraviolet absorber, a light stabilizer, a silane coupling agent, and a coating surface improving agent. In addition, a thermal polymerization inhibitor, a leveling agent, a surfactant, a colorant, a storage stabilizer, a plasticizer, a lubricant, a solvent, a filler, an anti-aging agent, a wettability improver, a release agent and the like can be blended.

Specific examples of the photosensitizer include, for example, triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethyl. Examples thereof include isoamyl aminobenzoate.
Specific examples of commercially available photosensitizers include, for example, Ubekrill P102, 103, 104, 105 (above, manufactured by UCB).

Here, as commercially available products of antioxidants, for example, Irganox 1010, 1035, 1076, 1222 (above, manufactured by Ciba Specialty Chemicals), Antigen P, 3C, FR, GA-80 (Sumitomo Chemical Industries ( Etc.).
Examples of commercially available ultraviolet absorbers include Tinuvin P, 234, 320, 326, 327, 328, 329, 213 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Seesorb 102, 103, 110, 501, 202. 712, 704 (manufactured by Sipro Kasei Co., Ltd.).

Commercially available light stabilizers include, for example, Tinuvin 292, 144, 622LD (manufactured by Ciba Specialty Chemicals Co., Ltd.), Sanol LS770 (manufactured by Sankyo Co., Ltd.), Sumisorb TM-061 (Sumitomo Chemical ( Etc.).
Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and the like. Examples of commercially available products include SH6062, 6030 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.), KBE903, 603, 403 (above, manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

  Examples of the coating surface improving agent include silicone additives such as dimethylsiloxane polyether. Commercially available products include DC-57, DC-190 (above, manufactured by Dow Corning), SH-28PA, SH-29PA, SH-30PA, SH-190 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.) KF351, KF352, KF353, KF354 (manufactured by Shin-Etsu Chemical Co., Ltd.), L-700, L-7002, L-7500, FK-024-90 (manufactured by Nihon Unicar Co., Ltd.) and the like. It is done.

5). Liquid resin composition of the present invention The resin composition of the present invention can be produced by mixing the above-mentioned components by a conventional method. Specifically, the above components may be charged into a reaction vessel and stirred at 50 to 80 ° C. until a transparent liquid is obtained.

  The viscosity of the liquid resin composition of the present invention prepared as described above is usually 100 to 20,000 cp / 25 ° C, preferably 300 to 10,000 cp / 25 ° C, more preferably 400 to 5,000 cp. / 25 ° C. If the viscosity of the composition is too high, coating unevenness and undulation will occur when the composition is applied to the substrate, or the patterning property will deteriorate when the core layer is formed, and the desired shape will not be obtained. On the other hand, even if the viscosity is too low, it is difficult to obtain the target film thickness and the patterning property may be deteriorated.

6). It is possible to obtain a cured product (a resin composition of the present invention which is a cured product) by irradiating the resin composition of the present invention obtained as described in 5 above with radiation. it can. Examples of the radiation used include infrared rays, visible rays, ultraviolet rays, X-ray α rays, β rays, and γ rays, and ultraviolet rays are preferable.

  When the resin composition of the present invention is a cured product obtained by curing with radiation, it preferably has the following physical properties. When the resin composition of the present invention which is a cured product is used as a core layer of an optical waveguide, the refractive index at 25 ° C. and a wavelength of 824 nm is preferably 1.54 or more, and more preferably 1.55 or more. It is more preferable. When the refractive index is less than 1.54, when a waveguide is formed using the resin composition of the present invention for the core layer, good transmission loss may not be obtained.

  The resin composition of the present invention that is a cured product preferably has a glass transition temperature of 80 ° C. or higher, and more preferably 90 ° C. or higher. If the glass transition temperature is less than 80 ° C., sufficient heat resistance of the optical waveguide may not be ensured. Here, the “glass transition temperature” is defined as the temperature at which the loss tangent at the vibration frequency of 10 Hz shows the maximum value in the resonance type dynamic viscoelasticity measuring apparatus.

B. The optical waveguide of the present invention is an optical waveguide having a core layer and a clad layer formed by laminating on the core layer, and one or both of the core layer and the clad layer are the above-mentioned It consists of the resin composition of this invention, It is characterized by the above-mentioned. By using the resin composition of the present invention, an optical waveguide with low transmission loss, high adhesion to the substrate, and high long-term reliability can be obtained.

The manufacturing method of the optical waveguide of this invention is not specifically limited, A well-known method can be used. Specifically, the optical waveguide is manufactured as follows.
FIG. 1 is a cross-sectional view schematically showing an example of an optical waveguide including a clad layer made of the photosensitive composition of the present invention.
In FIG. 1, the optical waveguide 1 includes a substrate 10 such as a silicon wafer, a lower cladding layer 12, an upper cladding layer 16, and a core portion 14 protected by these cladding layers 12 and 16. Among these, any one or both of the lower clad layer 12 and the upper clad layer 16 are formed using the photosensitive composition of the present invention.

An example of a method for producing the optical waveguide 1 is as follows.
First, the resin composition of the present invention is applied to the surface of the substrate 10 by spin coating, and cured by irradiating with ultraviolet rays to form the lower cladding layer 12. And the other photosensitive resin composition for core part formation is apply | coated on the lower clad layer 12, and an ultraviolet-ray is irradiated through the photomask which has a predetermined line pattern from upper direction. As a result, only the portion irradiated with the ultraviolet light is cured, and the other uncured portion is removed by the developer to obtain the core portion 14.
Next, the optical waveguide 1 is completed when the resin composition of the present invention is applied to the upper surfaces of the lower cladding layer 12 and the core portion 14 and cured by irradiating with ultraviolet rays to form the upper cladding layer 16.

  In the production of the optical waveguide of the present invention, it is preferable to use a substrate, but the material (base material) of the substrate is not particularly limited and may be appropriately selected from known ones. Specifically, a silicon wafer, a glass plate, a polyimide substrate, a glass epoxy substrate, etc. are mentioned, and a silicon wafer, a glass epoxy substrate, etc. are preferable.

  The structure of the optical waveguide of the present invention is not particularly limited, and may have any known structure. As a typical structure, for example, the structure shown in FIG.

  The optical waveguide of the present invention has excellent optical transmission characteristics and excellent reliability characteristics required for the waveguide.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to these Examples. In the following description, “parts” and “%” represent parts by mass and mass%, respectively, unless otherwise specified.

(Preparation of photosensitive resin composition for optical waveguide formation)
Example 1
Each component described in Table 1 below was added to a flask and stirred at 60 ° C. until a uniform transparent liquid was obtained, to obtain a liquid resin composition (Resin 1).

Examples 2 and 3 and Comparative Examples 1 and 2
Liquid resin compositions (resins 2 to 5) were obtained in the same manner as in Example 1 except that the types and ratios of the components to be added were changed as shown in Table 1 below.

<Measurement method of refractive index>
About the cured film which hardened | cured the liquid resin composition (resin 1-5) obtained in Examples 1-3 and Comparative Examples 1 and 2, the refractive index in 824 nm was measured with the following method. First, the liquid resin compositions (resins 1 to 5) obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were formed on a 4-inch silicon wafer substrate while adjusting the rotation speed and time using a spin coater. ) To a thickness of 7 μm to form a resin composition layer, and then irradiated with 1.0 J / cm ² of UV light from the mask aligner to the resin composition layer in a nitrogen atmosphere to obtain a cured film. . Next, the refractive index (824 nm, 25 ° C.) of this cured film was measured using a prism coupler made by Nippon Metricon.

<Evaluation method of coatability>
A resin composition layer was formed by applying a resin composition to a thickness of 50 μm on a 4-inch silicon wafer substrate while adjusting the number of rotations and time using a spin coater. It was left for 10 minutes at a humidity of 25%. After leaving, “x” indicates that “repelling” or “unevenness” was observed on the surface of the coating film, and “◯” indicates that no “repelling” or “unevenness” was observed.

The abbreviations in Table 1 indicate the following.
CC-15: Compound of the above formula (2), n = 15 (manufactured by Asahi Denka Kogyo Co., Ltd., quaternary polyether ammonium salt; Adekacol CC-15)
CC-42: In the above formula (2), n = 40 compound (Asahi Denka Kogyo Co., Ltd., quaternary polyether ammonium salt; Adekacol CC-42)
AA-6: Polymethyl methacrylate (PMMA) containing methacryloyl group (manufactured by Toagosei; Macromer AA-6)
V779: Tetrabromobisphenol A type epoxy diacrylate (manufactured by Nippon Iupika; Neopol V779)
TCDDA: Tricyclodecane dimethanol diacrylate (Mitsubishi Chemical; SA1002)
BR-31: Tribromophenoxyethyl acrylate (Daiichi Kogyo Seiyaku; New Frontier BR-31)
VP: N-vinylpyrrolidone (manufactured by BASF; VP)
NDDA: 1,9-nonanediol diacrylate (Daiichi Kogyo Seiyaku; LC9A)
IBXMA: Isobornyl methacrylate (manufactured by Osaka Organic Chemicals; IB-X)
Irg. 184: Cyclohexyl acetophenone (manufactured by Ciba Specialty Chemicals; Irgacure 184)
A203F: Polyoxyalkylene alkyl ether phosphate ester (Daiichi Kogyo Seiyaku; Prisurf A203F)
264-WAX: modified aliphatic dimethylethylammonium ethosulphate (manufactured by NOF; Elegan 264-WAX)

  From the results shown in Table 1, the resin compositions of Comparative Examples 1 and 2 to which an additive (surfactant) other than the compound represented by the formula (1) is added have poor coatability on a substrate, particularly a silicon wafer. On the other hand, in the resin compositions of Examples 1 to 3 to which the compound represented by the formula (1) was added, the coating property was good, and the application to the substrate was achieved by the addition of the compound represented by the formula (1). It can be seen that the performance is improved.

(Production of optical waveguide)
Examples 4 to 6, Comparative Examples 3 and 4
Using a spin coater, the resin 2 prepared in Example 2 was applied to a thickness of 50 μm on a 4-inch silicon wafer substrate while adjusting the number of revolutions and time. Layer) was irradiated with 1.0 J / cm ² of ultraviolet light from a mask aligner under an air atmosphere. Next, after applying the resin 1 prepared in Example 1 to a thickness of 50 μm on the lower clad layer using a spin coater, 1.0 J / cm ² of ultraviolet light in an air atmosphere was applied to 50 μm. The coating layer was irradiated through a photomask having a linear shape with no branching in width. The coated layer after irradiation was developed with acetone for 3 minutes, and then the substrate was heated in an oven set at 70 ° C. for 10 minutes to form a core part. Further, the resin 2 was again applied thereon so as to have a thickness of 50 μm, and then the substrate was irradiated with ultraviolet rays to form an upper clad layer, thereby obtaining a channel waveguide.

Examples 4 to 6 and Comparative Examples 3 and 4
A channel waveguide was produced in the same manner as in Example 4 except that the resin composition forming the clad layer (lower clad layer) and the core part was changed to the resin composition shown in Table 2, respectively.

The transmission loss and long-term reliability of the channel waveguides obtained in Examples 4 to 6 and Comparative Examples 3 and 4 were evaluated. The results are shown in Table 2 below.
<Evaluation of transmission loss>
After the end face of the waveguide was cut by cleavage, 850 nm light was inserted through a multimode fiber (50 μm diameter), and the waveguide loss was measured by the cutback method. Cutback was performed by measuring four points in steps of 1 cm from a waveguide length of 5 cm. The obtained light intensity was plotted with respect to the waveguide length, and the loss value was calculated from the slope. When the obtained loss value was 1.0 dB / cm or less, “◯” was evaluated, and when the loss value was higher than that, “X” was evaluated.

<Evaluation of long-term reliability>
1. High-temperature and high-humidity test The produced optical waveguide was cut to a length of 3 cm, 850 nm light was inserted and the initial insertion loss was measured, and then left in a constant temperature bath at a temperature of 85 ° C. and a relative humidity of 85% for 1000 hours. Thereafter, the waveguide was taken out and adjusted for 24 hours at a temperature of 25 ° C. and a relative humidity of 50%, and then the insertion loss was measured again. Compared with the initial insertion loss, the case where the amount of change exceeds 1 dB is indicated as “X”, and the case where the change is within 1 dB is indicated as “◯”.

2. Heat cycle test Cut the manufactured optical waveguide into 3cm length, insert light at 850nm, measure the initial insertion loss, and then repeat the heat cycle test at -40 ° C and 85 ° C at 30 minute intervals in a short time. Carried out. After 100 cycles of the test, the waveguide was taken out, adjusted for 24 hours at a temperature of 25 ° C. and a relative humidity of 50%, and then the insertion loss was measured again. Compared with the initial insertion loss, the case where the amount of change exceeds 1 dB is indicated as “X”, and the case where the change is within 1 dB is indicated as “◯”.

The abbreviations in Table 2 indicate the following.
PJ3001: photosensitive acrylic resin (manufactured by JSR; Opstar PJ3001)

  From the results in Table 2, it is clear that the optical waveguide having at least the lower cladding layer made of the resin composition of the present invention has a small transmission loss and a high long-term reliability.

According to the present invention, it is possible to provide a photosensitive resin composition for forming an optical waveguide in which repelling is suppressed and a uniform coating film can be obtained without performing pretreatment. Therefore, it is possible to produce a waveguide with a large area at low cost, which is very useful industrially.
Moreover, if the resin composition of this invention is used, the coating film with favorable adhesiveness with a board | substrate can be formed, and the optical waveguide with high long-term reliability can be produced, without peeling from a board | substrate etc. being seen.

It is sectional drawing which shows typically an example of the optical waveguide containing the clad layer which consists of a resin composition of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Optical waveguide 10 Substrate 12 Lower clad layer 14 Core part 16 Upper clad layer

Claims (3)

Following formula (1)

^(Wherein, R 1 to R ³ is an alkyl group of 1 to 5 carbon atoms, ^{R 4} is a hydrogen atom or a methyl radical, n represents a number of 5-50.)
A compound represented by
The photosensitive resin composition for optical waveguide formation containing a polymeric compound and a photoinitiator. The photosensitive resin composition for optical waveguide formation of Claim 1 which contains 0.001-10 mass parts of compounds shown by said Formula (1) with respect to 100 mass parts of polymeric compounds. An optical waveguide having a core layer and a clad layer, wherein either or both of the core layer and the clad layer are made of the photosensitive resin composition for forming an optical waveguide according to claim 1 or 2. .

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